3,574,851 United States Patent Office Patented Apr. 3, 1971 2 trihexyl (4-nitrosotolyl)ammonium bromide, 3,574,851 dimethylhexyl (4-nitrosotolyl)ammonium chloride, FUNGCDAL METHOD EMPLOYING NEW dihexylmethyl (4-nitrosotolyl)ammonium iodide, QUATERNARY AMMONUM HALDES Asher A. Hyatt, Lexington, Mass., assignor to Monsanio diethylpentyl (4-nitrosotolyl)ammonium fluoride, Research Corporation, St. Louis, Mo. butyldipropyl (4-nitrosotolyl)ammonium bromide, No Drawing. Original application Dec. 3, 1965, Ser. No. butylhexylmethyl (4-nitrosotolyl)ammonium chloride, 531,320, now Patent No. 3,390,178, dated June 25, trimethyl(4-nitrosoxylyl)ammonium fluoride, 1968. Divided and this application Dec. 20, 1967, Ser. triethyl (4-nitrosoxylyl)ammonium chloride, No. 721,893 tripropyl (4-nitrosoxylyl)ammonium bromide, nt. C. AOn 9/20 O tributyl (4-nitrosoxylyl)ammonium iodide, U.S. C. 424-329 2 Claims tripentyl (4-nitrosoxylyl)ammonium fluoride, trihexyl (4-nitrosoxylyl)ammonium chloride, dimethylhexyl (4-nitrosoxylyl)ammonium fluoride, ABSTRACT OF THE DISCLOSURE dihexylmethyl (4-nitrosoxylyl)ammonium chloride, A method of controlling soil fungi employing certain 15 diethylphentyl (4-nitrosoxylyl)ammonium bromide, new nitroso substituted aryl derivatives of trialkyl ammo butyldipropyl (4-nitrosoxylyl)ammonium iodide, nium halides. butylhexylmethyl (4-nitrosoxylyl)ammonium fluoride, trimethyl(4-nitrosonaphthyl)ammonium iodide, triethyl (5-nitrosonaphthyl)ammonium fluoride, This is a division of application Ser. No. 531,320 filed tripropyl (6-nitrosonaphthyl)ammonium chloride, Dec. 3, 1965, now Patent No. 3,390,178. tributyl (4-nitrosonapththyl)ammonium bromide, This invention relates to the reaction of nitroso sub tripentyl (5-nitrosonaphthyl)ammonium iodide, stituted aromatic hydrocarbon derivatives of dialkyl trihexyl (6-nitrosonaphthyl)ammonium fluoride, amines with alkyl halides and to the products thereof. dimethylhexyl (4 - nitrosonaphthyl)ammonium chloride, It is an object of this invention to provide new nitroso 25 dihexylmethyl (4-nitroSonaphthyl)ammonium bromide, substituted aryl derivatives of trialkyl ammonium halides. diethylpentyl (6-nitrosonaphthyl)ammonium iodide, It is another object of this invention to provide com butyldipropyl (4-nitrosonaphthyl)ammonium fluoride, pounds useful as biological toxicants such as fungicides, butylhexylmethyl (5-nitrosonaphthyl)ammonium plant growth regulators, defoliants, insecticides and bromide, bactericides. 30 trimethyl(3'-nitrosobiphenlyl)ammonium chloride, According to the invention, there are prepared new triethyl (2'-nitrosobiphenylyl)ammonium fluoride, and useful compounds having the formula: tripropyl (3'-nitrosobiphenylyl)ammonium bromide, tributyl (4'-nitrosobiphenylyl)ammonium iodide, R. 69 tripentyl(4'-nitrosobiphenylyl)ammonium chloride, R-N-R, Xe 35 trihexyl (3'-nitrosobiphenylyl)ammonium fluoride, RNO dimethylhexyl (2'-nitrosobiphenylyl)ammonium. wherein R1 represents bivalent aromatic hydrocarbon bromide, radicals of from 6 to 12 carbon atoms, each of R2, R3, dihexylmethyl (4 - nitrosobiphenylyl)ammonium iodide, and R4 represents alkyl radicals free of aliphatic un and so forth. saturation of from 1 to 6 carbon atoms and X represents 40 Useful nitroso-substituted aromatic hydrocarbon deriv a halogen element of atomic weight below 130. atives of dialkylamines are, for example: Preparation of the presently provided novel com N,N-dimethyl-p-nitrosoaniline, pounds is effected by contacting the alkyl halide with the N,N-dihexyl-p-nitrosoaniline, nitroso substituted aromatic hydrocarbon derivative, N-hexyl-N-methyl-p-nitrosoaniline, according to the following equation: N,N-diethyl-m-nitrosoaniline, N,N-dipropyl-o-nitrosoaniline, N,N-dibutyl-m-nitrosoaniline, is N,N-dipentyl-m-nitrosoaniline, R-N-R, -- RX --> t X N-ethyl-N-pentyl-p-nitrosoaniline, RNO RNO 50 N-butyl-N-propyl-p-nitrosoaniline, wherein R1, R2, R3, R4 and X are as defined above. N-methyl-N-propyl-o-nitrosoaniline, There are shown below a number of the specific new N,N-dimethylp-nitrosotoluidine, compounds of the invention. It is not intended that this N,N-dihexyl-m-nitrosotoluidine, be a complete listing of all compounds of the invention, N-hexyl-N-methyl-o-nitrosotoluidine, but that it merely be illustrative thereof: 55 N.N-diethyl-m-nitrosotoluidine, trimethyl (p-nitrosophenyl)ammonium iodide, N,N-dipropyl-p-nitrosotoluidine, triethyl(o-nitrosophenyl)ammonium bromide, N,N-dibutyl-o-nitrosotoluidine, tripropyl (m-nitrosophenyl)ammonium chloride, N,N-dipentyl-m-nitrosotoluidine, tributyl (p-nitrosophenyl)ammonium fluoride, N-ethyl-N-pentyl-p-nitrosotoluidine, tripentyl (o-nitrosophenyl)ammonium iodide, 60 N-butyl-N-propyl-o-nitrosotoluidine, trihexyl (m-nitrosophenyl)ammonium bromide, N-methyl-N-propyl-m-nitrosotoluidine, dimethylhexyl (p-nitrosophenyl)ammonium chloride, N,N-dimethyl-p-nitrosoxylidine, dihexylmethyl (o-nitrosophenyl)ammonium fluoride, N,N-dihexyl-p-nitrosoxylidine, diethylpentyl (m-nitrosophenyl)ammonium iodide, N-hexyl-N-methyl-p-nitrosoxylidine, butyldipropyl (p-nitrosophenyl)ammonium bormide, N,N-diethyl-m-nitrosoxylidine, butylhexylmethyl (o - nitrosophenyl)ammonium chloride, N,N-dipropyl-o-nitrosoxylidine, trimethyl(4-nitrosotolyl)ammonium fluoride, N,N-dibutyl-p-nitrosoxylidine, triethyl (4-nitrosotolyl)ammonium iodide, N,N-dipentyl-m-nitrosoxylidine, tripropyl (4-nitrosotolyl)ammonium bromide, N-ethyl-N-pentyl-p-nitrosoxylidine, tributyl (4-nitrosotolyl)ammonium chloride, 70 N-butyl-N-propyl-p-nitroxylidine, tripentyl (4-nitrosotolyl)ammonium fluoride, N-methyl-N-propyl-m-nitroxylidine, 3,574,851 3 4. 4-nitroso-N,N-dimethylnaphthylamine, (ml.) of 2-propanol is gradually added 23.7 g. (about 4-nitroso-N,N-dihexylnaphthylamine, 0.17 mole) of iodomethane. The mixture is refluxed for 4-nitroso-N,N-diethylnaphthylamine, two and one-half hours to insure complete reaction and 4-nitroso-N,N-dipropylnaphthylamine, then filtered. The crude residue is washed several times 4-nitroso-N,N-dibutylnaphthylamine, with each of 2-propanol, acetone, and ether, then dried. 4-nitroso-N,N-dipentylnaphthylamine, 5 The resulting product is trimethyl (p-nitrosophenyl)- 4-nitroso-N-ethyl-N-pentylnaphthylamine, ammonium iodide, a uniformly green crystalline solid 4-nitroso-N-butyl-N-propylnaphthylamine, weighing 27 g. (about 55% theoretical yield), soluble in 4-nitroso-N-methyl-N-propylnaphthylamine, dimethylsulfoxide and melting at 154-155° C. 4'-nitroso-N,N-dimethylbiphenylylamine, Elemental analysis of this product confirms the assigned 4'-nitroso-N,N-dihexylbiphenylylamine, O empirical formula C9H13INO: '-nitroso-N-hexyl-N-methylbiphenylamine, Calculated (percent): C, 37.0; H, 4.5; I, 43.5. Found 4'-nitroso-N,N-diethylbiphenylamine, (percent): C, 36.8; H, 4.0; I, 43.5. 4'-nitroso-N,N-dipropylbiphenylylamine, 4'-nitroso-N,N-dibutylbiphenylylamine, EXAMPLE 2. 4'-nitroso-N,N-dipentyl-biphenylylamine, 15 This example describes the utilization of a compuond -nitroso-N-ethyl-N-pentylbiphenylamine, of this invention as a bactericide. 4'-nitroso-N,N-diphenyl-biphenylylamine, To test bactericidal activity, inoculations of S. aureous, 4'-nitroso-N-methyl-N-propylbiphenylylamine, S. typhosa, and A. niger, are made on agar substrates sup porting the growth of these microorganisms, to which has and so forth. been added varying amounts of trimethyl (p-nitroso Useful alkyl halides are, for example: iodomethale, phenyl)ammonium iodide. The inoculated plates are fluoroethane, 1-chloropropane, 1-bromobutane, 1-iodo maintained under conditions supporting growth of these pentane, 1-fluorohexane, 2-chloropropane, 1-bromoiso microorganisms. At concentrations of 1 part per 1,000 and butane, 2-iodo-2-methyl-propane, 2,2-dimethyl-1-fluoro 1 part per 10,000 in the agar, the ammonium compound propane, 1-bromoisopentane, and so forth. causes substantially complete suppression of growth and In carrying out the process of this invention, the nitroso compound is simply contacted with the alkyl halide until reproduction of each of the microorganism species. the reaction is complete. It is an advantage in moderat EXAMPLE 3 ing the reaction to add one of the reactants slowly and gradually to the other, though the reactants may optionally 30 To test defoliant activity, Black Valentine bean plants, be added all at once, preferably together with a solvent 4 to a pot, are grown to the stage of having 1 mature or diluent, Solvents or diluents which may be used to trifoliate and 1 partially opened trifoliate, and then sprayed moderate the reaction and to facilitate stirring, and so With trimethyl (p-nitrosophenyl)ammonium iodideasan forth, are alcohols, such as methanol, ethanol and pro aqueous emulsion, at rates of 0.1 and 1.0 pound per acre panol, for example. 35 (lbs./A.), using a dilution of 30 gallons per acre, after The ratio of reactants may very, molar ratios of the which the plants are maintained in a greenhouse within nitroso compound to the alkyl halide compound of at temperature limits of 70°-90° F. The plants are de least 1:10 to about 10:1 may be used, but since the re foliated in the 50% range at both rates. Defoliation in action is equimolar, advantageously a 1:1 ratio of re the 51.75% range is observed when the same compound actants is employed. Excess reactant may be removed 40 is applied to soybean plants at the rate of 10 lbs./A. at the end of the reaction by, for example, extraction or EXAMPLE 4 distillation. o This example illustrates the use of a compound of this Useful temperatures for conducting the preparation are, invention for the control of plant species. for example, the reflux temperature of the reaction mix Aluminum pan flats are filled with mixtures of two ture where solvents are used or any desired temperature 45 third one-quarter mesh sieved soil, and one-third sand. from below 0° C. up to below the decomposition point Over one-third of the soil surface of each pan are scattered of the ingredients of the reaction mixture. Atmospheric 20 seeds each of different kinds of grasses; seeds of broad pressure is satisfactory for conducting the reaction, though leaf plants are randomly scattered over the remaining sub- or super-atmospheric pressures may be used if de Surface. The seeds are then covered with soil to the pan sired, ranging from 0.05 millimeter of mecury to about top and the pan is sprayed with an aqueous solution of 5,000 pounds per square inch. fertilizer and insecticides. The surfaces of the boxes are No catalyst is required. Reaction time may vary. In next sprayed with 30 ml. of a mixture of trimethyl (p- general, it will depend on the nature of the reactants used nitrosophenyl)ammonium iodide in acetone at a rate equal and on the temperature of the reaction mixture. Ordinarily to 25 lbs./A. Then the pans are placed in water and al reaction times will vary from less than one minute to sev 55 lowed to absorb moisture until the soil surface is com eral hours. pletely moist, after which they are held in a greenhouse The present new compounds are generally stable, well under standard conditions of moisture and sunlight. After defined products, soluble in sulfoxides, such as dimethyl ten days, the number and species of plants which have sulfoxide and diethylsulfoxide, for example. germinated and grown are observed. The new compounds are useful for a variety of agri 60 The ammonium compound produced substantially com cultural and industrial uses; for example, trimethyl (p- plete suppression of plant germination and growth on pig nitrosophenyl)-ammonium iodide may be used as a Weed While it produced no effect on sugar beets and mammalian toxicant and herbicide and is particularly radishes. effective as abactericide. EXAMPLE 5 The invention will be further described with reference 65 to the following specific examples. These examples are This example illustrates the use of a compound of this given for purposes of illustration only and are not to be invention as a pesticide for the destruction of lower animal taken as in any way restricting the invention. life forms. In insecticidal screening, activity for control of southern EXAMPLE 1. 70 armyworms (Prodenia cridania) is demonstrated as fol lows. Lima bean leaf discs (7 mm. in diameter) are pre This example illustrates the preparation of a compound pared by evaporating one microliter of an acetone solu in accordance with this invention. tion containing trimethyl - (p-nitrosophenyl)ammonium To a reaction flask containing 25 grams (g.) (about 0.17 iodide at a concentration of 10 mg/ml. on the surface of mole) of N,N-dimethyl-p-nitrosoaniline in 200 milliliters 75 each leaf disc. A second instar armyworm larve is engaged 3,574,851 5 6 with each leaf disc by using a 78 inch plastic cap (the leaf alkylbenzene sulfonate emulsifier may be used to prepare disc is small enough to permit complete consumption by Such dispersions or emulsions. The products may also be the larva). The plastic caps containing the leaf discs and applied as oil-in-water emulsion sprays. The present prod larvae are each individually put into clear plastic contain lucts may also be dissolved or dispersed in liquified gases ers and held for 48 hours at ambient temperature. At the Such as fluorochloroethanes or methyl chloride and ap end of this period a 30% kill is produced by the ammonium plied to plants or other pest organism hosts from aerosol compound, when tested in the above manner. bombs. Instead of employing liquids as carriers, and diluents, herbicidal dusts which contain the present novel EXAMPLE 6 compounds as active ingredients may be prepared, for This example illustrates the use of a compound of this O example, by incorporating the new products of this inven invention as a fungicide. tion with a solid carrier such as talc, bentonite, fuller's To screen for fungicidal activity against Rhizoctonia earth, and so forth. solani, a soil fungus causative of seedling blight, corn The amount of the active toxicant compound in the meal sand cultures of this organism are blended into composition as applied will vary with the active ingredi autoclave-sterilized soil to achieve essentially a mono 5 ents, the manner of application, the species to be de organism soil-type. Paper cups containing 30 g. samples stroyed and the resistance of the plants to be sprayed, of the mono-organism soil-type are each individually for example, and formulation and ratio of applications are drenched with 4 ml. of a liquid containing 231 parts per suitably adjusted in accordance with these factors. million (p.p.m.) of trimethyl (p-nitrosophenyl)ammonium It is apparent that this invention may be extended to iodide, the product as provided in Example 1. The final 20 areas beyond those specifically described and that many concentration based on soil weight is 30 p.p.m. The paper widely differing embodiments can be made without de cups containing the drenched soil samples together with parting from the spirit and scope thereof as defined herein. paper cups containing undrenched soil samples are placed Therefore, it is not intended to be limited except as in into an incubation chamber at 90%-100% relative hu dicated by the appended claims. midity for 48 hours. At the end of this time the cups are 25 What is claimed is: removed from the incubation chamber and the samples 1. A method for controlling the growth of Soil fungi observed for fungus growth. comprising applying to the soil a fungicidal amount of a Substantially complete suppression of fungus growth compound of the formula and reproduction is observed for the samples treated with the product of Example 1. 30 R e EXAMPLE 7 R-N-R, Xe RNO This example illustrates the use of a compound of the present invention as a mammalian toxicant. wherein R represents bivalent aromatic hydrocarbon radi The ammonium compound provided as described in cals of from 6 to 12 carbon atoms, each of R2, R3 and R4 Example 1 is placed in solution by dissolving 100 milli 35 represents alkyl radicals of from 1 to 6 carbon atoms and grams (mg.) of the compound in 10 ml. of an aqueous X represents a halogen element of atomic weight below solution containing 10% of a polyethylene glycol having 130. a molecular weight of 300. This solution is diluted with 2. A method of claim 1 wherein R2, R3 and R4 are each water to provide solutions of varying concentrations which methyl, RNO is p-nitrosophenyl and X is iodine. are injected into mice intravenously. At 100 milligrams/ 40 kilogram (mg/kg.) (10 ml./kg.), the animals are killed, References Cited while at the lower rate of 32 mg./kg. (3.2 ml/kg.) the UNITED STATES PATENTS animals exhibit decreased locomotor activity. The ratio 2,954,314 9/1960 Metzger et al. ------424-329 of median lethal dose to median effective dose (LD50/ 45 MEDs) is determined to be 3.2. 3,028,301 4/1962 Winicon ------424-329 The presently new compounds of this invention are gen 3,390,178 6/1968 Hyatt ------260-567.6M erally applied for herbicidal and toxicant use in the form of sprays or aerosols. Useful sprays may be prepared by ALBERTT. MEYERS, Primary Examiner dispersing the present products in Water with the aid of a V. D. TURNER, Assistant Examiner wetting agent, to prepare aqueous dispersions which may 50 be employed as sprays. For example, a Solution containing U.S. C.X.R. cyclohexanone and a polyalkylene glycol ether long chain 71-70, 121