CA2033554A1 - Bisphosphoryl substituted hydrazines and their use as pesticides - Google Patents

Abstract

Abstract of the Disclosure This invention relates to bisphosphoryl N-substituted hydrazine compounds and to compositions thereof which are useful as pesticides. The compounds of this invention are effective against mites and insects, especially the corn rootworm, when applied either to the soil or foliage of the plant to be protected.

Description

2~33~
Bisphosphoryl 5ubstituted Hydrazines and Their Use as Pesticides Background of the Invention 1. Field of the Invention.
This invention relates to novel bisphosphoryl derivatives of N-substituted hydrazine, and to compositions thereof which are useful in controlling agricultural pests such as insects, especially the corn rootworm.
C)f the insects and other pests which attack the corn plant, the corn rootworm is particularly difficult to control. Corn rootworms are the larvae of beetles of ~e genus Diabrotica which cause damage to , .
corn plants, especially in field where one corn crop follows another in successive seasons. The adult beetles lay eggs in the soil of a maturing crop where the eggs lie dormant until Spring; the hatching larvae then feed on ~e roots of young corn plants reducing yield or causing ~e plants to topple over under inauence of climatic conditions. The fallen stalks cannot be harvested by mechanical means, and significant loss of yield results. Control of soil insects such as the corn rootworm is difficult because most pesticides are quickly inac~vated by soil bacteria and fail to control the insect population throughout the growing season.

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We have Çound that bisphosphoryl N-substituted hydrazine compounds are active in the soil for a ~ufflcient period of time to control the corn rootworm and have low toxicity to mammals.
2. Description of the Prior Art.
Tolkmith, (U.S. Patent Z,968,6~8) described compounds of the general formula:
S S
O--NHNH--li R' ~ R' wherein R and R' may be radicals containing up to four carbon atoms which are lower alkoxy, mono-lower alkylamino radicals or di-lower alkylamino radicals wherein each of t~e alkyl groups will contain up to four carbon atoms R and R' may be the same or different radicals.
These compounds are active as herbicides and systemic insecticides, especially for ~e mexican bean beetle.
ToL~cmith, tU.S-, Patent 2,945,055) reported a general structure of ~ the type:
:~ S S
'` ~ 11 NHNH--P
. ~ R' wherein R and R' have the same definition as in U.S. 2,968,688. The '055 structures are unsymmetrical while the '688 compounds are symmetrical. ~eæ compounds were reported to be fungicides and , insecticides against the sou~ern armyworm. There is no reported activity ElgaiItSt the corn rootworm.
Englin, et al., CA 69 p. 488~, 52212 (1g68) describe the preparation of compounds represented by the following structure:
O O
--NIHNH O
~: P10 OR
wherein R is isobutyl. These products were prepared for evaluation as biocides.
Summarv of the Invention This invention relates to bisphosphoryl N-subs~dtuted hydrazine compounds and compositions thereof which are effective as pesticides when applied to the soil or foliage of a plant. These compounds and compositions provide a method for controlling the corn rootworm as well as other insect pests such as turf grubs.

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De~ailed PescriptionQ~e Invention lhe present invention comprises a compound represented by the general foImula:

~ i--N--N--i wherein Rl is selected from the group consisting of (Cl-Cg) alkyl which has no branching on the carbon adjacent to the oxygen, (C3-C~8) ~Ikenyl or (C3-C~) alkynyl wherein these subs~ituents may be substituted wi~
one or more halogen, cyano, (Cl~6) alkoxy, halo (Cl-C6) alkoxy, keto, carbo (Cl C6) aLkoxy or (Cl~6) acyl groups;

Y is oxygen or sulfur; and X2, X3 and X4 are independently a phosphorus to carbon bond, sulfur, oxygen, NH or NR; and R, R2, R3, and 1~4 are independently selected from the gro~p consisting of (s~ Clo3 aLkyl, (C3~l0) alkenyl, (C3~l0)alkynyl~ (C3~10) cycloalkyl and (Cl-C4) phenalkyl wherein these substituents may be substihlted with one or more (Cl~6) alkyl, halo (Cl~6) aLkyl, halogen, cyano, (Cl~6) aL~coxy, halo (Cl {~6) alkoxy, keto, carbo (Cl~6) aLkoxy or (Cl~6) acyl groups; and - / . . ~, ,:, - - . : ;

R3 and R4 may be pined to ~orm a heterocyclic ring; and Rs and R6 are independently selected from the group consisting of hydrogen, (Cl~lo~ aLkyl, (C3~10) alkenyl, (C3-Clo) aL~cynyl, (C6-C1o) aryl and (Cl-C4) phenalkyl wherein these substituents may be substituted by one or more halogen, cyano, nitro, (Cl-C6) alkoxy, halo (Cl-C6) alkoxy, carbo (Cl~6) alkoxy or (Cl~6) acyl groups; and with the proviso that only one of R5 and R6 may be hydrogen.
Typical compounds of the invention include, but are not limited to the examples shown in Table I.
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TABL~ 1 R1 ~R3 ~ i--N--N
X2/ 1 1 ~X~'~
R2 R ~F~

Cpnd. Rl R2 X2Ra ~ R~ x4 y Rs R6 Et Et OEt O Et O S H Me 2 Et Et OEt O i-Pr O S Me Me 3 Et Et OEt O Pr O S M e H

4 ~ ~ O Pr O ~ O S Me H
s Et Et O Et O Et P-C Bond S M e H
S Et Et O Me O Et P-C Bond S Me H
7 ~ ~ O Pr O ~ P-C ~nd S Me H
8 Me Me O Me O Me O S Me H
9 Me Me O Et O -CH2CMe3 0 S H Me Et Et O Et O -CH2CMe3 0 S Me H
11 Et -CH2CMe3 0 Et O sec-Bu S O H Me 12 Me Me O ~ O scc-Bu S O Me H
13 Me Me O Et O scc-Bu S O Me Me 14 ~ ~ O ~}CH2CMe2CH~ S Me H
~ ~ O ~ O ~ O S H CO2Me 16 ~ ~ O ~ O i-Pr O S Me H
17 Et ~ O ~ O i-Pr O S H Me 18 Me Me O ~ O -CH2CMe3 0 S Me H

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In a preferred embodiment, this invention comprises a cornpound selected from the group consisting of N,N'-bis-(O,~
diethylthiophosphoryl) N-methyl hydrazine; N-(O,O-diethylthiophosphoryl) N'-(~ethyl ~isopropylthiophosphoryl) N,N'-dimethyl hydrazine; N-tO,~diethylthiophosphoryl) N'-(O-ethyl O-propylthiophosphoryl) N-methyl hydrazine; N-(O,~dimethyl-thiophosphoryl) N'-(~ethyl ~(2,2 dime~hylpropyl-thiophosphoryl) N'-methyl hydrazine; and N-(O,~dimethylthiophosphonyl) N'-(O-ethyl S-secbutylthi~phosphoryl) N-methyl hydrazine.
In ano~er aspect, this invention comprises a pesticidal composition comprising a pesticidally effective amount of the compound of formula (I) of this invention and an agronomically acceptable inert carrier.
In yet another aspect, this invention comprises a method of controlling pests such as insects. especially soil insects such as the corn rootworms and turf grubs which comprises applying to said pest or to the soil or to t~e foliage of plants to be freed from infestation, a pesticidally effective amount of a compound having the formula (I) defined herein above.
l~e term "halo" by itself or as a part of another subs~tuent means chloro, fluoro, bromo and iodo.

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' The term "aLtsyl" by itself or as a part of another substituent, unless otherwise stated, means straight and branched chain groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, tertbutyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl.
The term "haloalkyl" by itself or as a part of another substituent is an alkyl group of the stated number of carbon atoms having one or more halo atoms bonded thereto such as chloromethyl, bromoethyl, trifluoromethyl and bromodifluoromethyl.
The term "cycloalkyl" by itself or as a part of another substituent, unless otherwise stated, means carbocyclic structures and alkyl substituted carbocycles such as cyclopropyl, cyclobutyl, cyclopentyl, cydohexyl and menthyl.
The term "alkenyl" means straight and branched chain groups containing at least one carbon to carbon double bond such as propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl and decenyl.
The term "alkynyl" means straight and branched chain groups containing a~ least one carbon to carbon triple bond such as propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and decynyl.
The term "heterocycle" or "heterocyclic ring" means a saturated or unsa~urated ring containing up to seven atoms at least one of which is phosphorus.

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The term "acyl" means a group having the structure: ~(=O)-R
wherein R is an alkyl group having from one to six carbon atoms. The term "carboalkoxy" means a group having the st~ucture -C(=O)~R wherein R is an alkyl group having from one to six carbon atoms.
The term "alkoxy" by itself or as a part of another substituent means a straight or branched aL~cyl group bonded to an oxygen atom and including straight and branched groups such as methoxy, ethoxy, isopropoxy, butoxy and neopentoxy.
The term "alkylthio" by itself or as a part of another substituent means a straight or branched alkyl group bonded to a sulfur atom and including such groups as me~yl~io, isopropylthio and secbutylthio.
The term "cycloalkoxy" by itself or as part of another substituent means carbocyclic structures and carbocyclic stluctures substituted by alkyl groups bonded to an oxygen atom and including such groups as cyclohexyloxy, cyclopentyloxy and men~yloxy.
The term "pesticidally or insecticidally e~fective amount" means a quantity of compound which causes a reduction of the pest or insect population or decreases crop damage compared to a control group.
As used in this disclosure, "corn rootworm" means the Western corn rootworm, Diabrofica virgffera virgifera and Diabrotic~ virgifera . :' .

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complex; the Northern corn rootworm, D~brotica barberi; and the Southern corn rootworm, Diabrotica undecimpunctata howardi.
As used in this disclosure, the term "phosphoryl" means both phosphate and phosphonate compounds and their sulfur analogs.
In certain cases the compounds of this invention possess asymmetric centers which give rise to optical enantiomorphs and diastereomers. The compounds may also possess acidic or basic moieties which may form salts or metal complexes; this invention includes such enantiomorphs, salts and metal complexes.
The potential symmetry of the compounds of this invention may result in the equivalence of several possible representations of the same molecule.
The compositions and compounds of this invention can be applied direct~y ~o the locus to be protected, as for example, the area around or upon economic plants infected with insects or to plants on whidl infestation is to be prevented. The compounds and compositions may be used ei~er as contac~ or systemic pesticides.
In the practice of the method of ~e invention, t~e ac~ive compound may be applied ~o the soil or foliage where it is absorbed by the plant, translocated to other plant parts and ultirnately ingested by t~e pest or Lnsects by means of ingestion of the plant part(s~. This means of applica~don is referred to as "systemic" applica~don.

.., ;/ - , ' ~, Alternatively, the ac'dve compound may be applied to the soil and contacted therein with the insects and other pests to be controlled; This means of application is referred to as "soil" application. In another alternative, the active compound may be foliarly applied to the plants to be freed from insects and other pests whidh feed on the foliage.
When using the compounds defined above, the method of invention is especially effective against soil insects when the active compound is applied on or in the soil in order to effect direct contact with the insects or other pests. By "pests" is meant organisms induding arthropods, which in turn includes insects and acarids which organisms attack agricultural plants.
For use as pesticides, the compounds of this invention can be used a solutions, suspensions or mixtures in organic solvents or formulations. For example, they can be formulated as wettable powders, emulsifiable concentrates, dusts, granular formulations or flowable emulsifiable concentrates. In such formulations, the compounds of this invention are present at a concentra~on of about 0.00001 t~ about 99%, preferably a~u~ 1 to about 95%, and are extended with an agronomically acceptable liquid or solid ca~rier. When desired, suitable surfactants are likewise incorporated. Surfactants commonly used in the art can be found in the John W. McCutcheon, Inc.

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~3~3 publication "D~tergents and Emulsifiers Annual." Allured Publishing Co., Ridgewood, N.J.
By "agronomically acceptable carrier" is meant any substance which can be utilized to dissolve, disperse or diffuse the chemical incorporated therein without impair}ng the effectiveness of the toxic agent and which does not create permanent damage to such environment as soil, equipment, and agronomic crops when utilized according to recommendations.
The compounds of this invention can be taken up on or mixed with a finely particled solid carrier, as for example, clays, inorganic silicates, carbonates, and silicas. Organic carriers can also be employed.
Dust concentrates are commonly made wherein compounds are present in the range of about 20 to 80%. For ultimate applica~ons, these concentrates are normally extended with additional solid to given an active ingredient content of from 0.1 to about 20%. Granular for nulations are being made using a granular or pelletized from of carrier, such as granular clays, vermiculite, charcoal l~r corn cobs, and may contain the active ingredient fr~>m about 1 to about 25% by weight.
Wettable powder formulations are made by incorporating the compounds of ~is inven'don in an inert, ~inely divided solid carrier along wi~ a surfactant whic~ can be one or mc~re emulsifying, wetting, dispersing, or spreading agents or a blend of these. Ihe compounds are ~ ~ ~ c~

usually present in the range of about 10 to about 80% by weight and surfactants in from about 0.5 to about 10% by weight. Commonly used emulsifying and wetting agents include polyoxyethylated derivatives of alkylphenols, fatty alcohols, fatty acids, alkylamines, alkylarene sulfonates and dialkyl sulfosuccinates. Spreading agents include such material as glycerol malmitan laureate and a condensate of polygylcerol and oleic acid modified with phthalic anhydride. Dispersing agents include such materials as the soclium salt of the copolymer of maleic anhydride and an olefin such as diisobutylene, sodium lignin sulfonate and sodium formaldehyde naphthalene sulfonates.
Water disposible granular products may be prepared by granulating or agglomerating a suitable wettable powder formulations which is compatable with the active ingredients. Agglomeration is carried out in a conventional manner such as by a pan agglomeratory.
Dispersible granular products are described in U.S. Pat. No. 3,954,439 and British Pat. No. 1,433,882.
One convenient method for preparing a solid formulation is to impregnate the compounds of this invention onto the solid carrier by means of a vola~ile solvent, such as acetone. In this manner, adjuvants, such as ac'dvators, adhesives, plant nutrients, synergists and various surfactants c~ also be incorporated.

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Emulsifiable concenkate ~ormulations are prepared by dissolv~g the compounds of this invention in an agronomically acceptable organic solvent and adding a solvent-soluble emulsifying agent. Suitable solvents are usually water-immiscible and can be found in the hydrocarbon, chlorinated hydrocarbon, ketone, ester, alcohol and amide dasses of organic solvents. Mixtures of solvents are commonly employed. The surfactants useful as emulsifying agents can constitute about 0.5 to about 10% by weight cf emuls;fiable concentrates and can be anionic, cationic or non-ionic in character. The concentration of the active ingredients can vary from about 10 to about 80%, preferably in the range of about 25 to about 50%.
For use as pesticidal agents, these compounds should be applied in an effective amount sufficient to exert the desired pesticidal activity by techniques well known in the art. In certain situations, however, it may be desirable and advantageous to apply ~e compounds direc~ly onto the loci to be protected or freed of pe~ts without the benefft of any substanlial amount of carrier. This is a particularly effective method when the physical nature of the toxicants is such as to permit what is known as "low-volume" applica~on, that is, when the compouIlds are in liquid ~orm or subshntially soluble in higher boiling solvents.
The applica~on rate will, of course, vary clepending upon the pu~pose of such application, the compound being utilized, ~e ; 14 ~, 2~3~
frequency of disseminaffon, and the Like. For use as insecticides, dilute sprays can be applied at concentrations ~>f about 0.01 to about 20 pounds of the active ingredients per 100 gallons of spray. They are usually applied at about 0.1 ~o about 5 pounds per 100 gallons. In more concentrated sprays, the active ingredient is increased by a factor of 2 to 40. With dilute sprays, applications are usually made to the plants until run-off is achieved, whereas with more concentrated or low-volume sprays, the materials are applied as mists.
For use as a soil insecticide, the compounds can be applied as a dilute liquid preparation or as a solid formulation, preferably a granular formulation, by broadcasting, sid~dressing, introduction into the seed furrow, soil incorpora~ion, or seed treatment. The application rate can be from about 0.05 to about 10 pounds per acre of active ingredient and for economic reasons, preferably from about 0.1 to about 2 pounds per acre.
l~e compounds of ~is invention can be utilized as the sole pesticidal agents or they can ~e employed in conjunction with other bactericides, fungicides, herbicides, insecticides, acaricides, and c~mparable pesticides.
The compounds of ~is inven!don may be prepared by a variety of reaction schemes.

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2~33~3 One method particularly useful for preparing the compounds is illustratecl is the following reac~don sequeI~oe.

PSC13 + RIOH bas~ _~ Rloi / (1) ~1 ~ R oi ~ + R20~ b~e , \ ~, :

R1\ Rl iCl 1 p i--NNH (3) ~2 R2 I I +/ia ~ NNH--P/
R2 Rg R~ ,~0 R2 R5 R6 \R4 ~ ':

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, ~ , 2 ~ 'c3 The above method is useful to react alcohols (as illustrated), mercaptans and arnin~ with thiophosphoryl chloride to prepare the corresponding thiophosphoryl analog (Steps 1 and 2). Phosphorus oxychloride may be subs~dtuted for thiophosphoryl chloride to prepare the corresponding phosphoryl compounds.
Bases to neutralize the hydrogen halide produced in the reaction may be chosen from organic or inorgan~c materials such as potassium carbonate, sodium hydroxide, sodium hydride, pyridine, and the like.
Reaction temperature for the above reactions may ~e varied from about -50C to about 120C, preferably from about 40C to about 60C. The proper base, solvent, and reaction parameters for a particular reaction may be selected on the basis of the chemical and physical properties of the reagents. The above synthetic method may be adapted to prepare alkyl phosphorus compounds as follows:
R3 X + PC13 + AlC13 ~ R3PCl2 (5) Cl R3--p~ + S -~ P~ (6) The dichlorot~io phosphonyl intermediate produced by reaction (6) may be used as the starting material ln reaction (2).

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?f~3~4 If desired, a second aLt~yl group may be introduced into the product of reaction ~5).
Cl R4 X ~ R3P AlC~3 D --P Cl (7) Cl R4 ~

P_~1 + S R3 j_Cl (8) ~e product of reaction (8) may be used as the starting ma~erial for reaction (3).
The oxygen analogs of the intermediates and starting materials in reactions (1) through (8) may be substituted for the thiophosphoryl compounds illustrated in the reactions. Likewise, other halogens may be substituted for the chlorine shown in the reactions. Further details of these preparations are set forth in l~xamples 1 to 9.
The required s~arting materials and intermediates to prepare the compounds of the inven~on are available from commercial sources or may be prepared by known reactions such as those illus~rated above and described in Examples A to T given below. Other suitable reaction sc~emes will be obvious to the chemist of ording skill. Typical preparations are also described in U.S. patents 2,968,688 and 2,945,055 ~3~
and Svnthesi~ of Carbon-PhosphorQus Bonds by Robert Engel, p. 172 CRC Press (1988).
The ~ollowing examples are intended only to further illustrate the invention and are not intended to limit the scope of the invention which is defined by the claims.

Preparation of In~rmediates Example D: Preparation of ~ethyl ~propyl chlorot~iophosphate To 30 g (167 mmole) of ~ethyl dichlorothiophosphate in 100 ml of tetrahydrofuran (THF) cooled to -70 C was added a solution of sodium propopoxide (from 7d~ g of 60% NaH (184 mmole) and 11 g (176 mmole) of l-propanol) in 50 ml of TE~. After warming to room temperature over 2 hours, the THF was removed in vacuo and the residue was partitioned between 50 ml die~hyl ether, 50 rnl hexanes, and 25 ml cold water. The organic layer was dried over magnesium sulfate, concentrated in vacuo, and distilled (bp 4~50 C 1 torr) yielding 20 g of the title compound, an oil. nmr 1.0 ~ 3H, 1.4 t 3H, 1.8 sextet 2H, 4.4M4H.

Ea~ample ~: Preparation of O,~diis~propyl chlorothiophosphate A solu'don of sodium isopropo~cide in THF was prepared by the reaction of 45 g (1125 mmole) of 60% sodium hydride with 84 ml (llûO

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mmole) of isopropyl alcohol in 400 ml of THF. This solution was added, with mechanical stirring, to 83.4 g (490 mmole) of thiophosphorylchloride in 300 ml of THF and cooled to ~0 C internal.
After the addition was complete the reaction mixture was slowly warmed to æs oc When gas chromatography showed the reaction to be complete the THF was removed in vacuo and the product partitioned between hexanes and water. The organic layer was dried over anhydrous magnesium sulfate and concentrated in vacuo yielding 93 g of the title compound, an oil. nrnr 1.4 d 12H, 4.9 m 2H.

Exarn~e F: Preparation of ~ethyl ~neopentyl chlorothiophosphate By substantially following the procedure of Example D, using neopentyl alcohol in place of 1-propanol, one obtains the title compound, an oil. nmr 1.0 s 9H, 1.4 m 3H, 3.9 m 2H, 4.4 m 2H.

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Example G: Preparation of O,~dipropylthiophosphoryl hydra~ine To 70 ml (1400 mmole) of hydrazine monohydrate and 1ûO ml of me~ylene chloride cooled to -10C internal was slowly added with mechanical stirring 100 g (460 mmole) o~ O,~dipropylchlor~
thiophosphab. After stlrring for 1 hour, ~e reaction mixture was diluted wi~ hexanes and ext~acted wi~ water. lhe organic layer was dried over anhydrous magnesium sulfate, ~iltered and concentrated in ,, ~, .

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vacuo yielding ~e title compound, an oil. nmr 1.0 t 6H, 1.8 sextet 2H, 3.5bdd2H,4.0m4H,4.7d lH.

Example H: Preparation of O~ethyl ~isopropyl chlorothiophosphate 8y substan~ially following the procedure of Example D, using isopropyl alcohol in place of 1-propanol, one obtains the title compound, an oil. nmr 1.4 m 9H, 4.3 m 2H, 5.0 m lH.

Example I: Preparation of O ethyl ~isopropylthiophosphoryl hydrazine By substantially following the procedure of Example G, using 0-ethyl ~isopropyl chloro~iophosphate one obtains the title compound, an oil. nmr 1.4 m 9H, 3.5 bs 2H, 4.1 dq 2H, 4.8 bd lH, 4.8 m lH.

Example T: Preparation of ~ethyl ~secbutyl chloro~hiophosphate By substan~ally following the procedure of Example D, using secbu~hyl alcohol in place of 1-propanol, one obtams ~e title compound, anoil. nmr1.0m3H,1.4m6H,1.8m2H,4.2m4H,4.8m1H.

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Example ~ Preparation s)f O ethyl ~isobutyl chlorothiophosphate l~y substantially following ~he procedure of Example D, using isobutyl alcohol in place of l-propanol, one obtains the title compound, anoil. nmrl.Om6H,1.4m3H,2.1mlH,4.0m2H,4.3m~H.

Example N: Prepara1don of N-(O ethyl ~neopentylthiophosphoryl)-N-methyl hydrazine By substantially following the procedure of Example G, using methyl hydrazine and ~ethyl ~neopentyl chlorothiophosphate (Example F) one obtains the title compound, an oil. nmr 1.0 s 9H, 1.4 t 3H, 2.9 d 3H, 3.7 m 4H, 4.2 m 2H.

Example Q: Preparation of O,~dineopentyl chlorothiophosphate By substan~ally following the procedure of Example E using neopentyl alcohol instead of isopropyl alcohol one obtains the title compound, an oil. nmr 1.0 s 18H, 3.9 m 4H.

Example S: Prepara~on of ~ethyl ~butyl chloro~iophosphate By substantially following ~e procedure of Example D, using but,yl alcohol in place of l-propanol, one obtains ~he title compound, an oil. nmr l.O t 3H, 1.4 m SH, 1.8 m 2H, 4.2 m 4H.

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Exam~r: Preparation of ~e~yl ~neopentyl thiophosphate po7assium salt Sixty One grams (260 mmole) of O~thyl ~neopentyl chlorothiophosphate and 33.7 g (530 mmole) of 88% potassium hydroxide were m~xed in 300 ml of ethyl alcohol and stirred at 22 C for 60 hours. The precipitated potassium chloride was filtered off and the ethyl alcohol removed in vacuo. The resulting solid was washed with hexanes and diethyl ether yielding the title compound, a white solid.

Examplç U: Preparaldon of N-(O,~diethylthiophosphoryl)-N-methyl hydrazine Into a 1000 ml round bottomed flask was added 500 ml of methylene chloride and 103 g (2.21 mole) of N-methylhydrazine. To this was slowly added 40 ml of water. To the mixture was then added 174 g (0.92 mole) of O,~diethyl chloro~iophosphate with such cooling that the internal temperature remained below 40 oC. After stirring for two hours the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated in vacuo, yielding 184 g of ~e title compound, an oil. nmr 1.4 t 6H, 2.9 d 3H, 3.6 bs lH, 4.1 dq 4H.

Example V: Preparation of N-(O,~diethylthiophosphoryl)-N,N'-dimethyl hydrazine Into a 500 ml round bottomed f~ask were plaoed 30 g (226 mmole) of 1,2-dimethylhydrazine, 100 ml of methylene chloride and 108 g (678 mmole) of 25% aqueous sodium hydroxide. The mixture was cooled in an ice bath and then 42.5 g (226 ~unole) of diethyl chlorothiophosphate was added over the course of 30 minutes. The mixhlre was stirred and warmed to room temperature for 3 hours. The organic layer was separated, washed wi~ water and dried over magnesium sulfate and concentrated in vacuo yielding 50 g of the title compound, an oil. nmr 1.4t6H,2.6s3H,2.9d3H,4.1 m5H.

Preparation of Bisphosphoryl N-~ubstituted Hydrazines Example 1: N,N'-bis-(O,~diethylthiophosphoryl) N-methyl hydrazine By substantially following the procedure for Example 9 using 5.0 g (26 mmole) of N-(O,~diethylthiophosphoryl~N-methyl hydrazine (Example U) and 5.2 g (2~ mmole3 of O,~diethyl chlorothiophosphate one obtains 7.6 g of ~é title compound, an oil. nmr 1.4 $12H, 2.9 d 3H, 4.2 m 8H, 4.7 d lH.

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~: N-(O,~diethylthiophosphoryl) N'-(~ethyl O-isopropylthiophosphoryl) N,N'-dimethyl hydrazine Into 50 ml of l~IF was added 5.0 g (23 mmole) of N-(O,;) diethylthiophosphoryl) N,N-dimethyl hydrazine (Example V), 4.8 g (23 mmole) of ~ethyl ~}isopropyl chlorothiophosphate (Example H), and 2.5 g (24 mmole) of triethylamine. The mixture was refluxed for 18 hours, concentrated in vacuo, and partitioned between ethyl ether and water. The organic layer was dried over magnesium sulfate, concen~ated in vacuo, and chromatographed on silica gel yielding 1.2 g of the title compound, an oil.

Example 3: N-(O,'~diethylthiophosphoryl) N'-(aethyl '~propyl~iophosphoryl) N-me~yl hydrazine By substantially following the procedure for Example 9 using 5.û
g (26 mmole) of N-(O,~diethylthiophosphoryl)-N-methyl hydra~ine (Example U) and 5.6 g (28 mmole) of ~et~yl ;) propyl chloro~iophosphate (Example 1~) one obtains 8.0 g of the title compound, an oil. nmr 1.0 t 3H, 1.4 t 9H, 1.8 m 2H, 2.9 d 3H, 4.2 m 8H., 4.7dlH.

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Exam~le ~: N-(C),~dimethylthiophosphoryl) N'-(~ethyl O-neopentylthiophosphoryl) N'-me~yl hydrazine A mixture of 9.9 g (41 mmole~ of N-(~ethyl O-neopentylhiophosphoryl) N-methyl hydrazine (Example N) and 6.6 g (41 mmole) of O,~dimethyl chlorothiophosphate, in 6 g (76 mmole) of pyridine was warmed in a water ba~ at 60 oC for 1 hour and then cooled. The reaction mixture was paffi~doned between ether and dilute aqueous hydrochloric acid. I~e organic layer was dried, concentrated, and chromatographed on silic gel using 5% ethyl acetate in hexanes yielding 2.0 g of ~e title compound, an oil. nmr 1.0 s 9H, 1.4 t 3H, 2.9 d 3H,3.8d6H,4.2m2H,4.8dlH.

Example 12: N-(O,~dimethyl~iophosphoryl) N'-(~ethyl ~secbutyl chloro phosphoryl) N-methyl hydrazine.
A oil suspension of 2.7 g (66 mmole) of 60% sodium hydride was twice washed with hexanes and then resuspended in 20 ml sf TE~. A
solution of 5.7 g (33 mmole) of O,~dime~ylthiophosphoryl hydra~ine in 10 ml of THF ~vas slowly added. Gas is evolved. After the deprotonation was complete, as evideIlced by cessation of gas evolution, 8.0 g (33 mmole) of ~e~yl ~secbutyl chloro phosphate was added. ~ter stirring for 1 hour the mixture was quenched with methanol, and partitioned between ether and water. I~e organic layer , . . . . . .
~, .

was dried over magnesium sulfate, ~tered, concentrated in vacuo, and chromatographed over silica gel yielding 1.0 g of the title compound, anoil.nmrl.l t3H,1.4m5H,1.7m2H,2.9d3H,3.4mlH,3.8m6H, 4.2m2H,4.7d lH

Biolog~c_ethods Biological Met_od A: Co~n Rootwo~m ScreenJng Test A parent solution containing 600 parts per million (ppm) of the test compound was made by dissolving the test compour d in a solvent ~aoetone: methanol,l:l) and adding water to give an acetone:methanol:
water system of 5:5:90 and then a surfactant was utilized at the equivalent of 1 ounce per 100 gal. of test solution. The surfactant consisted of a 1:1 mixture of an aL~cylarylpolyetheralcohol (Rohm and Haas Co. Triton~9 X-155j and a modified phthalic glycerol alkyl resin (Rohm and Haas Co. Triton~ ~1956).
Tes~ s~ugions were made by serially diluting the 6ao ppm parent solution with water and surfactant to give conoentrations of 150, 38, 10, 2.5, and 0.6 ppm.
Ten ml of each test solution were pipetted into 190 gm of a non-sterile loamy soil (pH 5.5 to 7.0) contained in a 16 oz glass jar. This application provided soil concentra~ions of 8, 2, 0.5, 0.125, and 0.03 ppm.

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Each jar was shaken to insure uniform distribution of chemical in the soil. Soil moisture ranged from 18% to 22%.
In this soil, organophosphate and carbamate soil insecticides (e.g., Dyfonate~ and Furadan~), used as test standards, effectively controlled the corn rootworm. This soil was considered a "non-aggressive soil".
The southern corn rootworm, Diabrotica undecimpunctafa howardi, was used as the test insect.
Two presoaked corn (Zea m~ys var. Golden Cross Bantam) seeds were placed in the bottom of a 1 oz. plastic cup and covered with about 30 gm. of treated soil. The soil surhce of each cup was inoculated with southern corn rootworm eggs resulting in a larval challenge of 5û to 70 larvae per cup. The cups were dosed with ~ght fitting snap caps.
The test cups were held for 10 days at 27C and then the percent kill relative to the infested check was determined. Mortalities obtained were plotted on logarithmic probability paper (No. 3228, Codex Book Co. Inc., Norwood, Mass.). The estimated concentration eliciting a 90%
mortality (LC90) was establishecl from the best eye-fitted line to the plotted mortality data.

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Biolo~Me~d B: Corn Rootworm Foliar Sy~temic Application Te~t A parent solution containing 600 parts per rnillion (ppm) of the test compound was made by dissolving the test compound in a solvent ~acetone: methanol,l:1) and adding water to give an acetone:methanol:water system of 5:5:90 and then a surfactant was utilized at the equivalen~ of 1 ounce per 100 gal. of test solution. The surfactant consisted of a 1:1 mixture of an alkylarylpolyetheralcohol (Rohm and Haas Co. Triton ~ X-155) and a modified phthalic glycerol alkyl resin (Rohm and Haas Co. Triton ~ ~1956).
Test solutions were made by serially diluting the 600 ppm parent solution with water and surfactant to give concentrations of 120 and 60 ppm.
The southern corn rootworm, Diabrotica undecimpunctata howardi, was used as the test inseet.
Corn (Zea mays, var. Golden Cross Bantam) plants in the 6-leaf stage, ~owing in individual 8 inch plastic pots in the greenhouse, were infested wi~ southern co~n rootworm eggs. Rootworm eggs, suspended in a 0.125% agar solution, were pipetted into ~he soil to a depth of approximately 4 cm providing an in~estation of appro~amately 400 eggs per plant . / .: .

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The test soil was non-sterile Iowa topsoil with a natural population of microorganisms that cause enhanoed microbial degradation of oertain organophosphate and carbamate soil insecticides (e.g. Dyfonate~ and Furadan~) used as test standards. This "aggressive soil" rendered these chemicals ineffective when applied to the soil for controlling the corn rootworm.
Three days post-infestation wi~ corn rootworm eggs, the soil surface of each pot was masked with an absorbent material and the plant sprayed to runoff with ~he test solution using a DeVilbiss atomizer at 20 psig. Four plan~ts were sprayed at each concen~ation.
When dry, each treatment was maintained under greenhouse conditions. Plants were watered as needed.
Fourteen days post-spraying with the test compound the plants were uprooted, the roots thoroughly rinsed with water to remove the soil, and rated for corn roohvorm larval feeding damage using the following modified Iowa Corn Root Rating System:

7, Damage Rating Description of Root System No noticeable feeding damage 2 Feeding scars present but no root pruning 3 At least one root pruned but less than an entire node of roots pruned 4 At least one full node of roots pruned but less than two full nodes 5 Two or more full nodes pruned Each root system in the group of four treated plants was scored individually and a group average was calculated. A treatment provided acceptable corn rootworm control with an average root damage rating of 1.0 to 3.0 and unacceptable control with an average root damage rating of >3.0 to 5Ø
The average root system damage ratings were converted to percent control relative to the infested check.

Biologicel Method C~ o~ ootwolm At PlantiIIg Soil Application Test A test solution containing technical compound to provide a row applicalion rate (40 inch distance beh~een rows) to soil of 0.5 lb ai/acre was made by dissolving 46 mg of test compound in 20 ml of solvent (acetone:methanol,1:1), adding 580 ml of water, and then a surfactant , at ~e equivalent of 1 ounce per 100 gal of test solution. The surfactant consisted of a 1:1 mixture of an allcylarylpolyetheralcohol (Rohm and Haas Co. Triton~ X-155) and a modiAed phthalic glycerol aL~yl resin (Rohm and Haas Co. Triton~ 56).
Solutions for lower application rates of 0.25, 0.125, and 0.0625 Ib ai/acre were made in the same manner using proportionately less technical compound.
Two corn (Ze~ mays var Golden Cross Bantam3 seeds were planted approximately one inch deep in the center of the soil contained in an 8 inch plastic pot. ~nmediately after planting, 150 ml of the test solution was poured evenly over the soil surface in each pot. Four pots were treated at each application rate. Ea~h treatment was maintained under greenhouse conditions. Pots were watered as needed. Upon seed germination, plant stand was reduced to one plant per pot.
The southern corn rootworm, Diabrotica undecimpunctata howardi, was used as the test inseet.
The test soil was non-sterile Iowa topsoil wi~ a natural population of microorganisn~s that cause enhanced microbial degradation of certain organophosphate and carbamate soil insecticides (e.g. Dyfonate(~9 and Furadan~9) used as test standards. This "aggressive soil" rendered ~ese chemicals ineffective when applied to the soil for controlling the corn rootworm.

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~ our weeks post-planting, each pot was infested with southern corn rootworm eggs. Rootworm eggs, suspended in a 0.125% agar solu~on, were pipetted into the soil to a depth of approximately 4 cm providing an infestation of appro~amately 400 eggs per plant.
Seventeen days post-in~estation with corn rootworm eggs, the plants were uprooted, the roots thoroughly rinsed with water to remove the soil, and rated for corn rootworm larval feeding damage using the following modified Iowa Corn Root Rating System:
Damage Rating ~escription of Root System No noticeable feeding damage 2 Feeding scars present but no root pruning 3 At least one root pruned but less than an entire node of roots pruned 4 At least one full node of roots pruned but less than two full nodes 5 Two or more full nodes pruned Each root system in the group of four treated plants was scored individually and a group average was calculated. A treatment provided acceptable corn roo~worm conhoi with an average root damage ra~g of 1.0 to 3.0 and unacceptable control with an average root damage ra~ng of >3.0 to 5Ø

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The average root system damage ratings were converted to percent control relative to the infested checlc. Mortalities obtained were plotted on logarithrnic probability paper (No. 3228, Codex Book Co. Inc., Norwood, Mass.). The estimated conoentration elicitirg a 90%
mortality (LC90) was established frorn the best eye-fitted line to the plotted mortality data.
Table 2 sets for~ the melting points and biological data obtained by methods A and C on corn rootworm as described above for the exemplary compounds of Table 1.

Biological Method D: Foliar Insecticidal Activity T~t ln evaluating the foliar insecticidal activity of the compounds of this invention agains~ insects and mi~es, the ~ollowing test procedures were employed.
A test solution containing 600 par~ per ~ullion (ppm) was made by dissolving the test compound in a solvent (acetone:methanol, 1:1), adding a surfactan~ and then water to give an aoetone:methanol:water system of 5:5:90. A 1:1 mL~ re of an alkylarylpolye~eralcohol (Triton~D X-155 sur~actant from Rohm and Haas Company, Philadelphia, PA) and a modified phthalic glycerol alkyl resin (Triton~
~1956 surfactant from Rohm and Haas Company, Philadelphia, PA~

was utilized at the equivalent of 1 ounce per 100 gal. of test svlution as a surfactant.
Analogous solutiQns were made by serially diluting the 6û0 ppm test solution with water and surfactant to give concentrations of 150, 38, 10, 2.5, 0.6, 0.15 and 0.038 ppm. Not all compounds were tested at each of the several concentrations stated above. Test concentrations of a compound were selected as those most likely to differentiate dose response of a particular compound toward a particular test insect.
Initial evaluations were made on one or more of the following p~sts:
Code Symbol CommonName LatinName AW Southern Armyworm Spodoptera eridania BB Mexican Bean Beetle Epilachna varivestis GPA Green Peach Aphid Myzus persicae TSM Two-Spotted Spider Mite Tetranychus urticae BW Boll Weevil Anthonomus grandis For the Mexican Bean B~etle and Southern armyworm tests, individual lima bean (Phaseolus limeniss var. Woods' Prolific) leaves were placed on moistened pie~es of filter paper in Petri dishes. I~e ;: leaves were then sprayed with the test solution using a rotating turntable and allowed to dry. The dishes were then infested wi~ 10 third instar larvae of either the Mexican Been Beetle or the Southern ::
~' Armyworm. The dishes were then covered. Percent mortality was determined for each species and spray conoen~ation at 48 and 96 hours after treatment.
For the mite test, infested bean (Phaseolus limensis var. Woods Prolific) leaf discs (1.25" in diameter) containing about 50 mites were placed ~n a Petri dish lid on a moistened piece of cotton. The leaves were then sprayed to thorough wetness with the test solution using a rotating turntable, held for twenty-four hours and then the percentage killed was determined.
For the aphid test, in~ested broccoli (Br~ssica oleracea iialica var.
MCicco ) leaves containing about 50 aphids were placed in a Petri dish lid on a moistened piece of cotton. The leaves were then sprayed to thorough wetness with the test solution using a rotating turntable, held for twenty-four hours and then the percentage killed was determined.
For the boll weevil test, 10 adult weevils were placed in a 0.5 pint glass Mason jar containing a small cube of apple. The weevils were confined to ~e jar by fiberglass screen mesh secured by a screw-type rim cap. The jars were then sprayed with the test solu~on using a rotating turntable; directing the spray through the mesh into the jar.
The peroentage killed was determined after ~orty-eight and ninety six hours.

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The mortalities obtained in this manner were plotted on logarithmic probability paper. The estimated concentration eliciting a 50 percent mortality (LC50) was established from the best eye-fitted line to the plotted mortality data.
The rotating turntable consists of a fixed, continuously operating spray nozzle under which targets are rotated at a fixed speed and distance. If the target is a Petri dish (such as for the bean beetle, armyworm, mite, or aphid tests), the distance from the nozzle is 15 inches. If the target is a Mason jar (such as for the boll weevil test), the distanoe from the noz~le is 7 inches. The nozzle is located 8 inches from the rotating shaft. The targets on individual platforms revolve around the shaft at 1 revolution per 20 seconds but only a brief portion of this time occurs in the spray pat~. targets pass only once under the no771e and ~en are removed to drying hoods.
The nozzle used is a 1/4 JCO Spraying Systems (Wheaton, Illinois) air atomizing nozzle equipped with a No. 2850 fluid cap and a No. 7û air cap. At the 10 psig air pressure used and wi~h liquid siphon feed, 0.5 GPH (gallons per hour) are delivered in a round spray pat~ern wi~ a 21 degree spray angle. Targets are misted wi~ spray droplets to the point that the droplets coalesce to form a uniform thin film insufficient to drown test organisms.
Results of foliar evaluation are set ~or~ in Table 3.

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TAB~ 2 Corn rootworm acti~rity of Bisphosphoryl Substituted Hydrazines Cpnd. CRW-LC90 CRW-% Control CRW-LC50 M.P.
Method A Method B Method C
Q.~ ~oun~l/a~e #/acre <2 NT I oil 2 0.78 30 1.2 oil 3 9.2 NT NT oil 4 I NT NT oil I NT NT oil 6 I NT NT oil 7 I NT NT oil 8 I NT NT oil 9 1.1 NT 0.37 oil I NT NT oil 11 I NT NT oil 12 5.8 NT NT o;l 13 I NT NT oil 14 I NT NT oil I NT NT oil 16 I NT 1.0 oil 17 I NT I oil 18 I NT NT oil I = inactive at highest rate tested NT = not tested ;

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Inseclicidal activity of Bis Phosphoryl Substituted Hydrazines LC 50/ppm Cpd. TSM GPA B B B 8 A W A W B W B W
48hrs. ~ 8 hs. Y~ ~h~

2 5.5 36 150 150 I I 740 150 13 150 I 600 38 I I 7~0 740 I = inactive at concentration tested - = not tested Although the invention has been described with regard to its preferred embodiments, which cons~dtute the best mode presently known to ~e inventors, it should be understood that various changes and modi~cations as would be obvious to one having ordinary skill ;n this art may be made wi~out departing from the scope of the invention, which is set forth in the claims.

Claims (3)

1. A compound selected from the group consisting of N,N'-bis-(O,O-diethylthiophosphoryl) N-methyl hydrazine; N-(O,O-diethylthiophosphoryl) N'-(O-ethyl O-isopropylthiophosphoryl) N,N'-dimethyl hydrazine; N-(O,O-diethylthiophosphoryl) N'-(O-ethyl O-propylthiophosphoryl) N-methyl hydrazine; N-(O,O-dimethylthiophosphoryl) N'-(O-ethyl O-(2,2 dimethylpropyl-thiophosphoryl) N'-methyl hydrazine; and N-(O,O-dimethylthiophosphoryl) N'-(O-ethyl S-secbutylthiophosphoryl) N-methyl hydrazine.

2. A pesticidal composition comprising a pesticidally effective amount of the compound of claim 1 and an agronomically acceptable inert carrier.

3. A method for controlling corn rootworm comprising applying to said corn rootworm or the habitat of said corn rootworm a pesticidally effective amount of the compound of claim 1.