United States Patent (19) 11 Patent Number: 4,670,596 Dreikorn Et Al
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United States Patent (19) 11 Patent Number: 4,670,596 Dreikorn et al. 45) Date of Patent: Jun. 2, 1987 54) DIPHENYLAMINE COMPOUNDS (56) References Cited (75) Inventors: Barry A. Dreikorn, Lawrence; U.S. PATENT DOCUMENTS Kenneth E. Kramer, Indianapolis, 4,304,791 12/1981 Clinton ................................ 424/330 both of indi. 4,407,820. 10/1983 Dreikorn et al. ................... 564/433 (73) Assignee: Eli Lilly and Company, Indianapolis, FOREIGN PATENT DOCUMENTS Ind. 868165 5/1961 United Kingdom ................ 424/304 Appl. No.: 765,423 Primary Examiner-Charles F. Warren 21) Assistant Examiner-John A. Sopp 22) Fied: Aug. 14, 1985 Attorney, Agent, or Firm-Kathleen R. S. Page; Leroy Whitaker Related U.S. Application Data (57) ABSTRACT 62) Division of Ser. No. 519,359, Aug. 1, 1983, abandoned. Novel alkyl-dinitrodiphenylamine compounds are use ful in controlling insects and arachnids. These com 51) Int. Cl.' ....................... CO7C 87/50; C07C 87/54 pounds are useful especially in the control of citrus rust (52) U.S. C. ..................................... 564/433; 558/418 mite. 58) Field of Search ........................ 514/658; 564/433; 260/465 E; 558/418 20 Claims, No Drawings 4,670,596 1. 2 DPHENYLAMINE COMPOUNDS R4 (II) This application is a division of application Ser. No. Xin 519,359, filed Aug. 1, 1983 abandoned. 5 BACKGROUND OF THE INVENTION R R2 This invention relates to certain substituted diphenyl NO amines, their use in controlling insects and arachnids (mites), and to compositions containing said diphenyl O wherein amines. In particular, this invention relates to certin R, R2, X, m, and n are defined as above and alkyl-dinitrodiphenylamines, which are active against R is C2-C6 alkyl or C3-C6 cycloalkyl. insects and mites. The 4,6-dinitro compounds of the formula (II) are preferred over compounds of the formula (III), which SUMMARY OF THE INVENTION 15 are 2,6-dinitrodiphenylamines: The present invention is directed to alkyl-dinitrodi phenylamines of the formula (I): (III) R (I) 20 Xn R ()--)-rk 25 NO2 wherein R, R2, X, m, n, and R“are defined above. (The 2,6-dinitrodiphenylamines are also compounds of the wherein: formula (I) when the R group in the para position is R1 is nitro, cyano, or trifluoromethyl; C2-C6 alkyl or C3-C6 cycloalkyl and the R3 in the ortho R2 is hydrogen or methyl; 30 position is nitro.) one R3 is nitro and the other R3 is C2-C6 alkyl or Preferred compounds of the formula (II) include: C3-C6 cycloalkyl; 2,4-dinitro-2'-t-butyl-4,6'-dinitrodiphenylamine; X is halo; 2,4,6-trichloro-2'-t-butyl-4,6'-dinitrodiphenylamine; m is an integer of from 0 to 5; and 2,4,6-tribromo-2'-t-butyl-4,6'-dinitrodiphenylamine; n is an integer of from 0 to 2; 35 and provided that: 4-trifluoromethyl-2'-t-butyl-4,6'-dinitrodiphenyla (a) not more than one of R is cyano; ne. (b) when R is trifluoromethyl, R cannot also be A preferred compound of the formula (III) is: 2,4,6- nitro; trichloro-4'-t-butyl-2',6'-dinitrodiphenylamine. (c) when Xisiodo, m cannot be greater than 3 and the This invention also includes a method of inhibiting a iodos cannot be on adjacent carbons; citrus rust mite which comprises applying to a locus of (d) at least one of m and n must be greater than 0, but the mite an effective mite-inactivating amount of a con the sum of m and n cannot be greater than 5; and pound of the formula (I). (e) R2 cannot be methyl when the 2 and 6 positions of In addition, a method of inhibiting an insect or arach 45 nid which comprises applying to a locus of the insector ring A are both substituted by groups other than arachnid an effective insect- or arachnid-inactivating fluorine or hydrogen. amount of a compound of the formula (II) is also a part This invention also provides a method of inhibiting of this invention. The compounds of formula (II) are the citrus rust mite which comprises applying to a locus particularly useful against mites, so this invention in of the mite an effective mite-inactivating amount of a 50 cludes a method of inhibiting a mite which comprises compound of the formula (I). Additionally, some of the applying to a locus of the mite an effective mite-inac compounds also inhibit insect or arachnid populations. tivating amount of a compound of the formula (II). Another aspect of this invention includes a formula The terms used throughout this application are de tion which comprises a compound of the formula (I) fined as follows. and an agriculturally-acceptable carrier therefor. 55 "C2-C6 alkyl" refers to straight and branched ali DETAILED DESCRIPTION OF THE phatic radicals of two to six carbon atoms, such as ethyl, INVENTION propyl, isopropyl, butyl, tertiary-butyl (t-butyl or 1,1- dimethylethyl), pentyl, hexyl, and the like. Preferred compounds of this invention include those "C3-C6 cycloalkyl” refers to saturated aliphatic rings wherein R2 is hydrogen and R3 is tertiary butyl (t- 60 of three to six carbon atoms, such as cyclopropyl, cy butyl). Even more preferred are compounds wherein X clobutyl, cyclopentyl, and cyclohexyl. is chloro, fluoro, or bromo and m is 3, while n is 0; or "Halo' includes bromide, chloride, fluoride, and io wherein R is nitro and n is 2, while m is 0. dide. When the R group in the para position is nitro and the R3 in the ortho position is C2-C6 alkyl or C3-C6 65 Preparation of Compounds of Formula (I) cycloalkyl, then the compounds of formula (I) are 4,6- The compounds of this invention can be prepared by dinitrodiphenylamines, which also can be written as known methods. One preferred method is to react a compounds of the formula (II): substituted aniline derivative of the formula: 4,670,596 4. component, such as, for example, 2-t-butyl-4,6-dinitro chlorobenzene, can be readily prepared from commer cially available 2-t-butyl phenol by nitration and chlori nation under appropriate reaction conditions. This typi cally is done stepwise first reacting 2-t-butyl phenol with nitric acid in a suitable reaction medium, such as where X, Rl, m, and n are as defined above with a 1,2-dichloroethylene. The resulting 2-t-butyl-4,6-dini substituted dinitrochlorobenzene of the formula: trophenol is then reacted with a halogenating agent, 10 such as phosphorus oxychloride or thionyl chloride. R The reaction preferably takes place in a suitable solvent, such as 1,2-dichloroethylene, or dimethylformamide CL (DMF). The following examples illustrate the invention, but 15 are not to be construed as limitations on it. All of the NO temperatures are in degrees Celsius. where R is defined above. The process is carried out by 2-(t-Butyl)-4,6-dinitrochlorobenzene reacting the aniline derivative with a base, such as so A solution of 1050 grams (g) of 2-t-butyl phenol dis dium hydride, sodium amide, potassium amide, and the 20 like, in an appropriate solvent, such as dimethylforman solved in 7 liters (1) of ethylene dichloride was cooled ide, dimethylsulfoxide, sulfolone, acetonitrile, or tetra to about -5 by placing the reaction vessel in a dry-ice hydrofuran. When sodium hydride is used as the base, /acetone bath. Nitric acid, in the amount of 1760 g, was as is preferred, the temperature is preferably maintained slowly added over a 1-hour time period to maintain the at about 0° to about -20° C. The resulting aniline salt 25 temperature between about -5° and about 0'. The then is reacted with the substituted dinitrochloroben reaction vessel was removed from the cooling bath and zene, which first is dissolved in an appropriate organic the reaction mixture was allowed to warm to room solvent, such as dimethylformamide. The addition of temperature and then stirred for about 16 hours. Then the dinitrochlorobenzene is conducted from about 0” to the reaction mixture was poured into about 12 l of about -20° C. After the addition, the temperature is 30 allowed to reach room temperature. Typically the com stirred ice-water. About one-half of the mixture was pounds of this invention are solids at room temperature removed and extracted with about 4 l of ether, and the and precipitate from the reaction mixture when water ether layer was recovered. This was repeated with the or ice water is added to the solution and the solution is remaining half of the reaction mixture and the ether acidified. The solid precipitate can be readily recovered 35 layers were combined. The ether solution was extracted by conventional techniques such as filtration and fur with water and then removed by evaporation under a ther purified, if desired, by washing and recrystalliza vacuum, resulting in an oil residue. Ethanol was added, tion procedures, and, where necessary, by column chro causing the product to precipitate. The solid precipitate matography. was recovered and the yield was 958g of the product: V Another general method of preparing the diphenyl 40 2-t-butyl-4,6-dinitrophenol. amines of this invention comprises dissolving the appro priate substituted aniline derivative, a substituted dini This product was dissolved in 3 l of ethylene dichlo trochlorobenzene, and an acid scavenger in a solvent, ride and then 1840 g of phosphorus oxychloride was such as ethanol, and refluxing the reaction mixture for a slowly added over a period of about 45 minutes. The period of time sufficient to complete the reaction. Ex 45 temperature of the reaction mixture was maintained cess of the aniline derivative can function as the acid below about 50” by means of a water bath.