Sulfenamides, such as 1,1,1-trichloro-N-[2-chloro-5-(trifluoromethyl)phenyl]-N-[2,4-dinitro-6-(t rifluoromethyl)phenyl]methanesulfenamide, useful for control of mites, plant diseases and insect eggs.

BACKGROUND OF THE INVENTION 
This invention relates to miticidal, fungicidal and ovicidal sulfenamides. 
British Pat. No. 1,455,207 discloses pesticidal diphenylamine derivatives 
of the formulas: 
##STR1## 
where X and R represent various substituents definitions. 
Belgian Pat. No. 846,205 discloses compounds with utility as rodenticides 
of the formula 
##STR2## 
where R, R.sub.1, R.sub.2 and R.sub.3 represent various defined 
substituents. 
Belgian Pat. No. 846,419 discloses compounds with utility as delayed-action 
rodenticides. 
##STR3## 
where R, R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 represent various 
defined substituents. 
SUMMARY OF THE INVENTION 
This invention relates to novel sulfenamides of formula (I) to methods for 
preparing them, and to compositions and methods for using them to control 
mites, fungus disease of plants and insect eggs. 
##STR4## 
wherein R.sub.1, R.sub.3 and R.sub.4 independently are H, F, Cl, Br, 
NO.sub.2, CF.sub.3, OCF.sub.3 or OCF.sub.2 CF.sub.2 H; 
R.sub.2 is H, F, Cl, Br, NO.sub.2 or CF.sub.3 ; 
R.sub.5 is H or F; 
Z is CCl.sub.3, CCl.sub.2 F, CCl.sub.2 CCl.sub.2 H or CCl.sub.2 CFCl.sub.2 
; 
provided that when R.sub.1 is NO.sub.2 or CF.sub.3, then R.sub.3 must be H 
or F; 
provided that no more than two of the substituents 
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are simultaneously Cl, Br, NO.sub.2, 
CF.sub.3, OCF.sub.3 or OCF.sub.2 CF.sub.2 H and when two NO.sub.2 groups 
are present, they are not ortho to each other. 
PREFERRED COMPOUNDS 
Preferred independently are the following groups of compounds of Formula 
(I) for reasons of lower cost, lower phytotoxicity, lower mammalian 
toxicity and/or greater miticidal or fungicidal activity. 
Z is CCl.sub.3 ; or 
R.sub.1 is F, Cl, Br, CF.sub.3, OCF.sub.3 or OCF.sub.2 CF.sub.2 H; or 
R.sub.2 is H, F, Cl or Br; or 
R.sub.3 =H, F, Cl or Br; or 
R.sub.4 is F, Cl, Br, CF.sub.3, OCF.sub.3 or OCF.sub.2 CF.sub.2 H. 
More preferred for the preceding reasons are compounds of Formula (I) where 
Z is CCl.sub.3 ; 
R.sub.1 and R.sub.4 independently are Cl, CF.sub.3, OCF.sub.3 or OCF.sub.2 
CF.sub.2 H; and 
R.sub.2, R.sub.3 and R.sub.5 are H. 
Specifically preferred for excellent activity, lower phytotoxicity and/or 
highly favored cost are: 
1,1,1-trichloro-N-[2-chloro-5-(trifluoromethyl)-phenyl]-N-[2,4-dinitro-6-(t 
rifluoromethyl)phenyl]-methanesulfenamide 
1,1,1-trichloro-N-[2-chloro-5-(trifluoromethoxy)-phenyl]-N-[2,4-dinitro-6-( 
trifluoromethyl)phenyl]-methanesulfenamide, mixture with the 
5-chloro-2-(trifluoromethoxy)phenyl isomer 
SYNTHESIS 
The compounds of the invention can be prepared by reacting compounds of 
Formula (II) with sulfenyl chlorides, ClSZ, in the presence of an acid 
acceptor in an inert solvent as outlined in the following scheme: 
##STR5## 
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are as previously 
defined. Organic bases such as trimethylamine, triethylamine, or pyridine 
or inorganic bases such as sodium or potassium hydroxide, sodium or 
potassium carbonate, or sodium hydride may be used as the acid acceptor. 
Any inert solvent such as toluene, dioxane, tetrahydrofuran, ethyl ether, 
methylene chloride, etc. may be employed. The reaction is substantially 
complete at ambient temperature and pressure. Elevated temperature may be 
used if necessary to shorten reaction time. 
The diphenylamines of Formula (II) can be obtained using the procedures 
described in British Pat. No. 1,455,207.

The following examples further illustrate the preparation of the compounds 
of this invention. All parts and percentages are by weight, and all 
temperatures are in degrees centigrade unless otherwise specified. 
EXAMPLE 1 
Preparation of 
1,1,1-trichloro-N-[2-chloro-5-(trifluoromethyl)phenyl]-N-[2,4-dinitro-6-(t 
rifluoromethyl)phenyl]-methanesulfenamide 
Sodium hydride (0.6 g, 57% mineral oil), washed free of mineral oil with 
hexane under a nitrogen atmosphere, is slurried in 25 ml of anhydrous 
tetrahydrofuran and cooled to 0.degree.. A solution of 
2-chloro-N-[2,4-dinitro-6-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-ben 
zenamine (4.3 g, 0.010 mole) in 25 ml of anhydrous tetrahydrofuran is then 
added dropwise with stirring at 0.degree.. When the addition is complete, 
the solution is allowed to warm to ambient temperature and stirred for one 
hour. Perchloromethyl mercaptan (1.9 g, 0.010 mole) is then added and 
stirring is continued for two hours. The reaction mixture is then poured 
into water, extracted with methylene chloride, dried over anhydrous 
magnesium sulfate and stripped under vacuum to afford an orange resin. 
Chromatography on silica gel utilizing 1-chlorobutane/hexane (1:1 by vol) 
as the eluent affords 3.5 g of 
1,1,1-trichloro-N-[2-chloro-5-(trifluoromethyl)phenyl]-N-[2,4-dinitro-6-(t 
rifluoromethyl)phenyl]methanesulfenamide as a yellow oil which crystallizes 
on standing, m.p. 134.degree.-137.degree.. 
Calculated for C.sub.15 H.sub.5 N.sub.3 O.sub.4 SF.sub.6 Cl.sub.4 : C, 
31.11; H, 0.87, N, 7.26. Found: C, 31.4; H, 0.94; N, 7.68. 
EXAMPLE 2 
Preparation of 
1,1,1-trichloro-N-[2-chloro-5-(trifluoromethoxy)phenyl]-N-[2,4-dinitro-6-( 
trifluoromethyl)phenyl]methanesulfenamide and 
1,1,1-trichloro-N-[5-chloro-2-(trifluoromethoxy)phenyl]-N-[2,4-dinitro-6-( 
trifluoromethyl)phenyl]methanesulfenamide as an approximately 50:50 mixture 
a. 
2-chloro-N-[2,4-dinitro-6-(trifluoromethyl)phenyl]-5-(trifluoromethoxy)ben 
zenamine and 
5-chloro-N-[2,4-dinitro-6-(trifluoromethyl)phenyl]-2-(trifluoromethoxy)ben 
zenamine as an approximately 50:50 mixture 
To a stirred solution of 2.12 g (0.01 mole) of 
2-chloro-5-(trifluoromethoxy)benzenamine and 
5-chloro-2-(trifluoromethoxy)benzenamine [obtained as an approximately 
50:50 mixture utilizing the procedure described in Chem Abstr. 51, 15517 
(1957)] in 15 ml of dimethylformamide is added 1.29 g (0.02 mole) of 85% 
KOH powder. After 15 minutes, this mixture (purple solution plus KOH) is 
added to a stirred, cooled (ice bath) solution of 2.71 g (0.01 mole) of 
2-chloro-3,5-dinitrobenzotrifluoride in 15 ml of dimethylformamide. The 
mixture is allowed to stir overnight at ambient temperature. 
The red mixture is poured into ice water, acidified with conc. hydrochloric 
acid, and extracted with 1-chlorobutane. The 1-chlorobutane extract is 
washed with water, twice with 6% potassium carbonate solution (a little 
solid is filtered off), dried and treated with activated carbon. The 
filtered solution is evaporated to afford 4.26 g (96%) of 
2-chloro-N-[2,4-dinitro-6-(trifluoromethyl)phenyl]-5-(trifluoromethoxy)ben 
zenamine and 
5-chloro-N-[2,4-dinitro-6-(trifluoromethyl)phenyl]-2-(trifluoromethoxy)ben 
zenamine (approximately equal amounts) as an orangish-red oil. 
b. 
1,1,1-trichloro-N-[2-chloro-5-(trifluoromethoxy)phenyl]-N-[2,4-dinitro-6-( 
trifluoromethyl)phenyl]-methanesulfenamide and 
1,1,1-trichloro-N-[5-chloro-2-(trifluoromethoxy)phenyl]-N-[2,4-dinitro-6-( 
trifluoromethyl)phenyl]methanesulfenamide as an approximately 50:50 mixture 
Sodium hydride (0.6 g, 57% in mineral oil), washed free of mineral oil with 
hexane under a nitrogen atmosphere, is slurried in 25 ml of anhydrous 
tetrahydrofuran and cooled to 0.degree.. A solution of the mixture 
obtained in part a. above (4.5 g, 0.01 mole) in 25 ml of anhydrous 
tetrahydrofuran is then added dropwise with stirring at 0.degree.. When 
the addition is complete, the reaction mixture is allowed to warm to 
ambient temperature and stirred for one hour. Perchloromethyl mercaptan 
(1.9 g, 0.01 mole) is then added and stirring is continued at ambient 
temperature for two hours. The reaction mixture is then poured into water, 
extracted with methylene chloride, dried over anhydrous magnesium sulfate 
and stripped to afford 5.5 g of a viscous orange resin. Chromatography on 
silica gel with 1-chlorobutane/hexane (1:1 by volume) as the eluent 
affords 4.2 g of 
1,1,1-trichloro-N-[2-chloro-5-(trifluoromethoxy)phenyl]-N-[2,4-dinitro-6-( 
trifluoromethyl)phenyl]methanesulfenamide and 
1,1,1-trichloro-N-[5-chloro-2-(trifluoromethoxy)phenyl]-N-[2,4 
-dinitro-6-(trifluoromethyl)phenyl]methanesulfenamide (in approximately 
equal amounts) as a glassy orange resin. 
EXAMPLE 3 
Preparation of a mixture of 
1,1,1-trichloro-N-[2-chloro-5-(1,1,2,2-tetrafluoroethoxy)phenyl]-N-[2,4-di 
nitro-6-(trifluoromethyl)phenyl]methanesulfenamide and 
1,1,1-trichloro-N-[5-chloro-2-(1,1,2,2-tetrafluoroethoxy)phenyl]-N-[2,4-di 
nitro-6-(trifluoromethyl)phenyl]methanesulfenamide 
a. Preparation of 
N-[5-chloro-2-(1,1,2,2-tetrafluoromethoxy)phenyl]-2,4-dinitro-6-(trifluoro 
methyl)benzenamine as a mixture with 
N-[2-chloro-5-(1,1,2,2-tetrafluoroethoxy)phenyl]2,4-dinitro-6-(trifluorome 
thyl)benzenamine 
1. 4-Chlorophenol reacts under basic catalysis with tetrafluoroethylene to 
give 1-chloro-4-(1,1,2,2-tetrafluoroethoxy)benzene as a colorless oil of 
b.p. 68.degree. at 12 Torr. [For example, see J. Am Chem. Soc. 73, 5831 
(1951) and Chem. Abstr. 73, 36584q.] 
2. 1-Chloro-4-(1,1,2,2-tetrafluoroethoxy)benzene is nitrated during 1 hour 
at 22.degree.-25.degree. with mixed sulfuric/90% nitric acids to provide a 
mixture of the two mononitro compounds, 
1-chloro-2-nitro-4-(1,1,2,2-tetrafluoroethoxy)benzene and 
1-chloro-3-nitro-4-(1,1,2,2-tetrafluoroethoxy)-benzene as a yellow oil 
b.p. 130.degree. at 13 Torr. 
3. The mixture of moninitro compounds is reduced with iron in aqueous 
acetic acid to provide the two isomeric benzenamine derivatives, 
5-chloro-2-(1,1,2,2-tetrafluoroethoxy)benzenamine and 
2-chloro-5-(1,1,2,2-tetrafluoroethoxy)benzenamine, as an oil of b.p. 
115.degree.-117.degree. at 13 Torr. 
4. To a stirred, ice-cooled solution of 6.09 g (0.025 mole) of the above 
mixed benzenamines in 37 ml of dimethylformamide is added 3.30 g of 85% 
KOH powder. After 20 minutes in the cold, the mixture is treated with a 
solution of 6.76 g (0.025 mole) of 2-chloro-3,5-dinitrobenzotrifluoride in 
37 ml of dimethylformamide. After 20 minutes in the cold, the mixture is 
allowed to warm to ambient temperature and stirred for 18 hours. The 
mixture is poured into 300 ml of ice water, acidified with conc. 
hydrochloric acid, and extracted with 1-chlorobutane. The 1-chlorobutane 
extracts are washed with water, and 6% potassium carbonate solution (4 
times), then dried over anhydrous magnesium sulfate, treated with 
activated carbon and filtered. The filtrate is stripped under vacuum to 
afford a mixture of 
N-[5-chloro-2-(1,1,2,2-tetrafluoroethoxy)phenyl]-2,4-dinitro-6-(trifluorom 
ethyl)benzenamine and 
N-[2-chloro-5-(1,1,2,2-tetrafluoroethoxy)phenyl]-2,4-dinitro-6-(trifluorom 
ethyl)benzenamine as a red oil. 
b. Preparation of a mixture of 
1,1,1-trichloro-N-[2-chloro-5-(1,1,2,2-tetrafluoroethoxy)phenyl]-N-[2,4-di 
nitro-6-(trifluoromethyl)phenyl]methanesulfenamide and 
1,1,1-trichloro-N-[5-chloro-2-(1,1,2,2-tetrafluoroethoxy)phenyl]-N-[2,4-di 
nitro-6-(trifluoromethyl)phenyl]methanesulfenamide 
Sodium hydride (0.6 g, 57% in mineral oil), washed free of mineral oil with 
hexane under a nitrogen atmosphere, is slurried in 25 ml of anhydrous 
tetrahydrofuran and cooled to 0.degree. C. A solution of the mixed 
benzenamine obtained above (4.8 g 0.01 mole) in 25 ml of anhydrous 
tetrahydrofuran is then added dropwise with stirring at 0.degree.. After 
the addition is complete, the reaction mixture is allowed to warm to 
ambient temperature and stirred for 1 hour. Perchloromethyl mercaptan (3.7 
g, 0.02 mole) is added and the mixture stirred for 15 hours. The reaction 
mixture is then poured into water, extracted with methylene chloride, 
dried over anhydrous magnesium sulfate and stripped to afford a dark oil. 
Chromatography on silica gel with 1-chlorobutane/hexane (1:2 by volume) as 
the eluent affords a mixture of 
1,1,1-trichloro-N-[2-chloro-5-(1,1,2,2-tetrafluoroethoxy)phenyl]-N-[2,4-di 
nitro-6-(trifluoromethyl)phenyl]-methanesulfenamide and 
1,1,1-trichloro-N-[5-chloro-2-(1,1,2,2-tetrafluoroethoxy)phenyl]-N-[2,4-di 
nitro-6-(trifluoromethyl)phenyl]methanesulfenamide as an orange glassy 
resin. 
The procedure described in Examples 1, 2, and 3 above may be used to 
prepare the compounds of Tables I, II, III, and IV. 
TABLE I 
__________________________________________________________________________ 
##STR6## 
R.sub.1 
R.sub.2 
R.sub.3 
R.sub.4 
R.sub.5 
m.p. 
__________________________________________________________________________ 
Cl H H CF.sub.3 
H 134.degree.-137.degree. C. 
Cl H H OCF.sub.3 
H 
OCF.sub.3 
H H Cl H 
Cl H Cl H H 153.degree.-155.degree. C. 
OCF.sub.3 
H H OCF.sub.3 
H 
OCF.sub.3 
H OCF.sub.3 
H H 
OCF.sub.2 CF.sub.2 H 
H OCF.sub.2 CF.sub.2 H 
H H 
OCF.sub.2 CF.sub.2 H 
H H OCF.sub.2 CF.sub.2 H 
H 
Cl H H Cl H 166.degree.-168.degree. C. 
H CF.sub.3 
Cl H H 65.degree.-70.degree. C. 
H H Cl H H 
F H Cl H H 
Br H H CF.sub.3 
H 
Br H H OCF.sub.3 
H 
134.degree.-139.degree. C. (for 1 isomer) 
OCF.sub.3 
H H Br H 
NO.sub.2 
H H Cl H 
Cl H NO.sub.2 
H H 
F H F H H 
H H H H H 
Br H Br H H 
H Cl H H H 
H Br H H H 
H NO.sub.2 
H H H 
F H CF.sub.3 
H H 
H NO.sub.2 
Cl H H 164.degree.-166.degree. C. 
F H F H F 130.degree.-133.degree. C. 
__________________________________________________________________________ 
TABLE II 
______________________________________ 
##STR7## 
R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 
______________________________________ 
Cl H H CF.sub.3 H 
H H H H H 
Br H CF.sub.3 H H 
OCF.sub.3 H H Cl H 
Cl H H OCF.sub.2 CF.sub.2 H 
H 
Cl H Cl H H 
______________________________________ 
TABLE III 
______________________________________ 
##STR8## 
R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 
______________________________________ 
Cl H H CF.sub.3 
H 
Cl H H OCF.sub.3 
H 
H H H H H 
Br H CF.sub.3 H H 
Cl H NO.sub.2 H H 
OCF.sub.2 CF.sub.2 H 
H H Cl H 
Cl H Cl H H 
______________________________________ 
TABLE IV 
______________________________________ 
##STR9## 
R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 
______________________________________ 
Cl H H CF.sub.3 
H 
H H H H H 
Br H CF.sub.3 H H 
Cl H H OCF.sub.3 
H 
OCF.sub.2 CF.sub.2 H 
H H Cl H 
______________________________________ 
FORMULATION 
Useful formulations of the compounds of Formula (I) can be prepared in 
conventional ways. They include dusts, solutions, suspensions, emulsions, 
wettable powders, emulsifiable concentrates and the like. Many of these 
may be applied directly. Sprayable formulations can be extended in 
suitable media and used at spray volumes of from a few pints to several 
hundred gallons per acre. High-strength compositions are primarily used as 
intermediates for further formulation. The formulations, broadly, contain 
about 1% to 99% by weight of active ingredient(s) and at least one of (a) 
about 0.1% to 20% surfactant(s) and (b) about 1% to 99% solid or liquid 
diluent(s). More specifically, they will contain these ingredients in the 
following approximate proportions: 
______________________________________ 
Percent by Weight 
Active 
Ingredient 
Diluent(s) 
Surfactant(s) 
______________________________________ 
Wettable Powders 
20-90 0-74 1-10 
Oil Suspensions, 
5-50 40-95 0-15 
Emulsions, Solutions 
(including Emulsifi- 
able Concentrates) 
Aqueous Suspensions 
10-50 40-84 1-20 
Dusts 1-25 70-99 0-5 
Granules and Pellets 
1-95 5-99 0-15 
High-Strength 90-99 0-10 0-2 
Compositions 
______________________________________ 
Lower or higher levels of active ingredient can, of course, be present 
depending on the intended use and the physical properties of the compound. 
Higher ratios of surfactant to active ingredient are sometimes desirable, 
and are achieved by incorporation into the formulation or by tank mixing. 
Typical solid diluents are described in Watkins, et al., "Handbook of 
Insecticide Dust Diluents and Carriers", 2nd. Edn., Dorland Books, 
Caldwell, N.J. The more absorptive diluents are preferred for wettable 
powders and the denser ones for dusts. Typical liquid diluents and 
solvents are described in Marsden, "Solvents Guide", 2nd. Edn., 
Interscience, New York, 1950. Solubility under 0.1% is preferred for 
suspension concentrates; solution concentrates are preferably stable 
against phase separation at 0.degree. C. "McCutcheon's Detergents and 
Emulsifiers Annual", MC Publishing Co., Ridgewood, New Jersey, as well as 
Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. 
Co., Inc., New York, 1964, list surfactants and recommended uses. All 
formulatiosn can contain minor amounts of additives to reduce foam, 
caking, corrosion, microbiological growth, promote sticking, etc. 
Preferably, ingredients should be approved by the U.S. Environmental 
Protection Agency for the use intended. 
The methods of making such compositions are well known. Solutions are 
prepared by simply mixing the ingredients. Fine solid compositions are 
made by blending and, usually, grinding as in a hammer or fluid energy 
mill. Suspensions are prepared by wet milling (see, for example, Littler, 
U.S. Pat. No. 3,060,084). 
For further information regarding the art of formulation, see for example: 
J. B. Buchanan, U.S. Pat. No. 3,576,834, Apr. 27, 1971, Col, 5, Line 36 
through Col. 7, Line 70 and Ex. 1-4, 17, 106, 123-140; 
R. R. Shaffer, U.S. Pat. No. 3,560,616 Feb. 2, 1971, Col. 3, Line 48 
through Col. 7, Line 26 and Examples 3-9, 11-18; 
E. Somers, "Formulation", Chapter 6 in Torgeson, "Fungicides", Vol, I, 
Academic Press, New York, 1967. 
EXAMPLE 1 
Wettable Powder 
______________________________________ 
1,1,1-Trichloro-N-[2-chloro-5-(trifluoromethoxy)- 
phenyl]-N-[2,4-dinitro-6-(trifluoromethyl)phenyl]- 
methanesulfenamide, 50/50 mixture with the 
5-chloro-2-(trifluoromethoxy)phenyl isomer 
40% 
Dioctyl sodium sulfosuccinate 
1.5% 
Sodium ligninsulfonate 3% 
Low-viscosity methyl cellulose 
1.5% 
Attapulgite 54% 
______________________________________ 
The ingredients are thoroughly blended, passed through an air mill, to 
produce an average particle size under 15 microns, reblended, and sifted 
through a U.S. Ser. No. 50 sieve (0.3 mm opening) before packaging. 
All compounds of the invention may be formulated in the same manner, and 
dispersed in water for application. 
EXAMPLE 2 
Wettable Powder 
______________________________________ 
1,1,1-Trichloro-N-[2-chloro-5-(trifluoromethyl)- 
phenyl]-N-[2,4-dinitro-6-(trifluoromethyl)- 
phenyl]methanesulfenamide 80% 
Sodium alkylnaphthalenesulfonate 
2% 
Sodium ligninsulfonate 2% 
Synthetic amorphous silica 3% 
Kaolinite 13% 
______________________________________ 
The ingredients are combined in an efficient blender, passed through a 
hammer mill to produce particles below 40 microns, and then reblended. The 
product is sifted through a U.S.S. No. 50 sieve (0.3 mm openings) before 
packaging. 
EXAMPLE 3 
Dust 
______________________________________ 
Wettable powder of Example 1 
10% 
Pyrophyllite (powder) 90% 
______________________________________ 
The wettable powder and the pyrophyllite diluent are thoroughly blended and 
then packaged. The product is suitable for use as a dust. 
EXAMPLE 4 
Aqueous Suspension 
______________________________________ 
1,1,1-trichloro-N-[2-chloro-5-(trifluoromethyl)- 
phenyl]-N-[2,4-dinitro-6-(trifluoromethyl)- 
phenyl]methanesulfenamide 25% 
Hydrated attapulgite 3% 
Crude calcium ligninsulfonate 
10% 
Sodium dihydrogen phosphate 0.5% 
Water 61.5% 
______________________________________ 
The ingredients are ground together in a sand mill until the solid 
particles have been reduced to diameters under 10 microns. The product may 
be diluted with water for spray application. 
EXAMPLE 5 
Dust Seed Coat 
______________________________________ 
1,1,1-Trichloro-N-[2-chloro-5-(trifluoromethyl)- 
phenyl]-N-[2,4-dinitro-6-(trifluoromethyl)- 
phenyl]methanesulfenamide 75% 
Permanent Red 2 B, Calcium Salt, 
5% 
Diatomaceous Earth 20% 
______________________________________ 
The ingredients are blended, coarsely hammer-milled and passed through an 
air mill to product particles of active ingredient that are all below 10 
microns in diameter. The product is reblended before packaging. 
EXAMPLE 6 
Slurry Seed Coat 
______________________________________ 
1,1,1-Trichloro-N-[2-chloro-5-(trifluoromethoxy)- 
phenyl]-N-[2,4-dinitro-6-(trifluoromethyl)- 
phenyl]methanesulfenamide, 50/50 mixture with 
the 5-chloro-2-(trifluoromethoxy)phenyl isomer 
50% 
Calcium ligninsulfonate 4% 
Trimethyl nonyl polyethylene glycol ether 
4% 
Rhodamine B 1% 
Permanent Red 2 B, calcium salt, extended 
1% 
on Blanc Fixe 
Diatomaceous earth 40% 
______________________________________ 
The liquid surfactant is sprayed on the diatomaceous earth, the other 
ingredients are then added thoroughly mixed together in an efficient 
blender. The mixture is then coarsely hammermilled and passed through an 
air mill to produce particles of active ingredient that are less than 10 
microns in diameter. The product is reblended before packaging. The 
product may be extended in water and applied to seed in a commercial seed 
treater. 
USE 
The compounds (I) of this invention show a high degree of pesticidal 
activity combined with substantially reduced phytotoxicity relative to the 
benzenamines (II) active against a similar range of pests. Many of the 
compounds (I) are also substantially less toxic to mammals (e.g. as eye 
injurants) than the corresponding benzenamines (II). 
The compounds of this invention are useful as miticides and can be used to 
protect plants from damage caused by these pests. More specifically, 
fruits, field crops, vegetables and ornamentals can be protected. 
When mites come into contact with the compounds of this invention, either 
in the form of direct sprays or by walking over surfaces which have been 
treated, they are killed if they have been exposed to a sufficiently high 
dosage. While most plants are able to tolerate the presence of very small 
numbers of mites without apparent adverse effect, the reproductive 
capacity of these pests is enormous. Generally, mite populations rapidly 
build up, easily out-stripping parasite and predator capabilities for 
control. Growers noting rapid mite build-up must take immediate action to 
prevent damage to economically important crops. Thus, a method is needed 
for immediately reducing mite build-up and thereby preventing damage to 
important crops. 
The method of this invention, namely, contact mites with a miticidally 
effective concentration, is a most desirable method for control of these 
pests. For instance, very small quantities of compounds are required for 
miticidal activity. 
The quantity of compound needed for miticidal activity will vary depending 
on the specific situation. Among the variables that must be considered in 
deciding on the quantity of chemical to be used are the specific compound 
itself, the specific mite to be controlled, weather conditions, the type 
of crop, the stage of development of the crop, the volume of spray applied 
population pressure, and the interval between applications. For plant 
protection, solutions or suspensions containing as little as 2.5 ppm of 
active ingredient in a spray solution may prove effective under a given 
set of circumstances. For field usage, however, in high-volume 
applications, aqueous spray preparations containing 5-2500 ppm of active 
ingredient are generally useful. Preferred are suspensions containing 
20-500 ppm, and most preferred are those containing 80-320 ppm. On an area 
basis, in general, 0.03 to 5.5 kilograms of active-ingredient per hectare 
are acceptable, preferably 0.03 to 3 kilograms, and most preferable 0.06 
to 2 kg. When applied in an orchard, spraying is continued until run-off 
is observed. 
It may be desirable or useful to mix the compounds of this invention with 
other agricultural pesticides or adjuvants. Such mixtures often increase 
the effectiveness of the application on mites and broaden the scope of 
control to embrace other pests such as insects, fungi, nematodes, or 
bacteria. Pesticides with which the compounds of this invention may be 
mixed to achieve broader-spectrum activity include: 
Fungicides: 
methyl 2-benzimidazolecarbamate (carbendazim) 
tetramethyl thiuram disulfide (thiuram) 
n-dodecylguanidine (dodine) 
manganese ethylenebisdithiocarbamate (maneb) 
1,4-dichloro-2,5-dimethoxybenzene (chloroneb) 
methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl) 
N-trichloromethylthiotetrahydrophthalimide (captan) 
N-trichloromethylthiophthalimide (folpet) 
Bactericides: 
tribasic copper sulfate 
streptomycin sulfate 
Acaricides: 
senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol ("Morocide") 
6-methyl-1,3-dithiolo[2,3-.beta.]quinoxolin-2-one ("Morestan") 
ethyl 4,4'-dichlorobenzilate (Chlorobenzilate.RTM.) 
1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol (Kelthane.RTM.) 
bis(pentachloro-2,4-cyclopentadien-1-yl) (Pentac.RTM.) 
tricyclohexyltin hydroxide (Plictran.RTM.) 
Nematicides: 
S-methyl 1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate 
(Vydate.RTM.) 
S-methyl 1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate 
N-isopropylphosphoramidic acid, O-ethyl-O'-[4-(methylthio)-m-tolyl]diester 
("Nemacur") 
Insecticides: 
3-hydroxy-N-methylcrotonamide (dimethylphosphate) ester (Azodrin.RTM.) 
methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol 
(Furadan.RTM.) 
O-[2,4,5-trichloro-.alpha.-(chloromethyl)benzyl]phosphoric acid, 
O',O'-dimethyl ester (Gardona.RTM.) 
2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, 
dimethyl ester (Malathion.RTM.) 
phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl 
parathion) 
methylcarbamic acid, ester with .alpha.-naphthol (Sevin.RTM.) 
methyl O-(methylcarbamoyl)thiolacetohydroxamate (methomyl) 
O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidylphosphorothioate 
(Diazinon.RTM.) 
octachlorocamphene (toxaphene) 
O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN) 
cyano(3-phenoxyphenyl)methyl 4-chloro-.alpha.-(1-methylethyl)benzeneacetate 
(Pydrin.RTM.) 
(3-phenoxyphenyl)methyl(.+-.)-cis,trans-3-(2,2-dichloroethenyl)-2,2-dimethy 
lcyclopropanecarboxylate (Ambush.RTM.) 
O-ethyl-S-(p-chlorophenyl)ethylphosphonodithioate (Curacron.RTM.) 
phosphorothiolothionic acid, O-ethyl-O-[4-(methylthio)phenyl]-S-n-propyl 
ester (Bolstar.RTM.) 
The agricultural chemicals listed above are merely exemplary of compounds 
that may be mixed with the active compounds of this invention. 
The compounds are especially suited for the protection of living plants 
such as fruit-bearing trees, nut-bearing trees, ornamental trees, forest 
trees, vegetable crops, horticultural crops (including ornamentals, small 
fruit and berries) and grain and seed crops. Apple trees, peach trees, 
cotton, citrus trees, bean and peanuts are particularly susceptible to 
mite damage and can be protected by application of the compounds of this 
inention. To assure control throughout the growing season (e.g., June 
through August in the Northern Hemisphere) multiple applicaions at desired 
intervals can be utilized. 
Many species of mites are controlled by the compounds of this invention. 
The following is a list of representative susceptible mites along with the 
types of damage that they can cause: Panonychus ulmi (European red mite) 
and Tetranychus urticae (two-spotted mite) which are commonly called 
"orchard mites," and which attack a great many deciduous trees, such as 
apple, pear, cherry, plum and peach trees; Tetranychus altanticus 
(Atlantic or strawberry mite), T. cinnabarinus (carmine spider mite) and 
T. pacificus (Pacific mite); which attack cotton and numerous other crop 
plants; Paratetranychus citri (citrus red mite) and others which attack 
citrus; Phyllocoptruta oleivora which causes citrus rust; Bryobia 
praetiosa (clover mite) which attacks clover, alfalfa and other crops; and 
Aceria neocynodomis which attacks grasses and other plants. 
The compounds of this invention are also useful as plant disease control 
agents. They are effective for the control of a broad spectrum of plant 
diseases as represented by but not limited to soil borne fungal pathogens 
Rhizoctonia solani and Phytophthora parasitica, a pathogen that infects 
seeds and seedlings, Helminthosporium oryzae, a fungus that attacks stems 
and leaves, Puccinia graminis, a fungus that causes leaf and fruit 
lesions, Venturia inaequalis, and a fruit and vegetable rotting fungus, 
Sclerotinia sclerotiorum. Diseases of a wide variety of ornamental, 
vegetable cereal and fruit crops are controlled by the compounds of this 
invention. 
Disease control is accomplished by applying the compound to the portion of 
the plant to be protected such as the roots, stems, foliage, fruit, seeds, 
tubers or bulbs, or to the media (soil) in which the plants to be 
protected are growing. 
Rates of application for these compounds will be influenced by many factors 
of the environment and must be determined under use conditions. Seed and 
seedlings can normally be protected when seed is treated at a rate of from 
0.06 to about 3 grams per kilogram of seed. Plants growing in soil treated 
at a concentration of from 0.1 to about 20 kg/ha can be protected from 
disease. Compositions of this invention may contain, in addition to a 
compound of this invention, conventional pesticides, such as insecticides, 
miticides, bactericides, nematicides, fungicides or other agricultural 
chemicals such as growth modifying agents. Representative examples of 
these are listed above. 
The compounds of this invention are also useful as insect ovicides. The 
species that may be controlled include but are not limited to beet 
armyworm (Spodoptera exigua), and southern armyworm (Spodoptera 
frugiperda), potato tuberworm (Phthorimaea operculella), cotton bollworm 
(Heliothis zea) and tobacco budworm (Heliothis virescens). 
Spray applications of 0.1-2 kg per hectare to foliage containing eggs will 
prevent further development of the embroyos thereby protecting the plant 
from the feeding effect of voracious larvae. Plants to be protected 
include a wide range of vegetable and field crops, ornamentals and forest 
trees. 
EXAMPLE A 
Test units consisted of plant pots containing two red kidney bean plants in 
the two-leaf stage per pot. The plants were infested with two-spotted 
mites and sprayed to run-off with solutions of 
1,1,1-trichloro-N-(2-chloro-5-trifluoromethylphenyl)-N-(2,4-dinitro-6-trif 
luoromethylphenyl)methanesulfenamide. Solutions were made by dissolving 
weighed quantities of the active ingredients in 10 ml. of acetone and then 
diluting to volume with water containing 1:3000 of a surfactant, 
Duponol.RTM.. Mortality was evaluated two days after spraying. 
______________________________________ 
% Spray 
Concentration % Mortality (2 Days) 
______________________________________ 
.001 100 
.0005 99 
.00025 96 
______________________________________ 
EXAMPLE B 
Bean plants, infested with two-spotted mites, were sprayed to run-off with 
the indicated concentration of 
1,1,1-trichloro-N-(2-chloro-5-trifluoromethoxyphenyl)-N-(2,4-dinitro-6-tri 
fluoromethylphenyl)-methanesulfenamide 50/50 mixture with the 
5-chloro-2-trifluoromethoxyphenyl isomer in Duponol.RTM.: water at 1:3000. 
Mortality after two days is set forth below. 
______________________________________ 
% Spray 
Concentration % Mortality (2 Days) 
______________________________________ 
.001 100 
.0005 97 
.00025 93 
______________________________________ 
EXAMPLE C 
Rhizoctonia solani infested soil was placed in a 900 cc cup. 
1,1,1-Trichloro-N-(2-chloro-5-trifluoromethoxyphenyl)-N-(2,4-dinitro-6-tri 
fluoromethylphenyl)methanesulfenamide 50/50 mixture with the 
5-chloro-2-trifluoromethoxyphenyl isomer was mixed in a section 2" 
wide.times.2" deep.times.4" long to simulate an in-the-row application. 
Five cotton seeds were planted in the treated soil. After 8 days, the 
cotton plants were removed and rated for disease control. 
______________________________________ 
Percent 
kg/ha 40" row Rhizoctonia solani Control 
______________________________________ 
1.5 100 
0.5 100 
Untreated Control 
0 
______________________________________ 
EXAMPLE D 
Portion of soil infested with Phytophthora parasitica were treated by 
mixing with various concentrations of 
1,1,1-trichloro-N-[2-chloro-5-(trifluoromethyl)-phenyl]-N-[2,4-dinitro-6-( 
trifluoromethyl)phenyl]-methanesulfenamide. These treated portions of 
infested soil and also portions left untreated were placed in pots and 
planted with tobacco seeldings about 5 cm tall. After four weeks, all of 
the tobacco seedlings in the untreated soil were dead with symptoms of the 
black shank disease. On the other hand, those seedlings planted in soil 
treated with 20 or 10 or 5 kg/Ha of the compound of this invention were 
growing well and showed no disease symptoms. 
EXAMPLE E 
Surface sterilized carrot sections were dipped 5 minutes in a solution 
containing 100 ppm of the 
1,1,1-trichloro-N-(2-chloro-5-trifluoromethylphenyl)-N-(2,4-dinitro-6-trif 
luoromethylphenyl)methanesulfenamide. Additional sections were dipped in a 
check solution which contained 500 ppm Trem.RTM. 014, 5 ml acetone and 30 
ml of sterilized water. 
After inoculation by placing a mycelial plug of Sclerotinia sclerotiorum on 
each carrot section, the test was held at 20.degree. for six days. 
The untreated carrot sections were completely invaded with the mycelial 
growth of the white mold fungus but the treated sections were totally free 
of growth by this disease causing organism. 
EXAMPLE F 
1,1,1-trichloro-N-(2-chloro-5-trifluoromethoxyphenyl)-N-(2,4-dinitro-6-trif 
luoromethylphenyl)-methanesulfenamide 50/50 mixtures with the 
5-chloro-2-trifluoromethoxyphenyl isomer was dissolved in acetone in an 
amount equal to 10% of the final volume and then suspended at 
concentrations of 16, 3, and 1.6 ppm in purified water containing 250 ppm 
of the sufractant Trem.RTM. 014 (polyhydric alcohol esters). This 
suspension was sprayed to the point of run-off on wheat seedlings. 
The following day the wheat seedlings were inocculated with a spore 
suspension of the fungus Puccinia graminis var. tritici and incubated in a 
saturated humidity chamber at 20.degree. for 24 hours, and then in a plant 
growth chamber for an additional 7 days when disease ratings were made. 
The plants treated with the compound of this invention were free of leaf 
infection (100% control) in contrast to the untreated plants which were 
covered with rust pustules. No injury was noted on treated wheat. 
EXAMPLE G 
1,1,1-Trichloro-N-(2-chloro-5-trifluoromethylphenyl)-N-(2,4-dinitro-6-trifl 
uoromethylphenyl)methanesulfenamide was dissolved in acetone in an amount 
equal to 10% of the final volume and then suspended at a concentration of 
16 ppm in purified water containing 250 ppm of the surfactant Trem.RTM. 
014 (polyhydric alcohol esters). This suspension was sprayed to the point 
of run-off on young apple seedlings in a vigorous state of growth. The 
following day, the apple seedlings were inoculated with a spore suspension 
of the fungus Venturia inaequalis and incubated in a saturated humidity 
chamber at 20.degree. for 24 hours, and then in a plant growth chamber for 
an additional 10 days when disease and plant injury ratings were made. The 
plants treated with the compound of this invention were free of leaf 
infection (100% control) in contrast to the untreated plants which were 
covered with scab lesions. 
EXAMPLE H 
1,1,1-Trichloro-N-(2-chloro-5-trifluoromethylphenyl)-N-(2,4-dinitro-6-trifl 
uoromethylphenyl)methanesulfenamide was dissolved in acetone base solvent 
and applied to rice seed infected with Helminthosporium oryzae. Treated 
seeds were allowed to dry, then planted. In Test 1 treated seed was placed 
directly on moist blotting paper, covered with polyethylene covers and 
allowed to germinate and grow at 21.degree.. This test was rated 2 weeks 
following planting. 
In Test 2 treated seed was planted in cups of sterile soil and allowed to 
germinate and grow in the greenhouse. Soil was kept moist. In this test, 
treatments were replicated 5 times. The test was evaluated 10 days 
following planting. 
In both tests: 
1. Disease control was determined on the basis of healthy plants. 
2. Crop phytotoxicity was shown as crop growth reduction and rated on a 
0-10 scale with 0 being no phytotoxicity and 10 being no growth. 
The following are the results of two rice tests: 
______________________________________ 
Rate, 
Test # g ai/kg % Healthy Plants 
Crop Growth Reduction 
______________________________________ 
1 0.06 90 0 
0.6 80 2 
1.3 60 5 
2.5 50 5 
2 0.075 58 2 
0.15 64 2 
0.30 74 1 
0.60 82 1 
Untreated 
Check -- 56 3 
______________________________________ 
EXAMPLE I 
Eggs of the potato tuberworm, Phthorimaea operculella, were laid on muslin 
cloth. Discs, each containing 50-75 eggs, were dipped for 10 seconds in 
the indicated concentration of 
1,1,1-trichloro-N-(2-chloro-5-trifluoromethoxyphenyl)-N-(2,4-dinitro-6-tri 
fluoromethylphenyl)methanesulfenamide extended in Dupanol.RTM.:water at 
1:3000. The discs were then placed in petri dishes for three days. Percent 
control (% eggs failed to hatch) is summarized below. 
______________________________________ 
% Concentration % Control (3 Days) 
______________________________________ 
.03 100 
.01 100 
Untreated Check 9 
______________________________________ 
EXAMPLE J 
Eggs of the beet armyworm, Spodoptera exigua, were laid on cellophane, 
Discs, each containing 50-75 eggs, were placed in petri dishes and lightly 
sprayed with the indicated concentration of 
1,1,1-trichloro-N-(2-chloro-5-trifluoromethylphenyl)-N-(2,4-dinitro-6-trif 
luoromethylphenyl)methanesulfenamide in acetone solution. Three days later, 
percent control (% eggs failing to hatch) was determined. 
______________________________________ 
% Concentration % Control (3 days) 
______________________________________ 
0.05 100 
0.005 50 
Untreated Check 0 
______________________________________