IL25275A - Method for controlling insects by means of aziridinyl phosphorus compounds - Google Patents

Description

Method for controlling insects by means of aziridinyl phosphorus compounds STAUFFSR CHEMICAL QQW&M C: 24115 R-50 METHOD This invention relates to certain organic compounds which may be used to control insects. More speci ically, the invention relates to the use of compounds of the general formula wherein is a member selected from the group consisting of azlrldinyl, alkoxy and lower alkyl containing from 1 to 6 carbon atoms; R is a member selected from the group consisting of alkoxy, alkylamino,/ alkenylamino, cyclohexylamino, alkoxyalkyl-amino, further characterized by the fact that when Ri is aziri-dinyl R is other than alkoxy; and X is selected from the group consisting of oxygen and sulfur.

The compounds of the present invention can be prepared by the reaction of the appropriate phosphorus containing mono-or di-chloride with one or two equivalents of ethyleneimine in the presence of a hydrogen chloride acceptor. Generally the reaction was conducted in the presence of an inert organic solvent, such as benzene, toluene and the like. Examples of operable phosphorus-containing compounds are substituted phos-phorothioic dichlorides, monochloro phosphates, dichlorophos-phates, monochlorothio phosphates, phosphoramidlc dichlorides, phosphoroamidothioic chlorides and the like.

It has been found that the compounds herein contemplated display excellent activity in the control of insect populations.

Not only are the compounds of value as lethal insecticides, but they exhibit a unique property of rendering the insects sterile, that is, control or eradication becomes possible by causing sexual sterility in the insect. Thereby, propagation of the species is severely inhibited.

In general, according to this invention the compounds have been found to control insects by killing, as well as by causing sexual sterility therein.. The compounds for effective control may be applied at varying rates either Incorporated in a food supply or by direct contact with the insects. A suitable sterllant may limit populations of insects either by sterilizing or by killing, depending upon the rate of dosage used.

The compounds of the present invention may be made in accordance with the following non-limiting example.

Example Preparation of P,P-bis(l-aziridinyl)-N-methylphosphino-thioic amide.

A 200 cc. 3-necked flask was provided with stirrer, thermometer, addition funnel and gas exit tube. The entire apparatus was flushed out with argon.

A solution of 9.4 g. (0.092 moles) of triethylamine and 4.0 g. (O.092 moles) of ethyleneimine in 40 cc. of dry benzene was charged to the flask and cooled to 0°C. A solution of 6.6 g. (0.040 moles) of methylphosphoramidothloic dichloride in 40 cc. of dry benzene was then added dropwlse at 0-4°C. to the amine solution with cooling. After completion of the addition, the cooling bath was removed and the reaction mixture was allowed to warm to room temperature. The mixture was heated to 35-40°C. and maintained at that temperature for 1 hour. The reaction mixture was then filtered and the triethylamine hydrochloride solid was washed with 5 cc. portions of benzene. After drying, the triethylamine hydrochloride weighed 10.7 g. (97. 3$ yield).

The combined benzene filtrate was concentrated on a rotary evaporator under reduced pressure at a temperature not exceeding 80°C. The residual liquid which was obtained was chilled in a freezer overnight and crystallized. There was obtained 6.7 g. (94.4 yield) of P, P-bis ( 1-aziridinyl ) -N-methyl-phosphinothioic amide, m.p. 70 .0-71 .5°C. - 5 g- of the above product was heated to boiling with cc. of anhydrous ethyl ether and 10 cc. of dry n-hexane.

The hot solution was decanted from a small amount of brown gummy product residue. On cooling, the -gvr-iduet crystallized out. After standing at room temperature for several hours, the crystals were filtered off and dried in the vacuum oven at 55-60 ° for about minutes. There was obtained 4.7 g. (85.4 recovery) of purified product, m.p. 71 - 0-72 . °C.

Anal.: Calcd. for C^H^^PS: C, 33 - 8 ; H, 6.82; N, 23 - 71; P, 17 - ^8 S, 18.09. Pound: C, 34.07; H, 6. 59; N, 23 - 7^; P, 17 - 0; S, 17 - 8 .

The following is a list of the compounds prepared following the a oredescribed procedure. Compound numbers have been assigned to each compound and are used throughout the balance of the application.

TABLE I Compound Number R Hi X 3 (CH3)2N N(CH2)2 0 4 (CH3)2N N(CH2)2 s (CH3)2N C2H5 s 6 C2H50 C2H50 0 7 C2H50 C H50 s 9 σ3Ηγθ C3H70 s C2H5NH N(CH2)2 0 11 CH2=CHCH2NH N(CH2)2 0 12 C6H NH N(CH2)2 0 13 CH30(CH2)3NH N(CH2)2 s * No. 1 prepared in the Example.

As previously mentioned, the herein described compositions prepared in the above-described manner are biologically active compounds which are useful and valuable in controlling various pest organisms. The compounds of this invention were tested in the following manner.

Insecticide Evaluation Test. The topical method of application was used to evaluate contact methods of insect control. The insect species Musca domestlca (Linn.), the common housefly, was used in this test as a representative insect. Ten anesthetized female houseflies were treated topically on the meso-thorax using a self-filling one lambda pipet. The candidate compounds were dissolved in acetone containing 0.002 percent peanut oil. After 48 hours the percent mortality of the treated houseflies was recorded and the LD-50 value was calculated using well-known procedures. These values are given in Table II in the column "HP" .

Sterilant Evaluation Test. Using the same species of houseflies, the compounds of the present invention were tested according to the instant ^est procedure in order to evaluate sterilant methods of insect control. One hundred newly emerged adult houseflies of both sexes were allowed to feed on a 1 concentration of the candidate compounds mixed into one teaspoon of granulated sugar. After 3 days of continuous feeding on the treated diet, the houseflies were maintained for four days on one tablespoon of untreated diet consisting of 6 parts powdered milk, 6 parts granulated sugar and one part powdered egg white.

The houseflies were given an opportunity to oviposit on the seventh day following initial exposure to the candidate compounds. The egg clusters were collected from the oviposi-tion medium and suspended in distilled water. Approximately 100 eggs were pipetted onto a 1-lnch square piece of moist black cloth. The eggs were then placed upon fresh larval media and reared through to the succeeding generations.

The compounds were evaluated on the basis of percent egg viability, pupal formation, and the number of adult flies emerging from the pupal stage. The criterion for choosing compounds for further evaluation is the complete mortality of the parent flies, or an SC-90 value. The SC-90 value is the percent of compound in the diet which allowed only 10 percent of the total eggs deposited to complete the life cycle and emerge as adult flies. The SC-90 values are given in Table II under "SC-90".

TABLE II Contact Activity Sterilant Activity Compound LD-50 SC-90 Number (ug/fly) (percent ) 1 25 0.03 2 (100) 0.01 3 (100) 0.05 4 8 0.1 8 0.5 6 10 >1.0 7 25 1.0 8 15 0.8 9 25 0.8 (100) 0.03 11 75 0.01 12 75 0.1 13 50 0.05 0 = partial control.

Prom these data it can be seen that these compounds are valuable insecticides. They may be used in the form of emulsions , non-aqueous solutions, wettable powders, vapors, dusts, dips, and the like, as may be best fitted to the particular utility. The mode of administration to a pest or its habitat are well known to those skilled in the art of insect control. The disclosure is not meant to limit the action of the compounds to one particular insect species or the mode of effect thereon .

Various changes and modifications may be made without departing from the spirit and scope of the invention described herein as will be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the appended claims.

Claims (1)

1. MOW particularly described and ascertained the natur of our said invention and in what manner the is to be we declare that what claim is A method for controlling insects comprising applying to an insect habitat an effective amount of a compound of the formula wherein is a member selected from the group consisting of alkoxy and lower alkyl containing from 1 to 6 carbon R is a member selected from the group consisting of dialkylamino alkylamino alken by the fact that amino and further characterized is aziridinyl R is other than and X is selected from the group consisting of oxygen and In a method according to Claim an insecticidal composition comprising an inert insecticidal adjuvant and an effective amount of a compound according to Claim The method of Claim wherein the compound is amide The method of Claim wherein the compound is amide The method of Claim wherein the compound is diethyl The method of Claim wherein the compound is phosphinic The method of Claim wherein the compound is Bated this 28th day of 1966 For Applicants insufficientOCRQuality