3,390,178 United States Patent Office Patented June 25, 1968 2 dimethylhexyl (4-nitrosoxylyl)ammonium fluoride, di 3390,178 hexylmethyl(4-nitrosoxylyl)ammonium chloride, TRIALKYL NITRosóstifSTITUTED AROMATIC diethylpentyl (4-nitrosoxylyl)ammonium bromide, QUATERNARY AMMONIUM HALIDES butyldipropyl (4-nitrosoxylyl)ammonium iodide, Asher A. Hyatt, Lexington, Mass., assignor to Monsanto butylhexylmethyl (4-nitrosoxylyl)ammonium fluoride, tri Research Corporation, St. Louis, Mo., a corporation of methyl(4-nitrosonaphthyl)ammonium iodide, Delaware triethyl (5-nitrosonaphthyl)ammonium fluoride, No Drawing. Filed Dec. 3, 1965, Ser. No. 531,320 tripropyl (6-nitroSonaphthyl)ammonium chloride, 2 Claims. (C. 260-567.6) tributyl (4-nitrosonaphthyl)ammonium bromide, This invention relates to the reaction of nitroso sub 10 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, di It is an object of this invention to provide new nitroso hexylmethyl (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 15 butyldipropyl (4-nitrosonaphthyl)ammonium fluoride, pounds useful as biological toxicants such as fungicides, butylhexylmethyl (5-nitrosonaphthyl)ammonium bromide, plant growth regulators, defoliants, insecticides and trimethyl(3'-nitrosobiphenylyl)ammonium chloride, bactericides. triethyl (2'-nitrosobiphenylyl)ammonium fuoride, According to the invention, there are prepared new tripropyl(3'-nitrosobiphenylyl)ammonium bromide, and useful compounds having the formula: 20 tributyl (4'-nitrosobiphenylyl)ammonium iodide, tripentyl (4'-nitrosobiphenylyl)ammonium chloride, R. 6B) trihexyl (3'-nitrosobiphenylyl)ammonium fluoride, dimethylhexyl (2'-nitrosobiphenylyl)ammonium bromide, RNoxe dihexylmethyl (4 - nitrosobiphenylyl)ammonium iodide, wherein R represents bivalent aromatic hydrocarbon 25 and so forth. radicals of from 6 to 12 carbon atoms, each of R2, R3, Useful nitroso-substituted aromatic hydrocarbon deriv and R4 represents alkyl radicals free of aliphatic un atives of dialkylamines are, for example: saturation of from 1 to 6 carbon atoms and X represents N,N-dimethyl-p-nitrosoaniline, a halogen element of atomic weight below 130. 30 N,N-dihexyl-p-nitrosoaniline, Preparation of the presently provided novel compounds N-hexyl-N-methyl-p-nitroSoaniline, is effected by contacting the alkyl halide with the nitroso N,N-diethyl-m-nitrosoaniline, substituted aromatic hydrocarbon derivative, according to N,N-dipropyl-o-nitroSoaniline, the following equation: N,N-dibutyl-m-nitroSoaniline, R3 35 N,N-dipentyl-m-nitrosoaniline, N-ethyl-N-pentyl-p-nitrosoaniline, R-N-R3 - RX - N-butyl-N-propyl-p-nitrosoaniline, NO kN O N-methyl-N-propyl-o-nitroSoaniline, wherein R1, R2, R3, R4 and X are as defined above. N,N-dimethyl-p-nitrosotoluidine, There are shown below a number of the specific new 40 N,N-dihexyl-m-nitrosotoluidine, compounds of the invention. It is not intended that this N-hexyl-N-methyl-o-nitrosotoluidine, be a complete listing of all the compounds of the inven N,N-diethyl-m-nitrosotoluidine, tion, but that it merely be illustrative thereof: N,N-dipropyl-p-nitrosotoluidine, trimethyl (p-nitrosophenyl)ammonium iodide, N,N-dibutyl-o-nitrosotoluidine, triethyl (o-nitrosophenyl)ammonium bromide, N,N-dipentyl-m-nitrosotoluidine, tripropyl (m-nitrosophenyl)ammonium chloride, N-ethyl-N-pentyl-p-nitrosotoluidine, tributyl (p-nitrosophenyl)ammonium fluoride, N-butyl-N-propyl-o-nitrosotoluidine, tripentyl (o-nitrosophenyl)ammonium iodide, N-methyl-N-propyl-m-nitrosotoluidine, trihexyl (m-nitrosophenyl)ammonium bromide, N,N-dimethyl-p-nitrosoxylidine, dimethylhexyl (p-nitrosophenyl)ammonium chloride, 50 N,N-dihexyl-p-nitrosoxylidine, dihexylmethyl(o-nitrosophenyl)ammonium fluoride, N-hexyl-N-methyl-p-nitrosoxylidine, diethylpentyl(m-nitrosophenyl)ammonium iodide, N,N-diethyl-m-nitrosoxylidine, butyldipropyl (p-nitrosophenyl)ammonium bromide, N,N-dipropyl-o-nitrosoxylidine, butylhexylmethyl (o-nitrosophenyl)ammonium chloride, N,N-dibutyl-p-nitrosoxylidine, trimethyl (4-nitrosotolyl)ammonium fluoride, N,N-dipenty-m-nitrosoxylidine, triethyl(4-nitrosotolyl)ammonium iodide, N-ethyl-N-pentyl-p-nitrosoxylidine, tripropyl (4-nitrosotolyl)ammonium bromide, N-butyl-N-propyl-p-nitrosoxylidine, tributyl (4-nitrosotolyl)ammonium chloride, N-methyl-N-propyl-m-nitrosoxylidine, tripenty (4-nitrosotolyl)ammonium fluoride, 4-nitroso-N,N-dimethylnaphthylamine, trihexyl (4-nitrosotolyl)ammonium bromide, 60 4-nitroso-N,N-dihexylnaphthylamine, dimethylhexyl (4-nitrosotolyl)ammonium chloride, 4-nitroso-N,N-diethylnaphthylamine, dihexylmethyl (4-nitrosotolyl)ammonium iodide, di 4-nitroso-N,N-dipropylnaphthylamine, ethylpentyl (4-nitrosotolyl)ammonium fluoride, 4-nitroso-N,N-dibutylnaphthylamine, butyldipropyl (4-nitrosotolyl)ammonium bromide, 4-nitroso-N,N-dipentylnaphthylamine, butylhexylmethyl (4-nitrosotolyl)-ammonium choride, 65 4-nitroso-N-ethyl-N-pentylnaphthylamine, trimethyl (4-nitrosoxylyl)ammonium fluoride, triethyl (4- 4-nitroso-N-butyl-N-propylnaphthylamine, nitrosoxylyl)ammonium chloride, 4-nitroso-N-methyl-N-propylnaphthylamine, tripropyl (4-nitrosoxylyl)ammonium bromide, 4'-nitroso-N,N-dimethylbiphenylylamine, tributyl (4-nitrosoxylyl)ammonium iodide, tripenty (4- 4'-nitroso-N,N-dihexylbiphenylylamine, nitrosoxylyl)ammonium fluoride, 70 4'-nitroso-N-hexyl-N-methylbiphenylylamine, trihexyl (4-nitrosoxylyl)ammonium chloride, 4'-nitroso-N,N-diethylbiphenylylamine, 3,390,178 3. 4. 4'-nitroso-N,N-dipropylbiphenylylamine, 4'-nitroso-N,N-dibutylbiphenylylamine, EXAMPLE 2 4'-nitroso-N,N-dipentylbiphenylylamine, This example describes the utilization of a compound 4'-nitroso-N,N-dipentylbiphenylylamine, of this invention as a bactericide. 4'-nitroso-N-ethyl-N-pentylbiphenylylamine, To test bactericidal activity, inoculations of S. aureus, 4'-nitroso-N-ethyl-N-propylbiphenylylamine, 5 S. typhosa, and A. niger, are made on agar substrates sup 4'-nitroso-N-methyl-N-propylbiphenylylamine, and so porting the growth of these microorganisms, to which has forth. been added varying amounts of trimethyl (p-nitrosophen yl)ammonium iodide. The inoculated plates are main Useful alkyl halides are, for example: iodomethane, tained under conditions supporting growth of these mi fluoroethane, 1-chloropropane, 1-bromobutane, 1-iodo 0 croorganisms. At concentrations of 1 part per 1,000 and 1 pentane, 1-fluorohexane, 2-chloropropane, 1-bromoiso part per 10,000 in the agar, the ammonium compound butane, 2-iodo-2-methylpropane, 2.2 - dimethyl-1-fluoro causes Substantially complete suppression of growth and propane, 1-bromoisopentane, and so forth. reproduction of each of the microorganism species. In carrying out the process of this invention, the nitroso compound is simply contacted with the alkyl halide until EXAMPLE 3 reaction is complete. It is an advantage in moderating the To test defoliant activity, Blank Valentine bean plants, reaction to add one of the reactants slowly and gradually 4 to a pot, are grown to the stage of having 1 mature to the other, though the reactants may optionally be added trifolate and 1 partially opened trifoliate, and then all at once, preferably together with a solvent or diluent. sprayed with trimethyl (p-nitrosophenyl)ammonium io Solvents or diluents which may be used to moderate the 20 dide as an aqueous emulsion, at rates of 0.1 and 1.0 pound reaction and to facilitate stirring, and so forth, are alco per acre (lbs./a.), using a dilution of 30 gallons per acre, hols, such as methanol, ethanol and propanoi, for ex after which the plants are maintained in a greenhouse ample. within temperature limits of 70°-90° F. The plants are The ratio of reactants may vary, molar ratios of the defoliated in the 50% range at both rates. Defoliation in nitroso compound to the alkyl halide compound of at 25 the 51-75% range is observed when the same compound least 1:10 to about 10:1 may be used, but since the reac is applied to soybean plants at the rate of 10 lbs./a. tion is equimolar, advantageously a 1:1 ratio of reactants is employed. Excess reactant may be removed at the end EXAMPLE 4. of the reaction by, for example, extraction or distillation. This example illustrates the use of a compound of this Useful temperatures for conducting the preparation are, 30 invention for the control of plant species. for example, the Teflux temperature of the reaction mix Aluminum pan flats are filled with mixtures of two ture where solvents are used or any desired temperature thirds one-quarter mesh sieved soil, and one-third sand. from below 0° C. up to below the decomposition point of Over one-third of the soil surface of each pan are scat the ingredients of the reaction mixture. Atmospheric pres tered 20 Seeds each of different kinds of grasses; seeds of sure is satisfactory for conducting the reaction, though 35 broadleaf plants are randomly scattered over the remain Sub- or super-atmospheric pressures may be used if de ing Surface. The seeds are then covered with soil to the sired, ranging from 0.05 millimeter of mercury to about pan top and the pan is sprayed with an aqueous solution 5,000 pounds per square inch. of fertilizer and insecticide. 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 40 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 lowed to absorb moisture until the soil surface is com several 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 agricul The ammonium compound produced substantially tural and industrial uses; for example, trimethyl (p-nitro complete Suppression of plant germination and growth sophenyl)ammonium iodide may be used as mammalian on pigweed while it produced no effect on sugar beets and toxicant and herbicide and is particularly effective as a radishes. bactericide. EXAMPLE 5 The invention will be further described with reference to the following specific examples. These examples are This example illustrated the use of a compound of this given for purposes of illustration ony and are not to be invention as a pesticide for the destruction of lower ani 5 5 mal life forms. taken as in any way restricting the invention. In insecticidal screening, activity for control of south EXAMPLE 1. ern armyworms (Prodenia eridania) is demonstrated as This example illustrates the preparation of a compound follows. Lima bean leaf discs (7 mm. in diameter) are in accordance with this invention. prepared by evaporating one microliter of an acetone so To a reaction flask containing 25 grams (g) (about (30 lution containing trimethyl (p-nitrosophenyl)ammonium 0.17 mole) of N,N-dimethyl-p-nitrosoaniline in 200 milli iodide at a concentration of 10 mg./ml. on the surface of liters (ml.) of 2-propanol is gradually added 23.7 g. each leaf disc. A second instar armyworm larva is en (about 0.17 mole) of iodomethane. The mixture is re gaged with each leaf disc by using a 78 inch plastic cap fluxed for two and one-half hours to insure complete re (the leaf disc is small enough to permit complete con action and then filtered. The crude residue is washed sev Sumption by the larva). The plastic caps containing the eral times with each of 2-propanol, acetone, and ether, leaf discs and larvae are each individually put into clear then dried. plastic containers and held for 48 hours at ambient tem The resulting product is trimethyl (p-nitrosophenyl)- perature. At the end of this period a 30% kill is pro ammonium iodide, a uniformly green crystalline solid duced by the ammonium compound, when tested in the Weighing 27 g. (about 55% theoretical yield), soluble 70 above manner. in dimethylsulfoxide and melting at 1549. 155° C. EXAMPLE 6 Elemental analysis of this product confirms the assigned This example illustrates the use of a compound of this empirical formula C19H11NO: invention as a fungicide. Calculated: C, 37.0%; H, 4.5%; I, 43.5%. Found: To Screen for fungicidal activity against Rhizoctonia C, 36.8%; H, 4.0%; I, 43.5%. 75 Solani, a soil fungus causative of Seedling blight, corn 3,390,178 5. 6 meal sand cultures of this organism are blended into auto may be used to prepare such dispersion or emulsions. The clave-sterilized soil to achieve essentially a mono-orga products may also be applied as oil-inwater emulsion nism soil-type. Paper cups containing 30 g. samples of the sprays. The present products may also be dissolved or mono-organism soil-type are each individually drenched dispersed in liquified gasses such as fluorochloroethanes with 4 ml. of a liquid containing 231 parts per million or methyl chloride and applied to plants or other pest (p.p.m.) of trimethyl (p-nitrosophenyl)ammonium iodide, organism hosts from aerosol bombs. Instead of employ the product as provided in Example 1. The final concen ing liquids as carriers and-diluents, herbicidal dusts tration based on soil weight is 30 p.p.m. The paper cups which contain the present novel compounds as active containing the drenched soil samples together with paper ingredients may be prepared, for example, by incorporat cups containing undrenched soil samples are placed into O ing the new products of this invention with a solid carrier an incubation chamber at 90%-100% relative humidity such as talc, bentonite, fuller's earth, and so forth. for 48 hours. At the end of this time the cups are removed The amount of the active toxicant compound in the from the incubation chamber and the samples observed composition as applied will vary with the active ingre for fungus growth. - - dients, the manner of application, the species to be de Substantially complete suppression of fungus growth 5 stroyed and the resistance of the plants to be sprayed, and reproduction is observed for the samples treated with for example, and formulation and ratio of applications the product of Example i. are suitably adjusted in accordance with these factors. It is apparent that this invention may be extended to EXAMPLE 7 areas beyond those specifically described and that many This example illustrates the use of a compound of the 20 widely differing embodiments can be made without de present invention as a mammalian toxicant. parting from the spirit and scope thereof as defined here The anmonium compound provided as described in in. Therefore, it is not intended to be limited except as Example 1 is placed in solution by dissolving 100 milli indicated by the appended claims. grams (mg.) of the compound in 10 ml. of an aqueous What is claimed is: solution containing 10% of a polyethylene glycol having 25 1. Compounds of the formula: a molecular weight of 300. This solution is diluted with water to provide solutions of varying concentrations R 69 which are injected into mice intravenously. At 100 milli grams/kilogram (mg./kg.) (10 ml./kg.), the animals are t R.Noxe killed, while at the lower rate of 32 mg/kg. (3.2 ml./ 30 kg.) the animals exhibit decreased locomotor activity. wherein R represents bivalent aromatic hydrocarbon The ratio of median lethal dose to median effective dose radicals of from 6 to 12 carbon atoms, each of R2, R3, (LD50/MED50) is determined to be 3.2. and R4 represents alkyl radicals of from 1 to 6 carbon The presently new compounds of this invention are atoms and X represents a halogen element of atomic generally applied for herbicidal and toxicant use in the 35 weight below 130. form of sprays or aerosols. Useful sprays may be pre 2. Trimethyl (p-nitrosophenyl)ammonium iodide. pared by dispersing the present products in water with the aid of a weetting agent, to prepare aqueous disper No references cited. sions which may be employed as sprays. For example, a solution containing cyclohexanone and a polyalkylene 40 CHARLES B. PARKER, Primary Examiner. glycol ether long chain alkyl benzene sulfonate emulsifier S. T. LAWRENCE III, Assistant Examiner.