3,776,950 Jnited States Patent Office Patented Dec. 4, 1973

2 to the nitrogen atom of the phosphorus imide. Thus, the

- - - 3,776,950 nitrogen atom of the N-cyanoimide in addition to carrying NCYANOPHOSPHINMOES the cyano group is doubly bonded to pentavalent phos Ronald A. Mitsch, St. Paul, Minn., assignor to Minnesota phorus. Mining and Manufacturing Company, St. Paul, Minn. No Drawing. Continuation-in-part of application Ser. No. The compounds of the invention have the structure 808,656, Mar. 19, 1969, which is a continuation-in part of application Ser. No. 482,585, Aug. 25, 1965, Y-R-Z. both now abandoned. This application Nov. 26, 1971, N Ser. No. 202,667 Y-R-2-p a N-CEN Int, C. C07d 27/56, 31/46, 63/00 10 Yi-R-2, U.S. C. 260-55 C S Claims

ABSTRACT OF THE DISCLOSURE wherein Z is a divalent linking group of the class con Novel substituted N-cyanophosphorus imides having a sisting of a carbon to phosphorus bond, relatively high degree of hydrolytic stability are prepared 5 by reacting a trivalent phosphorus compound with di fluorodiazirine in the presence of an inert solvent. Such -S-, -O- or Y-R-N- compounds have utility as pest control agents, corrosion each R is alkyl having 1 to 16 carbon atoms, alkenyl inhibitors, plasticizers, flotation agents and petroleum 20 having 2 to 6 carbon atoms, aryl having 6 to 14 carbon additives. atoms, alkaryl having 7 to 12 carbon atoms, aralkyl hav ing 7 to 15 carbon atoms or cycloalkyl having 3 to 6 car This application is a continuation-in-part of my co bon atoms; Y is halogen, nitro, cyano, carbonyl, acyl, pending application Ser. No. 808,656, filed Mar. 19, 1969 carboalkoxy, hydroxy and alkoxy, n is 0 to 3, provided now abandoned, which application was a continuation 25 that when R is methyl, n is zero or one and when R is in-part of my copending application U.S. Ser. No. 482,585 alkenyl, n is zero; two of said R groups when alkyl and filed Aug. 25, 1965, now abandoned. taken together with each other and the nitrogen linking This invention relates to novel organophosphorus radical to which they are attached can form a 5- to imides and more particularly to N-cyanoimide derivatives 6-membered ring system having a total of up to 9 carbon of organophosphorus compounds, and to a process of 30 atoms; and two of said R-Z-groups when alkyl, alkoxy, preparing said N-cyanoorganophosphorus imides. alkylmercapto or alkoxy-alkyl when taken together with Organic phosphorus compounds which contain an imide each other and the phosphorus atom can form a 5- to or imine group, and which are substituted by alkyl, aryl 6-membered ring system having a total of up to 12 car and other groups, are known and have been prepared bon atoms, of which 4 carbon atoms can form part of generally by the reaction of with phosphines. How 35 an aromatic ring fused to the said 5- to 6-membered ring. ever, these phosphorus imides are, in general, quite sus One of the R radicals can be substituted by another ceptible to hydrolysis, which is disadvantageous when corresponding substituted N-cyano-phosphorus imide they are to be used under conditions where the presence of moisture cannot be controlled. group, i.e., a group of the structure Recently, the preparation of N-cyanotriphenylphosphin 40 imide, (CH)P=NC=N, from the reaction of Y-R-Z. with triphenylphosphine, has been described by N Marsh et al., J. Am. Chem. Soc., 86, 4506 (1964). How Y-R-2-PN-CN ever, so far as is known to applicant, no organic phos / phorus compounds containing the N-cyanoimide group 45 bonded to phosphorus in the molecule was known prior so as to form, e.g., bis-N-cyanophosphorus imide sub to his invention thereof, nor have the stability and highly stituted compound. useful properties of this class of compounds been recog When the linking groups -Z- of the above formula nized. are a carbon to phosphorus bond, the compounds are An object of this invention is to provide novel and 50 named as phosphinimide derivatives, e.g., N-cyanotriethyl useful organic phosphorus compounds containing the phosphinimide. When the linking groups -Z- are -S- N-cyanoimide group bonded to phosphorus in the or -O-, the compounds are properly named as phos molecule. phoroimidates, e.g., N-cyano-S.S.S-tributyltrithiophos Another object of this invention is to provide a class phoroimidate or N - cyano - O,O,O-triphenylphosphoro of organophosphorus imides many of which have a 55 imidate, although they may, for convenience also, be relatively high degree of hydrolytic stability. designated as, e.g., N-cyanotributylmercaptophosphin A further object of the invention is to provide a novel imide or N-cyanotriphenoxyphosphinimide, respectively. process for the preparation of organic phosphorus com The compounds of this invention possess utility as pounds containing the N-cyanoimide moiety in the mole pest-control agents, including insecticidal and rodenti cule. Other objects of the invention will become apparent 60 cidal properties among their characteristics. Certain of from the disclosures hereinafter made. the compounds can also be used as herbicides, corrosion The novel compounds of the invention are character inhibitors, plasticizers, flotation agents and petroleum ized by the presence of a cyano group covalently bonded additives. 3,776,950 3 4. The N-cyanophosphorus imides of the above general cient to give a useful yield. Since difluorodiazirine is a formula are readily prepared by the reaction of a tri gas, even at -78° C., it is convenient to monitor the ex valent phosphorus compound of the general formula: tent of completion of the reaction by infrared examina tion of the volatile components of the mixture. In this way, the course of the reaction can be followed and when the characteristic absorption peak of the diazirine ring disappears or is greatly weakened, the process can be terminated. The products of the reaction are isolated by distil O lation, column chromatography or crystallization and combinations thereof. The two organophosphorus deriva in which Y, R and Z have the meaning set forth above, tives ordinarily have widely differing properties and with difluorodiazirine, having the formula: are easily separated from each other and from the start ing material. - 5 The trivalent phosphorus compounds useful as starting materials for the preparation of N-cyanophosphorus imides are available commercially or can be prepared by synthesis techniques well known to the art. Procedures for preparation of these materials are set forth in "Organo 20 phosphorus Compounds,” G. M. Kosolapoff, John Wiley This compound is disclosed in a publication by R. A. and Sons, Inc., New York, 1950. Mitsch, J. Heterocyclic Chem, 1, 59 (1964). The course In general, the trivalent phosphorus reagents useful as of the reaction is shown by the following general equation: starting materials vary considerably in their reactivity with difluorodiazirine. Starting materials which are sub 25 stituted with a multiplicity of electron-donating groups, Y-R-2 such as methoxy and dialkylamino groups, are highly re Y-R-Z F. N N Y-R-Z-P -- C Y-R-Z-PacN-CN active. In fact, compounds such as trimethylphosphite or / N tris(dimethylamino)phosphine can react explosively with Y-R-Z. N difluorodiazirine if suitable precautions of cooling or dilu 30 tion are not employed. On the other hand, trivalent phos -- phorus compounds which are substituted with electron withdrawing substituents are sluggish to react. The organic radicals of the trivalent phosphorus start ing compounds can be unsubstituted or substituted. 35 Among the substituents which can be present are halo, nitro, cyano, alkoxy, keto, carboxyl, acyl, carboalkoxy, hydroxyl and the like. These substituents do not inter The stoichiometry of the reaction thus requires two moles fere with the N-cyanophosphorus imide-forming reaction, of trivalent phosphorus compound per mole of difluoro and are not lost. Therefore the final products also can diazirine. Varying the stiochiometric quantities of the 40 contain such substituents in the organic radicals reactants used has little effect on the products obtained Y-R-Z. One to three substituents are allowable on the in the reaction, the yield being dependent on the amount organic radical except when the organic radical is an of reagent present in smallest amount. alkyl group having one carbon atom, e.g. methyl, then The process of the invention is conveniently carried only a single substituent is allowable. Further, com out by dissolving the trivalent phosphorus compound in 45 pounds containing more than one reactive, trivalent phos a solvent in which it has at least moderate solubility and phorus atom can be used as starting materials. These re which is inert with respect to the reactants and products act with difluorodiazirine in the same way to produce of the reaction at the temperature employed. In the case compounds which contain more than one N-cyanophos of a batch reaction, the difluorodiazirine, which is a gas phorus imide group, and such compounds are contem boiling at about -91° C., is then introduced, e.g., by 50 plated by and included within the scope of the invention. condensation or by pressurization. In a flow-through sys Trivalent phosphorus compounds containing groups such tem, the difluorodiazirine is bubbled through a solution of as peroxide moieties are not presently disclosed in the the selected trivalent phosphorus compound in an inert literature, and the compounds which would be formed solvent. The reaction is self-initiating and results in the from such starting reactants do not constitute a part of formation of a mixture of the substituted N-cyano 55 this invention. phosphorus imide and the corresponding pentavalent The inert solvent which is chosen for the preparation phosphorus difluoride. of any particular compound according to the invention The time and temperature required for the reaction will depend upon the trivalent phosphorus reactant and the vary widely, depending on the reactivity of the trivalent conditions to be used. That is, under the conditions used phosphorus reactant, the quantity of the reactants 60 it must be liquid, must be capable of dissolving at least utilized and the dilution. a moderate amount of the reactants, and must be inert The reaction is preferably carried out at a temperature with respect to the materials present. Among the suitable within the ring from about -100° C. to -- 100° C. In the solvents are dichloromethane, carbon tetrachloride, chlo case of highly reactive trivalent phosphorus compounds, roform, , benzene, chlorobenzene, diglyme, the reaction is conveniently run at -78 C. in a Dry-Ice 65 acetone, etc. The boiling point of the solvent is not critical cooled reactor whereas with less reactive reagents stirring for the reaction although the lower boiling solvents are at room temperature is convenient. However, tempera desirable because they facilitate isolation and recovery tures outside of the above range may be employed de of the N-cyanophosphorus imide products. pending upon the type of reactant and solvents utilized. The N-cyanophosphorus imides of the invention are Use of a pressure vessel may be required, as will be ap 70 generally colorless liquids or solids. They can be purified parent to the art from the highly volatile nature of the by high-vacuum distillation, recrystallization, solvent ex difluorodiazirine. W traction, sublimation, solid-liquid absorption column The reaction time is not critical but should be of suffi chromatography and other related known techniques. cient length to permit the reaction to be completed. Specific examples of the N-cyanophosphorus imides of Ordinarily, one hour to one week is in most cases Sufi 75 the invention include:

3,776,950 7 8 In order to disclose more clearly the process and com nitrogen temperature, degassed by reducing the pressure pounds of the invention in the best mode presently con in the reactor to less than 0.1 mm. of mercury, and 1.17 templated, a number of specific examples will now be grams of difluorodiazirine are added by condensing the given. All parts are by weight unless otherwise desig gas into the cold reactor. The apparatus and the reaction nated. mixture are then allowed to warm to room temperature, EXAMPLE 1. and stirring is begun and continued for 24 hours. At this This example illustrates the procedure used in prepar time, a colorless solid precipitate, comprising N-cyano ing the compounds of the invention from substituted triphenylphosphinimide, has appeared and is removed phosphines and difluorodiazirine, where all of the latter by filtering. The product is recrystallized twice from ben reactant is added initially and the process operates as a O Zene; about 3.15 grams (about 70 percent yield) of batch process. Triphenylphosphine is to be understood as colorless needles are obtained, melting at 194-196° C. representative of a broad range of benzene-soluble phos Analysis.-Calculated for CHNP (percent): C, phines. It will be understood that the nature of the phos 75.5; H, 4.97; N, 9.3; P, 10.3. Found (percent): C, 75.7; phines will determine the solvent to be used in the reaction H, 5.0; N, 9.7; P, 10.2. mixture, while the temperature employed and the time 5 The triphenylphosphorus difluoride which is the other during which the reaction is carried out depend both part of the reaction remains in the filtrate from the re upon the reactivity of the substituted phosphine which is action mixture, while a small amount of this material is employed and the yield required. also recovered from the filtrate from recrystallization of A solution of 7.86 grams of triphenylphosphine and 25 the desired product. ml. of benzene is placed in a 50 ml. glass reactor fitted 20 The following table is illustrative of other phosphines with a polytetrafluoroethylene valve and containing a usable as starting materials and the resulting products magnetic stirring bar. The solution is cooled to liquid using the procedure of Example 1. TABLE II Phosphine starting material Product (CICH)sP (CICH)3PsNCN

("go")ÖH. s PaNCN (CH=CH-CH2)3P=NCN

({ X-CH), P ({ X-CH) 8 PNCN ..) PanCN (...) ( CHA C

PsNCN

M PsNCN CO 8 5. O PNCN N Y E. 3. C C -O { X-0 -NCN C-o-C-. &E, C C-on-on-onC (pH, CH-PsNCN

CH P=NCN N E.

3 776,950- 9 10 ------ABLE - Continued Phosphine starting material Product

Br Br

P P=NCN ki>) ( >)-se es ------...- : ...- O CEs-CH CHCH-i-NONCH ÖH, X--- (Cs. CHOCH

&H, CHO CH

N= N=N ( -//A- ( ==//N-I-P=NCN

CH CH

l H - Non

CH CH-CH M. N. C.H.P. C Claas I -CH cá, NCN

O4cs-1 3,776,950 11. 2 TABLE II-Continued Phosphine starting material Product catter? Char-NON

EXAMPLE 2. 20 EXAMPLE 3 The following is a specific example of a nitrogen-inter This example illustrates the procedure used in prepar rupted alkyl chain-substituted phosphine and is exemplary ing compounds of the invention from substituted phos of hetero-atom interrupted trivalent phosphorus com phites and difluorodiazirine. pounds in general. O,O-diethyl - O - (2 - ethylthioethyl)phosphite is to be A solution of 11.56 grams of tris(diethylaminomethyl) 25 understood as representative of a broad range of methyl phosphine and 40 ml. of methylene chloride is placed ene chloride soluble phosphites. It will be understood that in a 75 ml. glass reactor fitted with a polytetrafluoro the nature of the phosphites will determine the solvent ethylene needle valve and containing a magnetic stirring to be used in the reaction mixture, while the tempera bar. The solution is cooled to liquid nitrogen tempera ture employed, and the time during which the reaction ture, degassed by reducing the pressure in the reactor 30 is carried out, depend both upon the reactivity of the to less than 0.1 mm. of mercury, and 2.0 grams of di substituted phosphite which is employed and the yield fluorodiazirine are added by condensing the gas into the required. cold reactor. The reactor and reaction mixture are then Following the procedure outlined in Example 1, a allowed to warm to -78 C. and then stirring is begun solution of 9.04 grams of O,O-diethyl-O-(2-ethylthio at that temperature and continued for one day. 35 ethyl)phosphite, made by the procedure of Hoffman et The solvent is then removed by distillation and the al., J. Am. Chem. Soc., 80, 1150 (1958), dissolved in semi-solid crude product is subjected to two extractions 25 ml. of methylene chloride is reacted with 2.0 grams at 60° C. with heptane. Cooling the heptane extract of difluorodiazirine. The reaction mixture is stirred at initiates crystallization. Filtration is employed to collect room temperature for 4 days, after which the solvent and about 4 grams (about 61 percent yield) of a colorless 40 unreacted difluorodiazirine are removed by distillation. solid melting at 90-92 C. The oily crude product is purified by liquid column Analysis.-Calculated for CH3NP (percent): C, chromatography on a column composed of silica gel 58.4; H, 10.9; N, 21.3; mol, wt., 329. Found (percent): and employing chloroform and ethyl acetate as eluents. C, 57.2; H, 10.9; N, 21.4; mol. wt., 320. About 0.7 gram of purified N-cyano-O,O-diethyl-O-(2- Other nitrogen-interrupted alkyl chain-substituted phos 45 ethylthioethyl)phosphoroimidate is collected after evap phine products and their starting materials are set out oration of the ethyl acetate eluent. The product is identified below in Table III. by infrared spectroscopy.

TABLE Phosphine starting material Product; CH CH C-C)cá, C-C)cá,

Cas Cas C-C)cá, C-C)cá,

CE (CH)-sNCN (citi),P-( >-NCYoH,

N off, Yoh, 3,776,950 13 14 Further examples of compounds prepared from sub- The residue is heated to 90° C. under vacuum and the stituted phosphites according to the procedure described byproduct, tris(dimethylamino) phosphorus difluoride is in Example 3 are set forth in Table IV below. removed by fractionation. TABLE TV Phosphite starting materials Product (-(5-o).Cl (-(5-o)-seC

Co H /

( -o-P-O-K > l ) H(CH) O CH(CH3)

( l -).

/ op=NON (O Y-ocHCHCl (O Y4.NcNOCHCHCI

O O Y-o-cal, Y4icO-CE o/ o/ O O O/ Y-o-o: YosO-CI o/ o/ ({ X-CH,0}.CEO.--PN ( >-CH:o)CEO.--P=NCN17, EXAMPLE 4 Column chromatography of the residue employing This example is exemplary of phosphines to which 65 silica gel as the solid phase and mixtures of chloroform, nitrogen atoms are bonded directly to the trivalent phos- ethyl acetate and methanol as the eluents is utilized for phorus. According to the procedure outlined in Example preliminary purification of the desired N-cyanophosphorus 2, 6.52 grams of tris(dimethylamino) phosphine, made imide product. Final purification by recrystallization from by the procedure of Burg et al., J. Am. Chem. Soc., 80, butyl acetate affords about a 40 percent yield of a color 1107 (1958), dissolved in 2. of tly chloride 70 less solid melting at about 73-75° C. This material is ofis reacteddifluorodiazirine with stirring at in-78 a batch C. Theprocess low with temperature 2.0 grams is identified as N - cyanotris(dimethylamino)phosphinimide8 extremely important in this reaction owing to the high by infrared spectroscopy. reactivity of the phosphine. After stirring for 18 hours, The following table is illustrative of aminophosphines the methylene chloride solvent is removed by distillation. 75 and thiophosphites and their respective products. 3,776,950 15 16 TABLEW Aminophosphine starting material Product; ( 39-po Cas O Cas NA-P) NA-P-NCN) CH ( S) P ( S)

) Cl

( -//NA-P4.NcN CHShe son

CHO

--N CHCR N c L YoH, off, Cls so Cas) N-P(OCH) P M CH (CH)N-P-N O (CHS)P (CHS)PsNCN ({X-)-NON SC (CHO)P-S-CHs / s (CHO)P SaNoN (c 12Has s\-P (-(e-) (-(e-)-son/ J) J)s\-P-NCN 3,776,950 17 18 EXAMPLE 5 The compounds of this invention are useful as insect The compounds of the invention can also be prepared repellents and insecticides. They can also be used as by reaction of substituted organic trivalent phosphorus nematocides. For these purposes, they are applied directly derivatives with cyanogen azide. The following is a specific to the particular insect, e.g. flies, mosquitoes, etc., in example of the preparation of an N-cyanophosphorus 5 insecticidally effective amounts, or placed in the soil or imide by this process, S.S.S-tributyltrithiophosphite being other location where the insects are to be found. They exemplary of all of the trivalent phosphorus derivatives may be applied as such, or preferably are employed with which can be used to make the compounds of the inven inert solids to form powders or suspended in a suitable tion. liquid diluent. There can also be added surface active To a solution of 2.72 grams of cyanogen azide (pre O agents or wetting agents and inert solids in such liquid pared by adding 2.6 grams of to 4.2 grams formulations. Desirably, about 0.25 to 1 percent by of dissolved in 20 ml. of anhydrous weight of surface active or wetting agent is employed, acetonitrile) were added, dropwise, 11.92 grams of tri while the active ingredient, the organic N-cyanophos butyltrithiophosphite dissolved in 10 ml. of benzene. After phorus imides of the invention, are added in amount of addition of the thiophosphite was complete, the mixture 15 about 0.1 to 5 percent by weight of the entire composi was allowed to stir at room temperature for about 2 hours, tion. and thereafter the reaction mixture was filtered and the As the liquid carrier there can be employed organic filtrate evaporated to dryness in vacuum. The residue, Solvents, e.g. hydrocarbons such as benzene, toluene, about 12.7 grams of yellow-colored amorphous solid ma Xylene, kerosene, diesel oil, fuel oil, petroleum, naphtha terial, was taken up in 50 ml. of chloroform and the solu 20 and the like; ketones, e.g. acetone, methylethyl ketone, tion was poured onto a silica gel column. The material etc., chlorinated hydrocarbons such as carbon tetrachlo was chromatographed using chloroform and ethyl acetate ride, chloroform, trichloroethylene and perchloroethylene, as eluants. esters such as ethyl acetate, amyl acetate and butyl ace After a short forerun which was discarded, the rela tate, ethers, for example ethylene glycol monomethylether, tively light-colored eluents from the column were col 25 and the like; alcohols, e.g. methanol, ethanol, isopropanol lected as center cuts. These were evaporated to dryness, or amyl alcohol, ethylene glycol, propylene glycol and yielding N-cyano-S,S,S-tributyltrithiophosphoroimidate, a glycerine. Mixtures of water and organic solvents, as colorless oil. The structure is confirmed by infrared spec solutions or emulsions can likewise be employed. A very troscopy. The yield is about 64 percent of the theoretical. useful hydrocarbon solvent for the purpose is deodorized The following table further illustrates preparation of 30 kerosene. specific N-cyanophosphorus imide compounds of the in Undissolved or suspended in solvents, the compounds vention. In each case, the starting material is the respec of the invention can be applied as aerosols, e.g. by dis tive trivalent phosphorus derivative having the same radi persing them in air by means of a compressed gas such cals attached to phosphorus as are found in the product. as air, dichlorodifluoromethane, trichlorofluoromethane Essential process conditions are given. Column chroma 35 or other low molecular weight halogenated alkanes. tography or recyclization from suitable solvents is em Illustrating the repellent activity of the compounds of ployed for purification purposes. the invention against mosquitoes, the following tests were TABLE VI Process conditions Example Product M.P. or B.P. Temp,ftime Solvent 6------(CH)P=NCN 22° C.f48 hrs. Methylene oil, no?=1.4813 dichloride: 7------(CHsO)PsNCN 22° C.72hrs. Methylene B.P. 69/0.16mm. dichloride. 8.------CHO)?s=NCN 22° C./100 hrs. Carbon tetra chloride. 9------(CHO)sR=NCN 22° C.7 days Benzene. M.P.925-93.5 C, 10------(HaS):P=NCN 22°C./7 days Chloroform. O 1l----- on in soosa OCH 22° C.17 days Benzene. oN-( >-0--NONb C oil 12------OCH 22 C./7 days Methylene dichloride NE O-PNCN C oil 18------now-on-- OCs 22 C./7 days Benzene. Cl o--NON Cas

o 14------CE O CHCHS CH a8 C.124 hrs Methylene N dichloride. N- aNCN C N cá, CH ol 3,776,950 19 carried out. About 3 grams of N-cyanotributylphosphin imide dissolved in 20 ml. of acetone were applied to a TABLE VIII cotton stocking, a subject wearing the cotton stocking on Percent mortality his arm exposed it to active yellow fever mosquitoes, Concen- House flies Pea Aedes aegypti L., and stable flies, Stomoxys calcitrans L, tration, aphids, Mites, at intervals throughout the test period. The insects were 5 Compound mg/l. 2 hrs, 24 hrs. 48 hrs. 5 days repelled from the stocking, and no individual insect of (CHO). P=NCN...... { } E. g. S. either type settled upon its surface for 9 days after the Untreated control.------O 0 O O initial application. The same compound was sprayed on the surface of What is claimed is: granulated sugar, and the sugar was exposed to adult O 1. A compound having the formula house flies. Two concentrations of application were used, Q 0.5 percent by weight and 0.1 percent by weight. The 0.5 N percent by weight application gave 100 percent repellency Q-P=NCEN7 whereas even at 0.1 percent by weight, the repellency was 15 Q3 55 percent. wherein Q1, Q2, and Q are 3-hydroxyethyl, 2-hydroxy In order to demonstrate more fully the insecticidal and propyl, octyl, m-chlorophenyl, propenyl, isobutenyl, nematocidal properties of the compounds of the inven chloromethyl, benzyl, o-methoxyphenyl, o-, m-, p-tri tion, the following tests were carried out, and the results methylphenyl, ov-naphthyl, 3-indolyl, 9-bronoanthracy, are shown in Table VII. 20 4-biphenyl, butyl, p-(dimethylamino)-phenyl, or p-(di The minimal lethal concentration of the test chemicals ethylamino)-phenyl phenyl dimethylamino; or to 2-4 day old mosquito larvae (Aedes aegypti L.) is de wherein Q and Q are methyl and Q is p-bromophenyl, termined. Mosquito eggs are hatched in distilled water. or 6-phenethyl p-phenoxy-phenyl; or Dilutions of the test chemical are prepared in distilled wherein Q and Q are ethyl and Q is tolyl, p-hydroxy water at 100, 10 and 1 mg. W., and 9.0 ml. portions are 25 phenyl, or 2-thienyl; or placed in 1-dram shell vials. One milliliter of water con wherein Q and Q are phenyl and Q3 is o-(methoxymeth taining 4 to 8 mosquito larvae is added to each vial and yl)-6-phenethyl, m-carboxyphenyl or hexadecyl; or inspected for death or other changes at intervals for one wherein Q1 and Q are butyl and Q3 is (N,N-dimethyl day. amino)-phenyl; or In order to evaluate nematocidal activity of test chemi 30 wherein Q1 and Q are 2-pyridyl and Q is phenyl; or cals, the minimum lethal concentration to Panagrellus sp. wherein Q and Q are allyl and Q is p-bromophenyl; nematode worm is determined. Panagrellus is reared in Ot oatmeal medium at a temperature of 5-10° C. Dilutions wherein Q is p-methoxyphenyl, Q is p-bromophenyl, and of the test chemical are prepared in distilled water at 100, Q3 is phenyl. 10 and 1 mg.a.l., and 9.0 ml. portions are placed in 1 35 2. The compound N-cyanotriphenylphosphinimide, ac dram shell vials. One milliliter of water containing 50 to cording to claim 1. 70 nema is added to each vial. The nema are observed for 3. The compound N-cyanotributylphosphinimide, ac death or other changes at 24 and 72 hours. cording to claim . TABLE VI 4. The compound N-cyanotris (dimethylamino) phos 40 Minimum lethal phinimide, according to claim 1. concentration, mg/l. 5. Process for producing a compound according to (pp.m.5 claim 1, which comprises reacting a compound having the aedes Pana formula aegypti grellus Compound I. sp. 45 (CaO)3P=NCN 10 Q (CHS)3P=NCN 10 ------(CH)3PaNCN 00 QtrQs (CH5)3P=NCN ------100 (CH5O)3P=NCN 100 ------in which Q, Q and Qs have the same significance as set forth in claim 1, with difluorodiazirine in the presence of NCN O 100 50 an inert solvent. (CHO)PO CHS CH References Cited In order to demonstrate further the insecticidal activity of the N-cyanophosphorus imides of the invention against Marsh et al.: JACS, vol. 86, p. 4506 (1964). insects other than mosquitoes, the following tests were 55 carried out with (CHO)3P=NCN. The sample was dis HARRY I. MOATZ, Primary Examiner solved in acetone at concentrations of 10 and 5 mg./l. U.S. C. X.R. and dispersed in distilled water with the aid of an alkyl 260-239 E, 298 R, 293.69, 293.75, 294.9, 309, 319.1, aryl polyether alcohol wetting agent (available under the 326.15, 329 P, 347.7, 348 R, 518 R, 576, 606.5 P, 920, trademark "Triton X-100") as an emulsifier. The mixture 60 928, 936, 940, 947, 951, 954, 955, 956, 959; 424-200, is applied to the test insects as an aerosol. The results 202, 203, 204, 205, 209, 210, 211; 71-86, 87; 252-60, are shown in Table VIII. 388, 389, 390; 260-551 P UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,776,950 Dated December 4, 1973 Inventor(s) Ronald A. Mitsch It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: Col. 8, Table II, right Side of Table, equa. 9 should read: CH3 (y-o-y- as NCN

instead of:

C

()-O-(was )-- NCN CH3 Table VI, 4th line, Col. 17 reads: oil, nD2" = 1.4813 Should read: Oil n2D = l. 4813 Signed and sealed this 23rd day of April l974.

(SEAL) Attest : C.E.R. J. C. if A SHALL, DAN: w COmmissioner of Patents

2RM Po-1050 (10-69) US COMme oc so 6-pey

S. Gowraht PYC offic 98 98-3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,776,950 Dated December 4, 1973 Inventor(s) Ronald A. Mitsch It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: Col. 8, Table II, right Side of Table, equa. 9 should read: Fs (y-o-y- as NCN

instead of:

Table VI, 4th line, Col. 17 reads: oil, nD2' = 1.4813 Should read: oil nD24 = 1. 4813

Signed and Sealed this 23rd day of April l974.

EDWARD - FLETCHER, JR . C. At SHALL, DAilil Att3 Sting Officer Commissioner of Patents

2RM Po-105Q (10-69) Js COMM dict 8 or 6... p 6 US Gover Mt Pik Yi No of Fict 960 566-4