CA1060459A - Ring-substituted n-(2,2-difluoroalkanoyl)-o-phenylenedia-mines - Google Patents

Abstract

Abstract of the Disclosure Ring-substituted N-(2,2-difluorcalkanoyl)-o-phenylenediamine compounds are described herein. These compounds are useful as herbicides, insecticides, para-siticides, anthelmintic and nematocidal agents. The o-phenylenediamine compounds are prepared by acylation of the corresponding diamine to introduce the 2,2-difluoro-alkanoyl group.

Description

~-- lO~iQ459 RING-SUBSTITUTED N-(2,2-DIFLUOROALKANOYL)-o-PHENYLEN~DIAMINE COMPOUNDS
~ The present invention relates to novel ring-substituted N-(2,2-difluoroalkanoyl)-o-phenylenediamine compounds. These compounds are useful as herbicides, insecticides, parasiticides, anthelmintic and nemato-cidal agents.
The control of animal parasites is one of the oldest and most important problems of the animal husbandry industry. Many types of parasites afflict virtually all species of animals. Most animals are afflicted by free-flying parasites such as flies, crawling ectoparasites such as lice and mites, burrowing parasites such as bots ana grubs, and by microscopic endoparasites such as coccidia, as well as by larger endoparasites such as worms.
Thus, the control of parasites even in a single host species is a complex and many-sided problem.
The insect and acarina parasites which consume living tissues of a host animal are particularly harmful.
The group includes parasites of all the economic animals, including ruminant and monogastric mammals and poultry, and of companion animals such as dogs as well.
Many methods of control of such parasites have been tried. The screwworm has been practically eradicated in Florida by the release of great numbers of sterile male blowflies. The method obviously is applicable only to an easily isolated area. The free-flying insects are usually controlled by routine methods such as air-dispersed and contact insecticides and fly traps. The skin-inhabiting, crawling parasites are usually controlled by dipping, drenching, or spraying the animals with appropriate parasiticides.

~06Q459 Some progress has been made in the systemic control of some parasites, particularly those which burrow in or migrate through the host animal. Systemic control of animal parasites is accomplished by absorbing a parasiticide in the bloodstream or other tissues of the host animal. Parasites which eat or come into contact with the parasiticide-containing tissue are killed, either by ingestion or contact. A few phosphate, phophoramidate, and phosphorothioate insecticides and acaricides have been found to be sufficiently nontoxic to be used systemically in animals.
Rumanowski, U.S. Patent No. 3,557,211, discloses N,N-bis(acetyl)-o-phenylenediamines which are useful for the control of plants, insects and fungi.
It is one of the objects of this invention to provide compounds whiCh are effective systemic parasiticides.
The present invention is directed to novel ring-substituted N-~2,2-difluoroalkanoyl)-_-phenylene-diamine compounds of the formulae:
R3 ~ NH-R

(I) ~ NH-R
R4 ~

R ~ O
NH-R

R5 ~ NH_ n ~ NH-R

(III)R6 - ~ H_R2 wherein R is a 2,2-difluoroalkanoyl radical of the formula - C-CF2-Y, in which Y is hydrogen, chlorine, fluorine, ~3--difluoromethyl, perfluoroalkyl of Cl-C6, or a radical of the formula C C H
Z n in which each Z independently is hydrogen or halogen and n is O or l;
Rl is hydrogen, a radical of the formula-C-O-Yl in which yl is Cl-C4 alkyl or phenyl, benzoyl, ~:
furoyl, naphthoyl, or substituted benzoyl of the formula `` ~060~59 o ~ Z'p ----\~ Z~lq ~

in which each Z' independently iæ halo or nitro, Z"is Cl-C4 alkyl or Cl-C4 alkoxy, p is 0, l, or 2, q is o or l, and the sum of p and q is l-3; :.
R2 is ;
R
Rl Cl-Ca alkanoyl, C3-C4 alkenogl, -C3- C4 alkynoyl, halogenated C2-C4 alkanoyl beari~g on any :~
position or positions one or more halogen atoms, each lndependéntly selected~ sub~ect to the limitation that the alpha position bear at least one substituent moiety selected from the group consisting of hydragen and ~: . halogen of atomic weight from 35 to 127, both inclusi~e; ;~-~ 20 ~ each R3 independentlY is halogen;
:. R4 is nitro;
R5 is trifluoromethyl, difluoromethyl, or difluorochloromethyl, and in compounds of formula (II), R and R5 are meta to one another;
: R~ i8 Cl-C4 alkglsulfonyl and i8 located at the:4 or 5 pos1t~on, and any R4 group is meta to R~;
m 1s ~rom 0-4;
:~ : n is 0 or l; and in compound~ of formula (I), the sum of m and n is an integer of from 1-4;
: ` :

.
- .
X-3277~ ` _5_ '.

i ,. . .. . . :: . . . . . . . . . .

10~0~59 subject to the further limitation that where Rl or R2 is hydrogen, the ring position ortho to the -NH-Rl or -NH-R2 ~roup bears one of the designated R3, R4 or R5 moieties.
The compounds of formulae I, II and III are prepared by introduction Or the characteristic 2,2-difluoroalkanoyl group into the appropriate corres-ponding diamine starting materials. Introduction of this group can be achieved by any of numerous available acylation reactions, employing any of several types of acylating agents o~ the formula (IV) H0C-CF2-YJ
wherein Y is de~ined as hereinbefore, or the active derlvatlve thereof. The identity of the acylating agent is not critlcal; sultable acylating agents include the 2,2~difluoroalkanoyl halides:
(V) halo C - CFz - Y ;
and the 2,2-difluoroalkanolc anhydrides:
'S~ -(VI) o - C CF2 Y 2 wherein Y is de~ined as hereinbefore. The diamine starting materials with which thea~ylation reaction is carried out will vary.
Thus, a process for the preparation of the compounds of formulae I, II and III comprises acylating a compound selected from the group consisting o~ the compounds of the formulae:

~ .

106~459 ~ ~

~ NH2 (VII) ~ NH-R

R4n (VIII) ~ NH-Rl ;~
Rs Rn ~ NH2 (IX) ~ ~ NH-R2 R ~ -~ .
wherein the varlous symbols are derined as hereinbefore~
wlth an acylating agent of the formula (IV) H0~-CF2-Y
wherein Y i8 defined as abo~e or the active derivati~e thereof.

In the instance of the com~ound~ Or formulae I, II and III wherein R is hydrogen or wherein R2 is either hydrogen or the æame moiety as is represented by R, the starting diamine is a compound of one of the following formulae:

. Rm3 (X) ~ NNa Rn .

: X-3277B . -7-iO~0459 R~

(XI) ~ NH2 ~NH2 Rn4 `.
(XII) R~ ~ NH2 and either one acyl group is introduced (leaving Rl or R equal to hydrogen~ or two identical acyl groups are :
introduced (R and R are -C-CF2-Y).
Where, on the other hand, R is any other moiety than hydrogen and R2 18 any other moiety than hydrogen or the same 2,2-di~luoroalkanoyl moiety as ~8 represented by R, the appropriate diamine starting material is a compound already bearing the desir~d R
or R moiety of the formulae: -Rm3 (XIII) ` ~ NH2 NH-R
Rn : ~ . R~
NHz (XIV) . ~ NH-R
,s R~
(XV ~ Re~NH2 .

: X-3277B -8-~ ' . .

: :

`- 10ti0459 wherein the symbols are defined as hereinbefore, and the characteristic R group is similarly introduced by acylation.
It is noted that the R2 group can be a 2,2-difluoroalkanoyl group different from that represented by R, in which instance the groups are introduced sequentially.
While the synthetic routes described foregoing are convenient and preferred, yet other routes can be utilized. Thus, for example, in the instance where Rl is an acyl group, the Rl group is conveniently introduced in ~`
some instances after the R has already been introduced.
However, because of the activating effect on acylation of the alpha fluorine atoms, it is generally preferred that groups other than the 2,2-difluoroalkanoyl moiety already be present when this group is introduced. In the instance where R is formyl, the acylation is conducted with a mixed anhydride of acetic and formic acid. Alternately, other acylating agents by which formyl groups are introduced can be used.
The preparation of amides by the acylating of corresponding amines with various acylating agents is a known synthetic method. The present preparations are conducted in accordance with the known procedures for effecting this method. Thus, where the acylating agent is an anhydride, the reaction is conveniently conducted at room te~perature;
solvent, which can be excess anhydride, except in the case of amides where Rl or R2 is hydrogen, can be utilized. Where an acyl 1~045g halide is employed as acylating agent, the reaction i~ necessarily conducted in the presence of a h~drogen halide acceptor and preferably in the presence of an inert sol~ent, and the reaction mixture is preferably cooled, such as to temperatures of 0-10C. In the case of either acylating agent, the product is separated ln conventional procedures, and can be purified if desired>
likewise in con~entional procedures.
For the sake of unirormity, starting materials and products herein are named, where possible, as o-phenylenediamines. In accordance with common nomen-clature practice, the identification of ~arious sub-stituent positions i8 as follows:
(Nl ) (N2 ~
where either nitrogen atom bears an alkanoyl or other (R, Rl, R2~ substituent, the ring position numbers are identified as prime numbers to distingulsh them from ~; numbers o~ positions on the R, Rl, or R2 substituent.
In the foregoing definition of the compounds of ~ormulae I, II and III, as generally in the present ;~ ~pecification and claims, each of the terms "halo" and "halogen," when unqualified but as used both alone and in the composite term "halogenated alkanoyl," designates bromine, chlorine, fluorine, or iodine~ only.
An e~sential and distingui6hing structural feature of the compounds of formulae I, II and III is iO459 the 2,2-difluoroalkanoyl-radical (R); representatiYe of such radicals include the following:
difluoroacetyl trifluoroacetyl difluorochloroacetyl -pentafluoropropionyl heptafluorobutyryl nona- fluoro~aleryl

2,2,3,3-tetrafluoropropionyl undecafluorohexanoyl trideca~luoroheptanoyl pentadecafluorooctanoyl 2,2-difluoroproplonyl 2~2-difluorobutyryl 2~2-di n uoro-3-bromopropionyl 2,2-di~luoro-3-chloropropionyl 2,2-difluoro-3,4-dichlorobutyryl 2~2-difluoro-4-bromobutyryl 2,2,3-txi~luoropropionyl 2,2,3-trifluorobutyryl ~: 2,2,3,4-tetrafluorobutyryl 2,2-difluoro-3-bromo-4-chlorobutyryl Preferred R groups are trifluoroacetyl, difluoroacetyl, difluorochloroacetyl, and 2,2,3,3-tetrafluoropropionyl.
The starting materials to be employed in accordance with the preæent invention are prepared by known procedures, and some of them are com~ercially available. Those starting materials which are of the formula lObiQ~S9 4 ~ NH2 ~ N~2 Rn ~LNH2 ~NH2 RB~NH2 X XI XII

are prepared by a plurality of synthetic steps as are necessary to introduce the required moieties. Most conveniently, one or both of the NH2 groups are intro-duced by conversion of a halo group. Also, the amino group or groups can be introduced by nitration and subsequent reduction. These various synthetic steps are generally and most conveniently carried out with starting materials already bearing the requisite R3, R4, R5 and R~ moieties. However, it is sometimes preferred that these substituents, where, e.g., nitro or halo, be introduced simultaneously with the synthetic steps leading to the introduction of the amino groups.
Thus, for example, where the diamine is tetrasubstituted, the corresponding tetrasubstituted benzene is nitrated at each of the remaining ortho positions and the nitro groups then reduced. A 3-nitro-5-substituted diamine where the substituent is alkylsulfonyl is readily prepared by nitrating a 5-substituted-2-hydroxynitrobenzene to introduce a

3-nitro group, followed by conversion of the hydroxy group to a chloro, amination, and selective reduction.
Those of the compounds of formula I or II
wherein R2 i~ a moiety other than hydrogen or the same acyl moiety as R generally are prepared from diamine starting materials already bearing the requlsite R
moiety These starting materials are themselves prepared from the corresponding diamine starting materials described above, by reaction with an appro-priate acyl ha ide or, in the instance of Rl or R2 representing -C-Y'~ with an appropriate loweralkyl or phenyl halo~ormate. Alternately, however, these starting materials can be prepared from o-nitroanilines:

Rm f~ NO2 I~NH2 h R4 f R4 . .
~02 ~liH2 R

. R~ ~ N2 . by. acylation and subsequent reduction~ both in pro-! . cedure6 well known in the prior art.

, , .

, .

-- . . .

All o~ the compounds of formulae I, II, and III are adapted to be employed as herbicides. These compounds can be utilized to achieve broad herbicidal action; hence, in its broadest sense, the present invention is directed to a process Or applying to a - plant part, which can be a stem, leaf, flower, fruit, root or seed or other similar reproductive units Or a plant, a growth-inhibiting amount o~ one of the ring-substituted (N-2,2-difluoroalkanoyl)-o-phenylenediamine compounds of formulae I, II or III. However, these compounds can also be utilized to take advantage of Relective patterns of herbicidal activity. As will be -evident to those skilled in the art, a mixture of more thàn one of the compounds can also be employed to achieve herbicidal action. When employing a mixture~
an appropriate reduction should be made in the amount Or each individual compound sb that the mixture pro-vides only the desired herbicidal e~fect.
It is not critical to the herbicldal utility of the compounds that complete destruction o~ undesir-able vegetation be obtained, it being adequate ir the growth of the unwanted vegetation is merely inhibited.
Especially where selective action is sought, inhibitlon falling short of actual killing is adequate, partlcularly when combined with naturally occurring conditions such ~ -as limited moisture which more adversely affects the vegetation selectively inhibited than the crop plant.
~ The compounds of formulae I, II, and III are suited to a wide variety of herbicidal application~.

.

10~ 459 Thus, for example at rates which evoke the selective action ~f the compounds, which rates are deflned more completel~ hereinbelow, the compounds can be used as selective herbicides in crop plants, such as, for example, cotton, corn, sorghum and soybeans. In such use, application can be made preemergent to both crops and weeds, or, preferably by means of a directed spray application technique~ postemergent to the crop plant but both preemergent and postemergent to the weeds.
In another application, the compounds of formulae I, II and III can be used to give broad herbicidal action on non-crop land, including inter-mittently non-crop strips of contour-farmed land For such usage on so-called fallow land, application can be made in spring to suppress vegetative growth until a fall or following spring planting, or in the fall to suppress vegetative growth until a spring or following fall planting. ~urthermore, in another applicatlon, the compounds can be utilized to control weeds in tree crop plantings, such as plantings of the various citrus trees. In all of these various applications, and yet others for which the compounds are suited, another ad-vantage is that the compounds need not be disced into the soil being treated, it being adequate if one of the compounds, or a formulation containing one of the com-pounds, is merely spread onto the top ~urface. However, where desired or convenient, the compounds can be disced into, or otherwise mechanically mixed with the soil. In addition to the foregoing terrestrial em-bodiments, the present compounds can also be utilized 1060~59 as aquatic herbicides.
The use of the compounds of formulae I, II
or III as a herbicide can in some instances be carried out with unmodified compound; however, for good results, it i8 generally necessary that the compound be employed in modified form, that is, as one component of a com-position ~ormulated to implement the plant growth-inhibiting effects. Thus, for example, the aCtiYe agent can be mixed with water or other liquid or liquids, preferably aided by the usage of a surface active agent. The active agent can also be incorpor-ated on a finely divided solld, which can be a surface active substance, to yield a wettable powder, which can subsequently be dispersed in water or other liquid, or incorporated as part of a dust whlch can be applied directly. Other ways Or preparing formulations are known in the art and can be employed for these compounds.
The exact amount of the active agent employed is not critical and will vary, depending upon the type of growth-inhibiting effect desired, the identity of the plants concerned, the particular active agent used, and weather conditions. In general, a broad growth-inhibiting effect is obtained with rates of trom 0.5 to 20 pounds or more of active agent per acre, and such rates are suitable and effective forcontrol of vegetative growth on fallow land. When it is desired to obtain a selective growth-inhibiting effect on weed~
in areas containing crop plants such as corn, soybeans, and cotton, rates of from 0.5 to 10 pounds generally give good results. When in the typical mode of ` iO6Q459 operation, the active agent is employed as a composition comprising the agent, the exact concentration of active agent in the composition is not critical, except that the concentration and total amount o~ formulation em-ployed be adequate to supply the appropriate amount of active agent on a per acre basis. In general, good results are obtained when employing formulations con-taining the active agent in a concentration o~ ~rom 0.5 to 10 percent or higher, in the instance o~ a liquid formulation; and in a concentration of ~rom 1.0 to 5.0 percent or higher, in the instance of a dust, powder, granule, or other dry ~ormulation. More concentrated ~ormulations can be prepared and are o~ten preferred in that they can serve, depending upon the partlcular application contemplated and the particular concentration, both as a concentrated ~ormulation for purposes o~ ship-ment and storage, and as an ultimate treating com-position. Thus, ~or example, formulations o~ten pre-~erably contain a surface active agent and the present active agent, the latter being present in an amount o~
~rom 0.5 to 99.5 percent, by weight, or an inert, ~inely divided solid and the present active agent, the latter being present in an amount o~ from 1.0 to 99 percent, by weight. Such formulations, as indica~ed, can be employed directly in certain applications, but can also be diluted and subsequently employed in many other applications.
Liquid compositions containing the desired amount o~ active agent are prepared by dissolving the ~60459 substance in an organic liquid or by dispersing the substance in water with or without the aid of a suitable surface active dispersing agent such as an ionic or non-ionic emulsifying agent. Such compositions can also contain modifying substances which serve as a "spreader" and "sticker" on plant foliage. Suitable organic liquid carriers include the agricultural spray oils and the petroleum distillates 6uch as diesel fuel, kerosene, fuel oil naphthas, and Stoddard solvent.
Among such liquids, the petroleum distillates are generally preferred. The aqueous compositions can con-tain one or more water i~miscible solvents for the toxicant compound In such compositione~ the carrier compri6es an aqueous emulsion, e ~., a mixture of water, emulsifying agent and water immiscible solvent. The choice of dispersing and emulsifying agent and the amount thereof employed is dictated by the nature of the com-position and by the ability of the agent to facilitate the dispersion of the active agent in the carrier to produce the desired composition. Dispersing and emul-si~ying agentæ which can be employed in the compositions include the condensation proaucts o~ alkylene oxides with ~` phenols and organic acids, alkyl aryl sulfonAtes, poly-oxyalkylene derivatives or sorbitan esters, and complex ether alcohols. Representative sur~ace active agents which are suitably employed in implementing the present invention are identified in U.S. Patents 3~095,299~
- second column, lines 25-36; 2,655,447, column 5; and 2,412,510, columns 4 and 5.

` `

if~ ~ 4 5 9 In the preparation of dust compositlons, the active lngredlent of formulae I, II~ or III i8 lntimately dispersed in and on a finely di~lded solid such as clay, talc, chalk, gypsum, lime~tone, vermi-culite fines, or perlite. In one method Or achie~ing such dispersion, the flnely divlded carrier is mechani-cally mixed or ground with the active agent.
Similarly, dust compositions containln2 the toxicant compounds can be prepared with various Or the ~olid surface active dispersing agents such aB ben-tonite? fuller' 8 earth, attapulgite and other clays.
Depending upon the proportion~ of ingredient~ t~ese dust compoeitions can be employed as concentrates and ~ubsequently diluted with additional solid ~urface active dispersing agents or with chalk, talc, or gyp~um to obtain the desired amount of active ingredient in a composition adapted to be employed for the suppression of the growth of the plants. Also, such du~t composi-tions can be dispersed in water, with or without the aid of a dispersing agent, to form spray mixtures.
Formulations containing the present acti~e agents of formulae I, II or III are often advantageously further modified by incorporation therein of an effective amount of a surfactant which facilitates the disper~ion and spreading of the formulation on the plant leaf surfaces and the incorporation of the formulatlon by the plant The acti~e agent can be dispersed in soil or other growth media in any convenient fashion. Appli-cations can be carried out by simply mixing with the - `

~o~o~s9 media, by applying to the sur~ace of soil and thereafter dragging or discing into the soil to the desired depth, or by employing a liquid carrier to accomplish the penetration and impregnation. The application o~ spray and dust compositions to the surface of soil, or to plant part~ or the above ground surfaces of plants can be carried out by conventional methods, e.g., powder dusters~ boom and hand sprayers andspray dusters, whether surface or air-borne. However, while such con-ventional modes of application can be used~ they are notrequired. It i8 an advantage of the compounds Or formulae I, II and III that they are active and effecti~e as herbicide8 when merely placed on the surfàce of the soil~ without any additional step to as~ist incorporation.
Thus, the compounds are of substantially the same e~fi-cacy regardless of whether they are applied to the surface only, or whether they are applied to the surrace and subsequently disced into the soil.
The distribution of the active agent in soil can also be accomplished by introducing the agent into the water employed to irrigate the soil. In such procedures, the amount of water is varied with the poroæity and water holding capacity of the soil to obtain a desired depth of distribution of the agent.
The compounds of formulae I, II and III
exhibit low mammalian toxicity relative to corres-ponding benzimidazoles. In addition, the compoundg Or formula I, II, or III may be dispersed as an àerosol composition containing one or more of the present active agents as an active compound. Such a com-~60\4S9 posltlon is prepared according to con~entional methods wherein the agent is dispersed in a solvent, and the re~ultant dispersion mixed with a propellant in liquid state. ~uch variables as the particular agent to be used and the nature of the vegetation whlch is to be treated will determine the desirability of the solvent and concentration of the agent therein. Examples of suitable solvent~ are water, acetone, isopropanol, and 2-ethoxyethanol.
Sati6factory results are obtained when the active agent Or formulae I, II or III, or a composltion compri~ing such acti~e agent, i8 combined with other agricultural materials intended to be applied to plant~, plant parts, or their habitats. Such materials include rertilizers, fungicides, insecticides~ other herbicides, 7' and 80il conditioning agent~.
Various Or the compounds of formulae I, II or III to be employed as actlve herbicidal agents were evaluated for preemergent application to various species of plants. In thi~ evaluation, a soil was prepared consi~ting of one part masonry sand and one part ~hredded top 80il blended together in a cement mlxer.
One gallon of thi~ soil was placed in a 25 x 35 cm.
galvanized flat and was patted down with a bench brush until level. A three-row marker was used to make 2 l/2 cm. deep rurrows ii approximately two-~irths Or the flat. Crop seeds consistlng o~ rour kernels o~
corn, ~l~e cotton seeds, and fiYe soybean seeds were placed in these furrows. A ~our-row template was then .

placed on the remaining soil and the indicated approximate numbers of each of the following seeds were planted, one species to each section: foxtail (millet). 80-100 seeds;
velvetleaf (40-50 seeds); rough pigweed (150-250 seeds);
and large crabgrass (100-150 seeds).
Sufficient soil was added to cover the entire flat. Thus, the weed seeds were covered to a depth of about 6 mm. and the crop seeds were covered to a depth of about 3 cm.
In assaying the effect of the composition as preemergent herbicides, a flat prepared as above, taken either on the day of planting or on the next day, was placed in a chamber equipped with a turntable and an air exhaust. The herbicidal composition, either a spray-type emulsion or a wettable powder, was applied to the flat with a modified DeVilbiss atomizer hooked to an air source. Twelve and one-half milliliters of the composition under test were applied to each flat either on the day of planting or the succeeding day. Injury ratings and observations as to type of injury were made eleven to twelve days after treatment. The injury rating scale used was as follows:
0--no injury l--slight injury 2--moderate injury 3--severe injury

4--death When more than one determination was carried out at a given rate, an average value was calculated for the ~06Q459 in~ury rating. Each compound evaluated was formulated a~ a spray by one of the following procedure~. In one test the particular compound was wetted by grindlng ln a mortar with one part of polyoxyethylene sorbltan monolaurate. Five hundred parts o~ water were added slowly to the resultant creamy paste to give an agueous dispersion with a surfactant concentration of 0.2 percent. This dispersion was entirely satisfactory for spray application. In a second procedure the compound was dissolved in one volume o~ acetone, and the acetone solution was diluted with nineteen volumes o~ water containing 0.1 percent of polyoxyethylene ~orbitan mono-laurate.
In the following table setting ~orth the results o~ the evaluation, column 1 gives the name o~
the compound under test; column 2, the rate in pounds per acre at which the compound was applied to the test flat; and the remaining columns~ the in~ury to the particular plant seeds or seedlings as measured by the ~oregoing scale.

X-3277~ -23-06~4S9 a ,1 ~ r~ ~ ~.
~ .
.,~
~ .
X N N ~ ~ ~1~ N

b ~ ~ :1- ~t .,1 P~

V ~ ~ ~ ~ ~N ~ CU ..

a~ a~ l h a o ,1 o~ N I ~1 0 0 ~ ~q , .:
h ;~
H O
~ h o o o ,~ o , ,~ o ,~
El ~
o b~ ~ , h ,1 ~1 ~1 0 ,~ O O O

h h al :: .~ ¢
H u a~ a~ ao CD 0 ~ CU ~1 ;~ _~
. .
h I O I a ~i O o _I I h _I r-l H 0 ~ I 1/~ 0 0 h~l ~ h 01 0 h h h h ~: Id I h ~
,s~ ~ O rl h^ o 0 ~ 0 o a ~1 ~ 0 0 ~
U ~d 0 U h ~rl q-l 0 ,s:~ U r1 1~ 0 ~rl l~J h rl ~J O E3 rl ~3 P
O ~ ~:1 0 ~1 0 h ~ I O rl ~ I O -1 h 0 al h ~ ~ ~ ~ ol h h 0 I~-rl h ~
O ~ 1:~ 0 c~ - I O
:~ ~ a~ a~ 0 ~ o ~ ~
,~ - 01 ~ q~ ~O h q~ u~ a~ ~^ ~ 0 q~ h w Pll~ 1 0 :~ ~ o I
O h - a~ h O h OJ h O ~-1 h 0 0 CU h O
E~ l h ~ æ ~ ~ ~ E~ h .c ~ o h ~3 ~ 0 ~1 : o ~ ol ~ a~ CU5 ~ a ol 's'z X-3277:B -2)1-Representative compounds of formula I, II, or III were evaluated for postemergent applicatio~ to plants including corn and several weed species. The evaluation was carried out in accordance with the previous test procedures except that the test solutions were applied about 9-12 days after the preparation and seeding of the flats. The results are as set forth in the following table:

X-~277B -25-~060~s9 ` `:
~:
~:

::~
::
~l X ~ ~' `::

~ p~ ~ ~:
E~ : ' ~ ~ :
~ h H 0 ~3 ~ ~ ~ :1 ,$ ~ ~ :1 .:t ~ :t li!l ~ h .
~ O
~ ~ ~' ~
a ~o ~ ,~ N ~
.
~; a~
h h C~
oq c~ ~ CU ~ ~ CU~ ~J

~: H ;~
~: I I I ~ . ~. ' 0~10 ~ I ~ ..
~: ~ . h ~b ~3 ,I h I
- ~ d ~ I ~ 0 ,: : ~ ~ ~ O I
h- 0 ol o Ir~ ,l ~.
~ ol~ R~ o I ~1 0 ~
H H~I H h .-1 ~ h 0 .~ 0 ~d ,1 0 R ~ ~ I
o a~ 1 0 1 ol ~ ~ o Eo~aO~ 1 ~: ~ hh 01 ~ ~ l ~ I h O O Q~ O I
o U~ ,l , 0 R q~ ~ q ~ m ~ q) cu ~ ~ 0 I I 0 _~ ~. o o . O h b ~rJ h ~ ~ E3 h N
Pl E~ --p, o E3 ~ ` 1 0 1 0 :~
. O rl - R l - rl - .q rl h ~1 ~rl C) ~ Z ~

X- 3277~ - 26-1(~6Q4S9 N2-(2,2,3,3-Tetrafluoropropionyl)-Nl-methoxy-carbonyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine was evaluated as a postemergent herbicide. The e~alu-ation was carried out in accordance with the test pro-cedures de 8 cribed hereinbefore, but with a 8 ingle, higher application rate (15 pounds per acre~ and with different species (tomato, crabgrass, pigweed). The specified compound gave a complete kill of each Or the named specieR. The above de~cribed herbic~dal .compounds can be formulated and employed with known herbicides of other classes. The ratio of the individual components ..
of such composit1ons to one another is not critical;
all ratios provide compositions that have userul plant growth alterlng properties. However, generally pre-~erred compositions are those ~hereln a ~ubstantial portion of each component is present--such as compo-sition~ wherein the ratio of the components ranges from 1:10 to 10:1, especially from 1:5 to 5:1.
Known herbicides with which the compounds of ~ormul~ I, II or III are preferably combined include:
N,N-di-n-propyl-2,6-dinitro-4-(trifluoromethyl) aniline, N,N-di-n-propyl-2,6-dinitro-4-methylaniline~ -::~; N-ethyl-N-butyl-2,6-dinitro-4-(trifluoromethyl) aniline, N,N-di-n-propyl-2,6-dinitro-4-(methylsulfonyl~
:~ : aniline, N,N-di-n-propyl-2,6-dinitro-4-sulfamoylaniline, N,N- al- _- propyl-2~6-dinitro-4-isopropylanil~ne~

.
X-3277B , -27-1(1604S9 :

N,N-di-n-propyl-2~6-dinitro-4-tert-butylaniline~

and N,N-bis(2-chloroethyl~-2,6-dinitro-4-methylaniline.

These possible combinations are exempllfied by the following procedure:

The combination Or Nl-(pentafluoropropionyl)-3'-nitro-5'-(tri~luoromethyl~-o-phenylened~amine and N,N-di-n-propyl-2,6-dinitro-4-(trlfluoro~nethyl)aniline was evaluated for preemergent application, employing ~arious species Or plants.
A soil was prepared consisting o~ one part masonry sand and one part shredded top soil blended together in a cement mixer. one gallon of thls ~oll ~a~ then placed in a 21 5 x 31 5 cm. gal~anized ~lat and was patted down with a bench brush until le~el Rows were marked, and seeds planted, one species to a row, except that in the case o~ the mixture, the mixture was ,.~ . . .
likewiRe seeded in one row The ~pecies employed were cotton (two separate rows), morning glory (I~omea ~ 20 ~urpurea), foxtail millet, ~imsonweed, velvetleaf, and a mixture o~ ~ickle pod, pigweed, cypressvine morning glory (I~omea quamoclit), and Crotolaria.

:: ~
A treated cover soil was then prepared. The compounds were separately formulated by suspending each in a 1:1 solution of acetone and ethanol containlng a small amount of a blend of two sulronate-nonionic sur-factants. Each suspension was then further diluted :
serially with an aqueous solut~on of the same blend Or surractants--to prepare a plurality of aqueous treatlng .

~. . . . . . .

solutions containing the respective compounds in various concentrations, in addition to the blend of eurfactants uniformly in a total concentration of 0.55 percent, and the acetone and ethanol uniformly each in a concentration of 4.15 percent Treating solution containlng each of the compounds were sprayed onto a portion Or soil of the same type as described above, while rotating ln a ceme~t mixer. The rotation was continued for 5-7 minutes.
Each portion of soil so treated was then spread over a flat to a depth of three-eighths inch.
Another flat was prepared and seeded in like manner, except that the cover soil was left u~treated to serve as a control All ~lats were held for thlr-teen days under normal greenhouse condltions, at which time ln~ury ratings and observations as to type of in~ury were made. The in~ury rating ~cale used was as follows:
0-----no in~ury 1-3---slight in~ury 4-6---moderate in~ury 7-9---severe in~ury lO----death B-----burned N-----no germination R-----reduced germination S-----stunting The following table reports the results of the evalu-ation of the treated flats. In the control flats, there were healthy stands of each of the test species.

~ '.' H O O O N 1~ 0 0 ~
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c~ ¢ ¢ ¢ ¢ ~¢ ¢ ¢ ~ ¢ m X- 3277B ~ 30-~()60459 ~ ike results are achie~ed when combining Nl-(pentafluoropropionyl~-3'-nitro-5'-(trifluoromethyl)-o-phenylenediamine or other of the novel compounds Or formula I, II, or III with other of the dinitroaniline compounds identified hereinabove. In general, good results are obtained when the combinations are employed to supply from 0.5 to 8.o pounds of the N-(2,2-di-fluoroalkanoyl~-o-phenylenediamine per acre, and from 0.25 to 2.50 pounds of the dinitroaniline per acre.
Essentially the same results as those re-ported in ~oregolng test~ are obtained ~hen e~aluating the iollowing other representative compounds of formula I, II or III:
Nl-Propionyl-NZ-(2,2-diiluoro-~-iodopropiongl~-

5'-(_ec-~utyl~ulfonyl~-o-phenylenediamine N -Triiluoroacetyl-N2-~-toluoyl-5',6'-di-chloro-o-phenylenediamine : N -Diiluorochloroacetyl-N2-hexanoyl-5'-(n-propyl 8ul ionyl~ phenylenediamine N -(3-Bromopropionyl~-N2-triiluoroacetyl-5'- .:
(ethylsulionyl~-o-phenylenediamine : :
N -(2,2-Difluoro-3-bromopropionyl~-N2-(2- :
chloro-4-tert-butylbenzoyl~-3'-nitro-5'-triiluoromethyl-o-phenylenediamine N -Triflu-oroacetyl-NZ-(methoxycarbonyl)-5',

6'-di~luoro-o-phenylenediamine N -Difluorochloroacetyl-N2-(phenoxycarbonyl)-; 3'-nitro-5'-(difluoromethyl~-o-phenylenediamine : X-3277B -31-1(~60459 N -Difluoroacetyl-N2-(~;~4-dichlorobenzoyl)-4'-chloro-o-phenylenediamine N -Pentafluoropropionyl-N -(5-bromo-m-toluoyl)-3',~',5',6'-tetrachloro-o-phenylenediamine .
N -Heptafluorobutyryl-N2-(sec-butoxycarbonyl)-4'-bromo-o-phenylenediamine Nl-Iodoacetyl-N2-trifluoroacetyl-5'-(methyl-sulfonyl)-o-phenylenediamine Nl-Trifluoroacetyl-N2-naphthoyl-3'-nitro-5'-tri~luoromethyl-o-phenylenediamine N -Trifluoroacetyl-N2-(~-n-butoxybenzoyl)-4'-tri~luoromethyl-6'-nitro-o-phenylenediamine Nl-Trifluoroacetyl-N2-(~-nitrobenzoyl)-4'-trifluoromethyl-6'-nitro-o-phenylenediamine Nl-Tri~luoroa¢etyl-N2-(2,4-dichloro-6-methoxy-benzoyl)-6'-nitro-o-phenylenedlamine Nl-Heptafluorobutyryl-3'-nitro-5'-trirluoro- .
~: methyl-o-phenylenediamine . .
Nl-Pentarluoropropionyl-3'-nitro-5'-tri-~luoromethyl-o-phenylenediamine N -Trifluoroacetyl-NZ-methoxycarbonyl-4'-trlfluoromethyl-6'-nitro-o-phenylenediamine N -Pentadecafluorooctanoyl-3'-nitro-5'-: trifluoromethyl-o-phenylenediamine Nl-Trifluoroacetyl-N2-benzoyl-3'-trirluoro-methyl-5'-nitro-o-phenylenediamine Nl-Trifluoroacetyl-N2-naphthoyl-4'-trifluoro-methyl-6'-nitro-o-phenylenediamine ~ , ' ' :, ~' ', . ;
: X-32773 -32-: ~ :

1060~S9 N -Trifluoroacetyl-N2-trichloroacetyl-3'-nitro-5'-(methylsulfonyl)-o-phenylenediamine N -Pentadecafluorooctanoyl- ~-acetyl-4'-(methylsul~onyl)-o-phenylenediamine N ,N2-Bis(heptafluorobutyryl)-4'-(methyl-8ulfonyl)-Q-phenylenediamine N -Trifluoroacetyl-N2-acryloyl-4'-(methyl-sulfonyl)-o-phenylenediamine Nl-Trifluoroacetyl-N2-propioloyl-4'-(methyl-æulfonyl)-o-phenylenediamine Nl-Trifluoroacetyl-N2-benzoyl-4'-(ethyl-sulfonyl)-6'-nitro-o-phenylenediamine Nl-pentafluoropropionyl-NZ-naphthoyl-4'-~methylsulfonyl~-Q-phenylenediamine Nl-Difluoroacetyl-N2-methoxycarbonyl-4'-(methylsulfonyl~-o-phenylenediamine N -Heptafluorobutyryl-N2-~-toluoyl-4'-(methylsulfonyl)-6'-nitro-o-phenylenediamine N -Tri~luoroacetyl-NZ-benzoyl-4',5'-dichloro-o-phenylenediamine N -Trifluoroacetyl-N2-naphthoyl-4'-nitro-o-phenylenediamine Nl-Trifluoroacetyl-N2-furoyl-5'-(methyl-: sulfonyl~-o-phenylenediamine N -Chlorodifluoroacetyl-N -furoyl-4',5'-dichloro-Q-phenylenediamine The compounds of formulae I and II also exhibit insecticidal and arachnicidal activity. This activity is most pronounced among compound~ of formula II. These compounds are useful for the control of insect and arachnid pests and, with proper selectlon of rates to avoid phytotoxicity, can be used for the control of those insect and arachnid pests found on the roots or aerial portion of plants. These compounds are active, ~or example, against such arachnids as red spider mlte, citrus mite, two-spotted spider mite, Pacific mite, clover mite, fowl mite, various species Or ticks, and various species o~ spiders. The compounds of this sub-genus are also active against insects of the variousorders including Mexican bean beetle, boll weev~l, corn rootworm, cereal leaf beetle, flea beetles, borers, ~olorado potato beetle, grain beetles, alfalfa weevil, carpet beetle, con~used ~lour beetle, powder post beetle, wireworms, rice weevil, rose beetle~ plum curculio, white grubs~ melon aphid, rose aphid~ white fly, grain aphid, corn leaf aphid, pea aphid, mealybugs, scales, leafhoppers, citrus aphid, spotted alfal~a aphid, green peach aphid,~bean aphid, milkweed bug, tarnished plant bug, box elder bug, bed bug, squash bug, chinch bug, house fly, yellow fever mosquito, stable fly, horn fly, cabbage maggot, carrot rust fly, Southern armyworm, codling moth, cutworm, clothes moth, Indianmeal moth~
leafrollers, corn earworm, European corn borer, cabbage looper, cotton bollworm, bagworm, sod webworm, fall armyworm, German cockroach, and American cockroach.
In addition to utilization for the control of pests on plants, the compounds of this sub-genus can also be included in inks, adhesives, soaps, polymerlc "

. .

materials, cutting oils or in oil or latex paint.~. Also, the products can be distributed in textiles, cellulose materials, or in grains, or can be employed in the impregnation of wood and lumber. Additionally, they can be applied to seeds. In yet other procedures, the products can be vaporized or sprayed or distributed as aerosols into the air, or onto surfaces in contact with the air. In such applications, the compounds manifest the useful properties hereinbefore described.
The process of using these insecticidal and arachnicidal compounds comprises contacting an insect or arachnid with an inactivating amount of one of the compounds of the present sub-genus. Contactlng c~n be effected by application of one or more of the pro-ducts to a habitat of the insect or arachnid. Repre-sentative habitats include soil~ air, water, food, vegetation, inert ob~ects, stored matter such as grains, and other animal organisms. The inactivatlon can be lethal, immediately, or with delay, or can be a sub-lethal one in which the inactivated insect or arachnid is rendered incapable of carrying out one or more of its normal life processes. Among known insecticides, this latter situation typical~y prevails when one of the syætems of the organism, often the nervous system~ ls seriously dixturbed; however, the precise ~echanism by which the compounds constituting the present active agent work is not yet known, and the insecticidal and arachnicidal effectiveness is not limited by any mode of operations.

X-3277B _35_ , , ~ ~ - . . ; ~. . .

~(~6~459 The utilization of an inactivating amount o~
one of the compounds of the sub-genus is critical to the insecticidal and arachnicidal effectiveneæs. The in-activating amount can sometimes be administered by em-ploying the compound in unmodified form. Frequently, however, the desirable insecticidal and arachnicidal properties of the compounds of the sub-genus can be utilized only, as in the instance of the herbicidal properties, when one or more of the compounds is formu-lated with one or more ad~uvant substances. Reference is made to the discussion hereinbefore concerning com-positions and adjuvants. Where the insecticidal and arachnicidal compound~ of formulae I and II are used for the control of plant-attacking insects and arach-nids, it is pre~erred that any ad~uvants be essentiQlly non-phytotoxic in the formulated composition.
The exact concentration of one or more of the compounds of the sub-genug in a composition thereof with one or a plurality of ad~uvants can vary; it is necessary only that one or more of the products be present in such amount as to make po3sible the applica-tion of an inactivating do~age to an insect or arachnid.
- In many sltuations, a composition comprising 0.000001 percent of the active agent is effective for the ~administration of an inactivating amount thereof to insect and arachnid pest organisms. Compositions having a higher concentration of active agent, such as a con-centration of from 0.000001 to 0.5 percent, can of couræe be employed. In still other operations, 10~0459 compositions containing from 0.5 to 98 percent by weight of one compound or from 0.5 to 98 percent of a total of more than one compound, are conveniently em- -ployed. Such compositions are adapted to be employed as treating compositions and applied to insects and arachnids and to their habitats, or to be employed as concentrates and subsequently diluted with additional -adJuvant to produce ultimate treating compositions.
one or more of the compounds of the sub-genus or a composition containing one or more of the compounds is applied to the pest~ to be controlled directly, or by mean~ of application to a portion or portions of their habitat in any convenient manner, for example, by means of hand dusters or spragers or by simple mixing with the food to be ingested by the organisms. Application to the foliage of plants i8 conveniently carried out with power dusters~ boom sprayers, and fog sprayers.
In such foliar applications, the employed compositions should not contain any appreciable amounts of any phytotoxic diluents. In large-scale operatlons, dusts, or low-volume sprays, can be applled from an airplane.
Also~ the use of compositions comprising one or more of - -the compounds of the sub-genus, an ad~u~ant, and one or more biologlcally active materials, such as other lnsecticides, fungicides, miticides, bacterlcides, and nematffcides are po~Rible.
Compounds e~aluated for the control of insects and arachnids, as reported in the following tests, were for~ulated ln accordance with the following procedure.
.

~ .

, . . ' .. ' ' ' . . . . . ~ A . .

~(~60459 Initially, 55 grams of a mixture of two nonionlc sul-fonate emulsifiers were mixed with 1 liter o~ cgclo-hexanone. Of the resulting mixture, 0.9 milliliter was subsequently further mixed with 90 milligrams o~ the sub~ect compound and diluted with distilled water to 90 milliliters, containlng the sub~ect compound at a con-centration of 1000 parts per million. For evaluation at lower concentrations, the mixture was further diluted with a dilution composition consisting o~ 4 liters of distilled water and a total of 1.8 milliliter Or the same two nonionic sulfonate emulsifiers.
~ he insecticidal and arachnicidal activity of the compounds of formulae I and II are illustrated by the following tests against repre~entative insects and arachnids.
Mexican Bean Beetle -E~ilachna varivestis (Coleoptera~
Cuttings of four six-day-old Bountliul snap bean plants containing two leaves with approximately 5 square inches of leaf surface were placed in water.
~he leaves were ~prayed to wetting with about 5-10 ml.
of a formulation containing a predetermined level of ; the test compound. Half of the formulation was sprayed ~ on the top surface and half on the bottom ~urface Or the ; leaf using a DeVilbiss atomizer at 10 pBi held at a distance of about 18 inches from the leaf. After the ; leaves had dried, they were cut from the stem and placea separately in petrL dishe~ Ten third instar, non-molting Mexican bean beetle larvae grown on Bountirul ,:

. . . . . . .

1(~604S9 snap beans were placed on each leaf. Controls consisted of two leaves sprayed with 5 ml. of a 500 ppm. formula-tion of S-(1,2-dicarbethoxyethyl~ 0,0-dimethyl phos-phorodithioate (reference standard), two leaves sprayed with the formulation without the active ingredient and two leaves were held as untreated controls. After 48 hours J a mortality count was made and the amount of feeding noted. Moribund larvae were countea as dead.
The following toxicity rating scale was used:
10Percent Dead Rating ~2I-30 2 The compounds so evaluated, the rates employed?
and the results of the evaluation are as set forth in . ~, the following table. Where more than one evaluation was carried out at a gi~en rate, the result reported for that rate is an a~erage of the several results.

,, , X-~277B _39_ ~: :
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, ~ ~ X- 3277B _ 40_ 106(~4S9 Southern Armyworm -Prodenia eridania (Lepidoptera) Ten uniform Southern armyworm larvae about 1-1.5 cm in length, grown on Henderson lima bean~, were placed on excized bean leaves in petri dishes. The bean leaves were obtained and sprayed with the insecticide in the same way as were the snap bean leaves in the Mexican bean beetle test. The reference standards in this instance were leaves sprayed with 5 ml. of 100 ppm. DDT
solution. Mortality counts were made 48 hours after spraying and again moribund larvae were counted as dead.
Mis~ing larvae which had probably been eaten were considered alive. The same rating scale was used as in the Mexican bean beetle test The compounds 80 eraluated, the rates em-ployed, and the results of the evaluation are a~ set forth in the following table. Where more than one -evaluation was carried out at a given rate, the result reported for that rate is an average o~ the 8e~eral re~ults TABLE V

Toxlcity Rating Rate in Parts Against Southern N -Difluorochloro- 1000 8.5 acetyl-3'-nitro-5'-trifluoromethyl-o-` phenylenediamine .. .. . . . . _ _ .

Melon Aphid -A~his ~ossY~ii (Hemiptera) ~ X-3277B 41-.~ ; .

Four blue hubbard squash seeds were planted per container in vermiculite and the containers watered from the bottom. A~ter six days, the two weakest plants were cut of~ and one cotyledon and the primary leaves removed from each of the two remaining plants. The remaining cotyledon was in~ested with 100 melon aphids ~rom a stocX colony by pinning the cotyledon against an aphid-infested squash cotyledon from the colony and allowing the aphids to trans~er. After transfer, the colony leaf was removed. Forty-eight hours later~ the ~ -infested leaves were sprayed to wetting with rormulations containing graded amounts Or the insecticide using a DeVilbiss atomizer at 10 psi held at 12-15 inches from the plant. Controls consist o~ two infested, unsprayed ~quash plants and two in~ested plants 8prayed to wetting with a formulation containing 100 ppm. Or S-(1,2-dicarb-ethoxyethyl) 0,0-dimethyl phosphorod1thioate as a referenoe standard. The mortality was estimated 24 hours after spraying by observation using a 10-power dissecting microscope. The same rating scale was used as before The compounds so evaluated, the rates employed, and the results of the evaluation are as set forth in ~ .
;~ the ~ollowing table. Where more than one evaluation was carried out at a given rate, the result reported for that rato is an average Or the several results.
~ .
, .

~:

: .
. ~ . .

1060~59i TABLE VI
Toxicity Rate in Parts Rating Against Compound Per Million Melon Aphid N1-Trifluoroacetyl-3'-1000 9.0 nitro-5'-trifluoro-methyl-o-phenylene- 500 9.0 diamine 250 9.0 100 8.o

7.0 N -Difluorochloroacetyl- 1000 9.0 3'-nitro-5'-trifluoro-10 methyl-o-phenylene_ 500 g.o diamine 100 8.
Nl-Trifluoroacetyl-3'-1000 9.0 trifluoromethyl-5'-nitro-o-phenylenediamine 500 9,0 250 9~0 : :

Two-Spotted Spider Mite -TetranYchus urticae (Acarina~
Two-æpotted spi-der mites were raised on green ~- bean plants, then transferred to squash plants. The squash plants were maintained for two days 80 that the ,- ~
, infestation was well established. The lnfected squash plants were then sprayed with a test formulation con-taining the sub~ect compound as in the preceding test methodæ. Mortality was determined by estimation 48 ~ ~ -houre after spraying. The same rating scale wa8 u8ed a8 in other test procedures.
The compounds 80 evaluated~ the rates em-ployed, and the reæultæ of the evaluation are as set ~ .

., , : : .

forth in the following table.

TABLE VII
Toxicity Rating Rate in Part~ Aeainst Two-CompoundPer Million Spotted S~ider Mite Nl-Trifluoroacetyl-1000 9.o 3'-nitro-5'-tri-fluoromethyl-o- 500 g.o phenylenediamine 250 9.0 100 9- "
5 8.5 Nl-Pentafluoro- 1000 9.0 propionyl-3'-nitro- ::
5'-trifluoromethyl-500 9.0 o-phenylenediamine 250 9- ::
100 9~
5 8-5 ::
Nl-Difluorochloro-1000 9.0 acetyl-3'-nitro-5'-trifluoromethyl-o-500 g 0 phenylenediamine 100 8.o 5 9 `
Nl-Trifluoroacetyl-1000 9.0 ~:: 3'-trifluoromethyl-5'-nitro-o-phenylene-500 9.0 diamine ' 100 9.0

8.o : : :

:: :
,, X-3277B _44_ -Milkweed Bug -Oncopelitis fasciatus (Hemiptera~
Ten adult milkweed bugs were chilled and placed in a test cage. The cages containing the bugs were sprayed with 5 ml. of a test formulation containing a predetermined amount of the insecticide, using a DeVilbiss atomizer at lO psi held 33 inches from the top of the cage. After the cage had been allowed to dry, the bugs were fed and watered for 48 hours A formulation containing 500 ppm. of 2-(1,2-dicarbethoxyethyl) 0,0- ;
dimethyl phosphorodithioate was used as a reference standard and two unsprayed cages were kept as controls.
Mortality counts were made 48 hours a~ter spraylng.
Moribund adult8 were considered dead. The 8~me rati~g ~cale Was employed as be~ore.
The compounds 80 evaluated, the rates employed and the results of the evaluation are as set forth in the following table.

TABLE VIII
Toxicity Rate in Parts Rating Against Com~ound Per Million Mil~weed Bu~
N -Trifluoroacetyl- lOOO 9.0 3'-nitro-5'-trifluoro-methyl-o-phenylene- 500 9.0 diamine 100 9. 0 .
8 . o Nl-Difluorochloro- 1000 9.0 acetyl-3'-nitro-5'-trifluoromethyl-o- 500 g o phenylenediamine X-3277~ -45-TABLE VIII (cont'd) Toxicity Rate ln Part6 Rating Against Com~ound Per Million Milkweed Bu~

Nl-Difluorochloro- 100 9.0 acetyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine N1-Trifluoroacetyl-3'-1000 9 trifluoromethyl-5'-nitro-o-phenylene- 500 9.0 diamine 250 9.0 Nl-Heptafluorobutyryl- 1000 9. 0 3'-nitro-5'-trifluoro-methyl-o-phenylene- 500 g,o diamine 250 9.0 100 9~
g.o House Fly -Musca domestica (Diptera) Rearing cages containing four-day-old adult house flies were chilled at 2-4C. for about 1 hour.
One hundred flies were transferred from the rearing cage to each test cage using a small 8COOp. The caged flies were kept for 1-2 hours at 21-27C. The cages were sprayed in the same manner as described for the milkweed bug with 5 ml. of the test formulation. Two unsprayed cages were held as controls and two cages were sprayed with a 50 ppm. DDT formulation as a reference stanaard.
Mortality counts were made 24 hours after spraying. All flies that did not fly or did not walk up from tke bottom of the cage were considered moribund. The same .

~060~s9 rating scale was employed as hereinbefore.
The compounds so evaluated, the rates em-ployed, and the results o~ the evaluations are as set ~orth in the followine table. Where more than one evaluation was carried out, the result reported ror that rate is an average o~ the several results.

. ,..-: :

TABLE IX

Toxicity Rate in Parts Rating Against Com~ound Per Million House_Fly : :.
Nl-Trifluoroacetyl- 1000 9.0 3'-nitro-5'-trifluoro-methyl-o-phenylene- 500 9.0 ~-diamine 250 9.0 --100 . 9~ 0 8.5 N~-Difluorochloro- 500 9.0 acetyl-3'-nitro-5i-trifluoromethyl-o- 250 9.0 phenylenediamine -100 9. 0 ':

~~
;~ ~ Boll Weevil -Anthonomus ~randis (Coleoptera) The procedure was identical to that employed for the Mexican bean beetle and the Southern armyworm, except that 10 adult boll weevils were placed on cotton leaves that had been dipped into formulations of the test compounds The same rating scale was used.

~ -:, .
~ X-3277B -47-The compounds so evaluated, the rates -employed, and the results obtained are as set forth in the following table. Where more than one evaluation was carried out, the result reported for that rate is an a~erage of the several results.

TABLE X

Toxicity Rate in Parts Rating Against Com~ound Per Million Boll Weevil _ N -Hepta~luorobutyryl-1000 9.0 3'-nitro-5'-trifluoro- :
methyl-o-phenylene- 500 9.0 diamine 100 9- : '

9.0 9.0 Nl-Pentafluoropropionyl- 1000 9.0 3'-nitro-5'-trifluoro-! methyl-~-phenylene- 500 9.0 d i amine 1: ,.
,, ,, 100 9~

8.5 8.5 Nl-Perfluorooctanoyl-1000 9.0 1~ : 3'-nitro-5'-trifluoro-'~ methyl-o-phenylene- 500 9.0 diamine 5 9.0 g.o , ~ .

X-3277~ -48-.

:~0459 ~:
Results essentially the same as those ~-:
reported in the above tables are obtained when evaluating in the same procedures the following compounds:
N -(2,2-Difluoro-3-bromopropionyl)-N2-(2-chloro-4-tert-butylbenzoyl~-3'-nitro-5'-trifluoromethyl-o-phenylenediamine Nl-Difluorochloroacetyl-NZ-(phenoxy- ~
carbonyl)-3'-nitro-5'-difluoromethyl-o-phenylenediamine ~:
Nl-Trifluoroacetyl-N2-naphthoyl-3'-nitro- : ;
5'-trifluoromethyl-o-phenylenediamine Nl-Trifluoroacetyl-N2-(~-_-butoxybenzoyl)- .
4'-trifluoromethyl-6'-nitro-o-phenylenedia~ine Nl-Trifluoroacetyl-N2-(~-nitrobenzoyl)-4'- . ~ :
tri~luoromethyl-6'-nitro-o-phenylenedlamine Nl-Hepta~luorobutyryl-3'-nitro-5'-tri-~luoromethyl-o-phenylenediamine N -Pentarluoropropionyl-3'-nitro-5'-tri-fluoromethyl-o-phenylenediamine Nl-Trirluoroacetyl-N2-methoxycarbonyl-4'- .-trifluoromethyl-6'-nitro-o-phenylenediamine N -Pentadecafluorooctanoyl-3'-nitro-5'-~; tri~luoromethyl-o-phenylenediamine ; Additionally, the compounds of formula II
are useful parasitlcides for the systemic control of insects and acarina which feed on living tissues o~
animals. ~hese compounds have the ability to permeate the living tissues of a host animal to which one o~
the compounds is administered. Insect and acarina . . . , . . . . .~ .. ... , ~ .. ; . . .. . .

1~)60459 parasites which consume blood or other li~lng ti~sues of the host animal ingest the compounds with which the tissue is permeated, and are thereby killed. It is probable that the blood is the agency through which the compound i6 dispersed through the host animal, but parasites such as screwworms, which do not suck blood, are killed by these compounds, indicating that the compounds permeate other tissue6 as well as blood.
Some parasites, such as most ticks, ~eed on living tissues of the host animal during most of the parasite's life. Other parasites, such as screwworms, ~ -feed on the host only in the larval stage A third group of parasites, such as the bloodsucking flies, feed on animal hosts only in the adult stage. Ad-ministration of the compounds Or ~ormula II to host animals kllls parasltes which feed on the living tissues of thè anima~s, no matter what the life stage o~ the ~eeding parasite.
~ll the ~pecies o~ insect and acarina para-sites which feed on the living tissues of animals are killed by the compounds of formula II. The parasipes which suck the host animal's blood, those which burrow into and feed on the animal's tissue, and those, like the larvae o~ the bot flies, which enter a natural ~- ; ori~ice of the host, attach to the mucous membranes~
and feed there~rom are all equally effectively killed.
For the sake of clarity, a number of specific parasites of various host animals which are controlled by using these compounds will be mentioned. The parasitiG life :: :

X-3277B _50_ : .

` ~0604~;9 stage and the means by which it infests the host animal arc g~ven for each parasite.
Parasites of Horses horsefly, adult, bloodsucking stable ~ly, adult, bloodsucking black fly, adult, bloodsucking horse sucking louse~ immature, adult, bloodsucking : -mange mite, nymph, adult, skin-burrowing scab mite, adult, skin-eating common horse bot rly, larva, migrating in alimentary canal chin fly~ larva, migrating in alimentary canal nose bot ~ly, larra, migrating in alimentary canal Parasites o~ Bo~ines horn fly, adult, bloodsucking cattle biting louse~ adult, skin-eatlng cattle bloodsucking louse, nymph, adult, bloodsucking ; tsetse ~ly, adult, bloodsucking .
stable fly, adult, bloodsucking horse fly, adult, bloodsucking cattle follicle mite, adult, skin-burrowing cattle tick, larva, ngmph, adult, bloodsucking ear tick? nymph, bloodsucking Gul~ Coast tick, adult, bloodsucking .~ Rocky Mountain spotted-fever tick, adult, 30 bloodsucking X-3277B . -51-10fà~459 lone star tick, adult, bloodsucking : --heel fly, larva, migrating through the body bomb fly, larva, migrating through the body blowfly, larva, infesting wounds assassin bug, bloodsucking Parasites of Swine hog louse, nymph, adult, bloodsucking chigoe ~lea, adult, bloodsucking Parasites of Shee~ and Goats bloodsucking body lou~e, adult, bloodsucking bloodsucXing foot louse, adult, bloodsucking sheep ked, adult, bloodsucking sheep scab mite, nymph, adult, skin-eatlng nose ~ly~ larva~ migratlng in the sinuses greenbottle fly, larvaJ infesting wouDds black blowfly, larva, infesting wounds secondary screwworm, larva, infesting wounds Parasites o~ Poultr~
: bed bug~ nymph~ adult, bloodsucking ~ : 20 Southern chicken flea, adult, bloodsucking :
.~ fowl tick, nymph, adult, bloodsucking chicken mite, nymph, adult, bloodsucking :- -scaly-leg mite, adult, skin-burrowlng depluming mlte, adult, skln-burrowlng Paraæiteæ o~ Dogs horse fly, adult, bloodsucking ~ : stable fly, adult, bloodsucking :~ ~ mange mlte, nymph, adult, skln-burrowing dog follicle mite,.adult, burrowing in hair follioles :~ X-~277B 52-~ .

~, . , . " . . ~ , . ~ - . . .

10~;0459 flea, adult, blooasucking It will be understood that the parasites mentioned above are not confined to the single host animal with which each is here identified. Most para-sites inhabit various hosts, although each parasite has a favorite host. For example~ the mange mite attacks at least horses, hogs, mules, humans, dogs, cats, foxes?
rabbits, sheep, and cattle. Horseflies freely attack horses, mules, cattle, hogs, dogs, and most other animals. Use of the compound~ of formula II kllls parasite~ of the types described above growing in the host animals mentioned above, and in other host an~imal~
as well. For example, these compounds are effective in cats, goats, camels, and zoo animals.
The host animals in which the~e compounds are preferably used are dogs, bovines, sheep, or horses for the control of ticks, ~leas, flies, or screwworms.
The time, manner, and rates at which the compound3 are effecti~ely administered may be ~aried over a wide range. Detailed explanation of the ways in which these compounds are used w111 be given herein-below.
The compounds are administered to the animals at rates from about 1 to about 100 mg./kg The best rate for killing a given parasite infesting a given animal must be determined individually, but ~t will be found that in most cases the optimum rate is within the preferred range of from about 2.5 to 50 mg./kg. The optimum rate for a given instance depends on such ; : , ~ X-3277B _53_ .
.
:

iO~;O~S9 factors as the health of the animal to be treated, the susceptibility of the parasite of primary concern, the expen~e which can be borne by the animal~ and the degree o~ control desired. Lower rates are safer ~or the host animal, less expensive, and often easier to adminlster, but are likely to give incomplete or minimu~ control Or the parasite so that reinfestation may occur. On the other hand, higher rates of administration give more complete control of the parasites, but are more ex-pensi~e and may impose a stress on the treated animals.
The compounds of formula II are efrectivewhen administered at any time of year to animals of any age. It is possible to administer these compounds to the anlmal8 contlnuou81y, as by constant feed~ng o~ a diet which contains one of the compounds, and thus assure thàt all parasites which contact the treated animal wlll be killed. Such admini~tration is by no means economical, ~`
and it will usually be found best to administer the compounds at such times as to give the best return of parasite control ror the compound expended. Certain parasites, such aæ cattle grubs, which are the larvae of the heel rly and the bomb fly~ have a known active season when they attack animals. If such a parasite is of primary importance, the compounds can be used , only during thht ~eason with assurance of year-round control Or the parasite. Other parasites, such as ticks, infest and bite animals essentially the year round. Control of such parasites can stlll be accom-plished ~ith relatively brief periods Or administratlon .

~06Q459 by administering the compound to ali t~e animals on a farm or in an area ~or a short period of tlme, such a8 for a few weeks. All the parasites of a generation are ; thus killed, and the animals can be expected to remain parasite-~ree for a considerable length Or time, for example until reinfested by parasites arri~ing with imported animals.
The compounds of formula II may be administered by any of the usual oral and percutaneous routes. It should be noted that many of the compounds are chemically ~ changed by passage through the rumen of a ruminant r animal. Oral administration to ruminant animals is therefore advisable only ir the compounds are protected ~rom the rumen en~ironment by a special formulation. Such ~ormulatlons wlll be dlscussed below ~he formulation and administration to animals of biologically-effecti~e compounds is a ~ery old and ; developed art. Some explanation of the di~ferent formulations and methods of administration will be given to enable all to practice parasite control using these compounds.
; -Percutaneous administration of formula II compounds is carried out in the ways usual in ; the animal veterinary art. It is convenient to use a . ~
~ater-soluble salt of the compound of formula II, so that no elaborate formulation is required. On the other hand, if a water-insoluble compound is desired, I ~ ~ it is practical to dissolve the compound in a physio-logically-acceptable solvent, such as the polyethylene glycols. It is likewise practical to formulate ¦ X-3277B -55-~ , , ,, . . , , . ,. , , ~,. .. . . . . . . .

an injectable suspension o~ the compound as a fine powder, ~uspended in a formulatlon of physiologically- -acceptable nonsolvents~ surfactants, and suspending agents.
The nonsol~ent can be, for example, a vegetable oil such as peanut oil, corn oil or sesame oil, a glycol such as a polyethylene glycol, or water, ~-`
depending on the compound chosen.
Suitable physiologically-acceptable ad~uvants ~;
are necessary to keep the compound o~ ~ormula II sus-pended. The ad~uvants can be chosen from among the emulsi~iers, such as salts Or dodecylbenzene sulrate and toluenesul~onate, ethylene oxide adducts of alkylphenol~ and oleate and laurate esters~ and from the dlspersing agents such as salts o~ naphthalene-sulronate, lignin sul~onate and fatty alcohol sul~ates.
Thickeners such as carboxymethyl cellulose~ polyvinyl-pyrrolidone, gelatin and the alginates are also used as adjuvants ~or ~n~ectable suspensions. Many classe~ of surfactants, as well as~those which have been discussed above, serve to suspend the compound. For example, ~ lecithin and the polyoxyethylene sorbitan esters are I ~ useful sur~actants.
. ~
Percutaneous administration is conveniently accomplished by subcutaneous, intramuscular, and even ntravenous in~ection o~ the injectable formulation.
Conventional needle-type in~ection aevices as well as needle-less air-blast in~ection devices are useful.
It is possible to delay or sustain the ,:1 permeation o~ the compound of formula II through the x-3277B -56-. ~
, ;
1~ .

~06Q459 animal'~ living tissues by proper formulation. For example, a very insoluble compound may be used. In that event, the slight solubility of the compound causes sustained action because the body fluids of the animal can dissolve only a small amount of the compound at any one time.
Sustained action of the compound~ of formula II can also be obtained by formulating the compound ln ~-a matrix which will physically inhibit dissolution.
The formulated matrix is in~ected into the body where it remains as a depot from which the compound slowly dissolves. Matrix formulations, now well known in the art, are formulated in waxy semisolids such as ~egetable WaXes and high molecular weight polyethylene glycols Even more effective su~tained action is ob-tained by introducing into the animal an implant containing one of the compound~ of formula II. Such implants are now well known in veterinary art, and are usually made of a silicone-containing rubber.
The compound is dispersed through a solid rubber implant or is contained inside a hollow implant. Care must be taken to choose a compound which is soluble in the rubber from which the implant is made, ~ince it is dis-persed by first dissolving in the rubber, and then ~:
leaching out of the rubber into the body fluids o~ the treated animal.
The rate at which the compound is released from an implant, and hence the length of time during , which the implant remains effective, is controlled with X-~277B -57-. .

.

~O~U459 good accuracy by the proper ad~ustment of the con-centration of the compound in the implant, the external area of the implant, and the formulation of the polymer from which the implant is made.
Administration of the compounds by means of an implant is a particularly preferred embodiment. Such administration is highly economical and efficacious, because a properly designed implant maintains a constant concentration of the compound in the tiæsues of the host animal. An implant can be designed to supply compound for several months, and is easily inserted in the animal.
No further handling of the animal or concern over the dosage is necessary after the insertion of the implant.
Oral administration of a compound of formula II may be performed by mixing the compound in the animal's feed or drinking water, or by administering oral dosage ~orms such as drenches, tablets, or capsules .
When a compound of formula II is to ~e ad- ;
ministered orally to a ruminant animal, it is necessary to protect the compound from the deleterious effect of ; the rumen processes. The veterinary art is now aware of effective methods for coating and en-~ ~ .
capsulating drugs to protect them from the rumen. For example, coating materials and methods are disclosed in Grant et al., U.S. Patent No. 3,697,640. Grant teaches a method of protecting substances from action : ~ . ..
` of the rumen by coating the substances with a film of cellulose propionate 3-morpholinobutyrate. Such a film can be used to protect the compounas of formula II.
.

X-3277B -58_ ~ .

iO604S9 Conveniently, tablets, or capsules containing a compound of formula II are coated with the film in a coating pan ~ -or a fluidized bed spray apparatus. Pellets of the parasiticide may be made, coated with the film, and filled into capsules. Alternatively, a solid mixture of the compound and the film-forming agent may be made and broken or ground into small particles, each of which comprlses the compound enclosed in a matrix of the film-forming agent. The particles may be filled into cspsules for oral administration9 or made into an oral suspension.
The formulation of veterinary additives in animal feed is an extremely well-known art. It i9 u8U
to formulate the compound first as a premix in which the compound of formula II is dispersed in a liquid or particulate ~olid carrier. The premix may con~eniently contain from about 1 to 400 g. of compound per pound, depending on the desired concentration in the feed. As the art is aware, many compounds of formula II can be hydrolyzed or degraded by constituents of animal feed.
Such compounds are routinely formulated in protectire matrices such as gelatin before addition to the premix.
The premix i8 in turn formulated into feed by dis-persing it in the feed mixture in a conventional mixer.

, ~ ~
The correct amount of compound, and hence of premix, to mix in the feed is easily computed by taking into acoount the weight of the animals, the approximate a-ount each animal eats per day, and the concentration of the compound in the premix.
Likewise, the amount o~ a compound to administer in the drinking water of animals is computed .

l X-3Z77B -59-1~

., ~ : - . , . . ~.
. .......... : . . :

10~(~4S9 by taking into account the animal's weight and the amount each animal drinks per day. It is most convenient to use a water-soluble salt of a compound of formula II as a drinking water treatment. If such a salt is not desired, then a su~pendable formulation Or the desired compound must be made. The formnlation may be a 8U8-pension in the concentrated iorm, which suspension i6 mixed into the drinking water, or may be a dry preparation which is mixed with and suspended in the drinking water.
In either event~ the compound must be in a finely-powdered form, and the formulation follows the same prlnciples discussed above for in~ectable suspensions.
The compounds can easily be formulated into tablets and capsules according to the conventional methods~ about which no teaching i8 required here.
Drench ~ormulations comprise the compound dissolved or dispersed in an aqueous liquid mixture. Aga~n, it is most convenient to make the drench by dissolving a water-goluble salt of a compound Or formula II. It is almost as convenient, however, and equally efficaciou~ to use a dispersion of the compound made in the same way that the drinking water formulations discussed above are made.
The examples im~ediately below show the effectiveness of the compounds of formula II ln con-trolling a number of pzrasites which normally afrect economic animals The compounds were tested again~t screwworms, which are larvae of the black blowfly, ~against the stable fly, against mosquitos, and against X-~277B -60-, 106(~S9 ~:

the adult American dog tick. The blow~ly and stable ~ly are in~ects; the dog tick is representQtive o~ the acarina.
The stable ~ly is a common free-flying, blood~
sucklng parasite; the lone star tick is a typical blood-sucking parasite which spends the nymphal and part Or the adult periods of the li~e cycle attached to the host animal, usually cattle. Blow~ly larvae, or screwworms, hatch ~rom eggs laid near a wound of the host anlmal by the free-flying insect. The lar~ae eat their way into ; the healthy ~lesh exposed by the wound and pass part o~
the life cycle therein, feeding on the host' B rleBh and blood.
The ~table ~ly is parasitic on hor~es, mules, cattle, hogs~ dog~ cats~ sheep~ goats~ rabbits~ and human~. The lone star tick i~ primarily a cattle parasite, but also attacks horses, mules, and sheep.
` ~ Blow~lg lar~ae attack any wounded animal, but are par-ticularly harmful to cattle, hogs, horses, mules~ sheep~ ~ -and goat~.
The following tests illustrate the efficacy the compounds Or ~ormula II when they are ad~inls-tered to cattle. In most instances, the tests reported below were carried out on induced in~e~tations o~ para-~ites.

: , : A calr was treated with 15 mg./kg. Or ~l , (2,~2,3J3-tetrafluoropropionyl~-3'-nitro-5'-trifluoro-methyl-g phenylenediamine a~ a single subcutaneous :: ' injection. The compound was administered as a dis-persion in lO percent polyvinylpyrrolidone.

X-3277~ -61-, , lO~iQ459 Adult stable flies were housed in chambers completely enclosed ln wire screen. Two or more chambers, containing from 60 to 100 stable ~lies, were placed in contact with the clipped back of the calf 24 hours a~ter aaministration of the compound. The flies were left to ~eed on the calf ~or the time indlcated, a~ter which the I chambers were obser~ed and the ~lies were le~t to ~eed j for another time period. The mortality of the flies were ~ determined by countlng the number o~ lire and dead rlies ! lo after the exposure. Each set was run separately.
¦ The mortality results were as follows:

Hours Post- Stable Fly ¦ Set Treatment Mortalit When the abo~e procedure was repeated using mosquitos, rather than stable ~lies~ the result was:
: ~
Hours Post-Set Treatment Mosauito MortalitY

~ '~' hen the abo~e procedure wa~ repeated u~ing ~ ~ 25 mg./kg. in 10 percent poly~nylpyrrolidone, the ; ~ 30 results were:
1~ X-3277B -62_ ;
-.

1()604Sg :

Hours Post-Set Pest ?reatment 1 mosquito 5 75 1 mosquito 24 100 2 mosquito 48 70 3 American dog tick 168 86 N -(2,2,3,3-tetrafluoropropionyl)-3'-nitro-5'-trifluoromethyl-o-phenylenediamine was tested at 10 mg./kg in sesame oil against stable rlies on a cal~.
The procedure was modified from the one described abo~e `
in that the wire chambers ~ere.placed on the back of the : calf 24 hours after àdministration of the compound. The - .~.
results are gi~en in the following table:
TAB L~3 X I
Time Alive ` Dead Percent ...
Day 1 :
6-hours 20 20 50 ~ 24 hours 0 40 100 .- ::
:~ Day 2 6 hours 3 ~7 92 : 2024 hours 0 40 100 . Day 3 6 hours 16 24 60 ..
24 hour~ ; 4 36 90 ; : : Day 4 6 hour.s 10 30 75 24 hou~s 0 40 100 Day 5 :: : 6 hours :24 hours 0 40 100 Day 6 6 hours -- -- __ ~ 24 hours 0 30 100 ~: Dag 7 6 hours. 3 37 93 24 hours 6 34 85 : : ' : ~:
~ X-3277B _~3_ .c i ::
,,,. . . : , ~ , ~ - :: :, . . .

10~0459 Time Alive Dead Percent Day 8 6 hour8 35 5 12 24 hours 15 25 62 Day 9 6 hours 20 10 33 24 hours 0 40 100 Day 10 6 hours 40 0 0 24 hours 40 0 0 ~ -Day 11 6 hours 40 0 0 24 hours 40 0 0 The tests reported immediately above demon-strate the long-lasting control of insect and acarina parasites which is obtained by the use of compounds Or ~ormula II. Administration o~ these compounds, even at quite low rates, has been shown to kill such parasites which ~eed on the treated animals even several days after administration of the compound. It is also notable that the control obtained was very complete, in that all, or essentially all, of the parasite8 whlch fed on the animal were killed.
The ~ollowing prpcedure reports representatlve ¦ results o~ a bio-assay test.
Larvae Or the black blowrly were used as assay organisms in a bio-assay test system. The tests were carried out by administering a compound Or thls in-vention as a single subcutaneous injection to a calr.
Samples of blood were withdrawn from the calf on successive days a~ter the administration of the compound~

and blowfly larvae were fed on the withdrawn whole X-3277B -64_ 1(~60~59 blood. The end point o~ the test was recorded as the last day on which 90 percent or more of the blow~ly lar~ae were killed. The results are gi~en in the following table.

' '" ~' ~, , ~:;; X-3277B -65-.

~ ~O~Q459 a~

h ~ :' o .~.
a1 ..
~rl C
C~ ~I Q~
a) h s~
I~ Co ~1 CO ~o o o o CO o~ CO CO
O
h Q~1 ~`
."

.. ., -_ Y

O U~ U~ O U~ ~ O
OJ CU

O
0 C~
~ h -I o ~ ,1 -d a) ,I d s~ ~
'~ d 5~ o ~ o ~, ~d O ~I h h d ~rl h ~ -1~
a~o ~1 a~ o ~1 o 0 ~3 ~ ha~ h o " a) ~ Oa O h :
1,, I ~ O ~ II
1~ I h ~: 0 U~ 0 h--` O
I O O ~1 a~ h r1 h ~I h h ~ ~ d ~ ~ .~1 ~
~1 I o ~ ~ ~ 0 . s:: ~ri h ~ O ~ al ~rl ~ .~ , h 1 ~3 ~
: O ~ O I I O - O ~J
P ~ - ol :1 ~ h . ~ ' CJ P~ I O a) o ~` o I ,1 ~ ~ ,1 ~ ,1 c~ h o h ~ ~1 h ~I h ~_ o I
,1 ,1 .,1 ~ ~ ~ t) h I

I, X- 3277B - 66-. , .. . .. .. . . . . . - :. .. .. ..

1060gSg An additional in vitro test for evaluating the parasite control of adult stable flies by use of the compounds o~ formula II is described hereinbelow.
Eighteen hour starved adult stable ~lies were placed ln a petrie dish or fly cage and exposed to blood bait pads.
The blood in the pads was collected from treated calves at desiænated time intervals, following treatment.
Mortality of the stable ~lies was determined at desig-nated time intervals after exposure to the blood bait pads. A percent mortality at these times was co~pared to the normal mortality obtained in petrie dishes or fly cages containing blood from non-treated calves (control~. The compound used in this test was N -(2~2,~,3-tetrafluoropropionyl~-3'-nitro-5'-trifluoro-methyl-o-phenylenediamine. The results are given in the ~ollowing table, .~ ~

.

:

' ' .. ~ .. .. , , . ~ . .

.~
td . . .
o .. , -.
~: ,; .
N C~ O O O N ~ O a) CO O O Oo~ CO O CO
C ~1 ~Ir-l ,1 h ~ ~.

~d : ' :
h o ~:1 a~ ~ o . ~-. .
~R ~ O
~o o m ~:
~ U~ ~ ~ C~ ~ ~ ~ ~ ~
u~ I ~ N N ^~ N N CU C~ CU
h ~ : . . -:: ' O o ~
~ P~ . ., H ~
H ~ i:
1 ~ h :',, ~; O I . , .
E l ~1 ~
~1 ~q .. .
O O C~ o C~ 14 t-- t-- C~ O CO
:~ ~ Iq O h .. ~0 ~o , ~, m P::
.

.

: :
~- ~ I ~ U I ~ ~
~ o ~ ~ o ~ . .

bl O ~ ~ O ~ O
0 ~3 ~ h ~ ,~

~ o .,~ h ~ ~ h ,- O U~ 1 0 :: ~ :

X- 3277B - 68_ .

106Q~S9 In the tests described above, the parasites were exposed to the treated animal's blood indirectly, instead of directly by feeding the parasites on the animal. The control obtained, however, i8 obviously as significant as if the parasites had sucked blood directly from the animal. The value in protecting animals from the very injurious parasite, the blowfly, is clearly demonstrated by the tests, since several days of parasite control were obtained from a single administration of a compound Or formula II.
In addition to herbicidal, insecticidal~
and parasiticidal activity, compounds of the pre~ent invention exhibit anthelmintic, and nemato¢idal activity.
The anthelmintic acti~ity is most pronounced among compounds Or ~ormula II. The nematocidal acti~ity ~-ls exhibited by compounds representati~e o~ formulae I, II and III.
In respect to the anthelmintic activity, the compounds Or formula II can be administered to warm-blooded animals for the control of internal parasites,partlcularly parasites of the intestinal tract such as Naemonchus contortus, Syphacia obvelata, and NematosPiroides dubius. Administration is conveniently by the oral route, and may take the form of inclusion .: :
in a diet, or of separate administration o~ the subJect ' compound alone or formulated as a tablet or bolus ~or administration. Typically, good results are obtained .
at dosages of from 5 to 500 mg./kg. for single do~es~
and at dosages of from 0.001 to 0.05 percent in the diet.

: :::

~0604S9 In representative procedures, Nl-trifluoroacetyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine was incor-porated in a modified mouse diet in a concentration of 0 01 percent. The modi~ied diet was fed to a group of four mlce; an unmodified diet was ~ed to another group of ~our mice to serve as a control. The mice of both groups were infected with Nematospiroides dubius about æeven hours after initiation of feeding. Feeding was continued for eight days; on the ninth day, all mice were necropsied and the upper intestines examined to ascertain the presence, and if present numbers~ of NematosPiroides dubius. In the group of mice on the modified diet, no larvae were seen; in the control group, an average of 28 larvae per mouse were seen. Like re8ults are obtainéd with other of the compounds o~
formula II
The compounds of formulae I, II and III can be used for the control of diseasescaused by fungal and nematode organisms such as root-knot nematode, stem nematode, fusarium root-rot, and Rhizoctonia. In general, control is achieved at rates of from 1 to 40 pounds per acre. In standardized testing procedures, ~- the following compounds were found to give complete or essentially complete control of root-knot nematode at the designated application rate:
N -trifluoroaoetyl-3',4',5',6'-tetrachloro-o-phenylenediamine (5 pounds per acre~ - -~ N -trifluoroacetyl- ~ -naphthoyl-4'-tri-- fluoromethyl-6'-nitro-o-phenylenediamine (20 pounds per acre~

~ .
' iO604S9 N -tri~luoroacetyl-N2-(~4-dichlorobenzoyl)-4'-trifluoromethyl-6'-nitro-o-phenylenediamine (20 pounds per acre).
The following examples illustrate the synthesis of the compounds of formulae I, II and III and will enable those skilled in the art to practice the present in-vention.
Example l 3,4,5,6-Tetrachloro-o-phenylenediamine (2.0 grams~ was dissolved in 50 milliliters of benzene and o.8 milliliter of triethylamine and the solution treated with trifluoroacetic anhydride (1.84 grams~.
The resulting reaction ~ixture was then heated to reflux, refluxed ~or 16 hours, condensed by evaporation to 20 milliliter~, and the desired N -trifluoroacetyl-3',4', 5',6'-tetrachloro-o-phenylenediamine product separated by filtration and recrystallized from chloro~orm, m.p., 245-47C.
Example 2 Finely ground 3-trifluoromethyl-5-nitro-o-phenylenediamine (2.2 grams), triethylamine (l.0 ml.), -and chloroform (10 milliliters) were mixed and stirred -~hile trifluoroacetic anhydride (2-3 milliliters in chloroform [20 milliliters]~ was added. The addition was carried out portionwise over a period of 20 minute~
and at room temperature. The resulting reaction mixture was filtered to separate the desired Nl-trifluoroacetyl-3'-trifluoromethyl-5'-nitro-o-phenylenediamine product which was recrystallized from benzene, m.p., 201-02C.
..

~0604S9 AnalYsis~ Calc. for CgH5F6N303 (percent~: C~ 34.o8; H, l.sR; N, 13.24.
Found: C, 34.24; H, 1.60; N, 13.24.
Exam~le 3 3-Nitro-5-trifluoromethyl-o-phenylenediamine ~! (5 0 grams~ was mixed with 15 milliliters of pyridine and the mixture cooled to 0C. Chlorodifluoroacetyl ~ -chloride (3 milliliters) was then added with stirring over a period of 20 minutes. After standing at 20C.
for about 1.5 hours, the reaction mixture was mixed with 150 grams of ice and 20 milliliters of hydro-chloric acid, which resulted in the precipitation of the de~ired Nl-chlorodifluoroacetyl-3'-nitro-5'-trifluoro-methyl-o-phenylenediamlne product. It wa~ separated by ~iltratlon and recrystallized from benzene, m.p., 186-88C.
Exam~le 4 ~ -Benzoyl-6-nitro-4-trifluoromethyl-o-phenylenediamine (3.2 grams) and excess trifluoroacetic anhydride were mixed and allowed to stand o~ernight.
Exce~s trifluoroacetic anhydride and the corresponding by-product acid were evaporated under ~acuum to separate the decired N -trifluoroacetyl- ~-benzoyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine product, which, -after recrystallization from benzene, melted at 193-95C.
.
Exam~le 5 Other compound~ representative of the pre~ent invention are readily prepared in the procedure~ of the ,. . . ... , ~ ~ - - : . . . . .

iO604S9 foregoing teachings and examples, using analogous starting materials. Such compounds include the following:
Nl-Trifluoroacetyl-3'-nitro-5'-trifluoro-methyl-o-phenylenediamine, m.p., 194-95C., prepared by rsacting trifluoroacetic anhydride with 3-nitro-5-trifluoromethyl-o-phenylenediamine.
Nl-Propionyl-N2-(2~2-difluoro-3-iodopropionyl)-5'-(sec-butylsulfonyl~-o-phenylenediamine, prepared by reacting 2,2-difluoro-3-iodopropionyl chloride with N -propionyl-5-(sec-butylsulfonyl)-o-phenylenediamine.
N ,N -Bis(trifluoroacetyl)-5'-(methylsulfonyl)-o-phenylenediamine, m.p , 179-81C., prepared by reacting trlfluoroacetic anhydride with 5-(methylsulronyl)-o-phenylenediamine.
N -Trlfluoroacetyl-N -~-toluoyl-5',6'-dichloro-o-phenylenediamine, prepared by reacting tri-fluoroacetyl chloride with N2-~-toluoyl-5,6-dichloro-o-phenylenediamine.
N -Trifluoroacetyl-N -acetyl-4'-(methyl-sulfonyl~-o-phenylenediamine, m.p., 200-01C., prepared by reacting trifluoroacetic anhydride with N2-acetyl-4-(methylsulfonylj-o-phenylenediamine.
Nl-Difluorochloroacetyl-N -hexanoyl-5'-(n-propylsulfonyl~-o-phenylenediamine, prepared by reacting difluorochloroacetic anhydride with N -hexanoyl-5~(n-propylsulf~nyl~-o-phenylenediamine.
-N -Trifluoroacetyl-3'-nitro-5'-chloro-o-phenylenediamine, m.p., 184-86C., prepared by reacting 30~ trifluoroacetic anhydride with 3-nitro-5-chloro-o-X-3277B _73_ ,~
' ' ' - ~06045;9 phenylenediamine. `
Nl-(3-Bromopropionyl)-N2-trifluoroacetyl-S'-(ethylsulfonyl)-o-phenylenediamine, prepared by reacting trifluoroacetic anhydride with Nl-(3-bromopropionyl)-5-(el:hylsulfonyl)-o-phenylenediamine.
Nl-(2,2-Difluoro-3-bromopropionyl)-N2-(2 chloro-4-tert-butylbenzoyl)-3'-nitro-5'-trifluoro-methyl-o-phenylenediamine, prepared by reacting 2,2-difluoro-3-bromopropionyl chloride with N2 _ (2-chloro-4-tert-butylbenzoyl)-3-nitro-5-trifluoromethyl-o-phenylene-diamine.
Nl-Trifluoroacetyl-N2-(methoxycarbonyl)-5',6'-difluoro-o-phenylenediamine, prepared by reacting tri-fluoroacetic anhydride with N2 _ (methoxycarbonyl)-5,6-difluoro-o-phenylenediamine.
Nl -Difluorochloroacetyl-N2-~phenoxycarbonyl)-3'-nitro-5'-difluoromethyl-o-phenylenediamine, prepared by reacting difluorochloroacetic anhydride with N2 _ (phenoxycarbonyl)-3-nitro-g-difluoromethyl-o-phenylene-diamine.
Nl-Difluoroacetyl-N2-(3,4-dichlorobenzoyl)-` 5'-chloro-o-phenylenediamine, prépared by reacting di-,~ .
fluoroacetic anhydride with N~ - (3,4-dichlorobenzoyl)-5-chloro-o-phenylenediamine.
N - Pentafluoropropionyl-N -(5-bromo-m-toluoyl)-3',4',5',6'-tetrachloro-o-phenylenediamine, prepared by reacting pentafluoropropionic anhydride with ~ q N~ - (5-bromo-_-toluoyl)-3,4,5,6-tetrachloro-o-phenylene- s diamine.
.:
~30 ~ .

; -74-, :, 106045~
Nl-Heptafluorobutyryl-N2-(sec-butoxycarbonyl)-4'-bromo-o-phenylenediamine, prepared by reacting hepta-~ fluorobutyric anhydride with N2-(sec-butoxycarbonyl)-4-bromo-o-phenylenediamine.
Nl-(2,2-Difluoropropionyl)-N2-t3-nitro-5-isopropoxybenzoyl)-5',6'-dichloro-o-phenylenediamine, prepared by reacting 2,2-difluoropropionyl bromide with N2-(3-nitro-5-isopropoxybenzoyl)-5,6-dichloro-o-phenylenediamine.
Nl-Trifluoroacetyl-N2-naphthoyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine, m.p., 200-04C., -prepared by reacting trifluoroacetic anhydride with N2-naphthoyl-6-nitro-4-trifluoromethyl-o-phenylenediamine.
Nl-Iodoacetyl-N2-trifluoroacetyl-5'-(methylsulfonyl)-o-phenylenediamine, prepared by reacting trifluoroacetic anhydride with Nl-iodoacetyl-5-(methyl-sulfonyl)-o-phenylenediamine.
Example 6 Other compounds of formulae I, II and III
prepared by the procedures of the previous examples and discussion are N~-Trifluoroacetyl-N2-(p-_-butoxybenzoyl)-4'-trifluoromethyl-6'-nitro-o-phenylenediamine, m.p., 172-74C.
N -Trifluoroacetyl-N2-(~-nitrobenzoyl)-4'-trifluoromethyl-6'-nitro-o-phenylenediamine, m.p., 210-12C.
Nl-Trifluoroacetyl-N2-(2,4-dichloro-6-methoxy-~benzoyl)-6'-nitro-o-phenylenediamine, m.p., 200-01C.

~.

. .

, .. , ., ~ ~ .. . .- .. .. ... . . .

- ~O~Q459 N -Heptafluorobutyryl-3'-nitro-5'-tri-fluoromethyl-o-phenylenediamine, m.p., 118-20C.
Nl-Pentafluoropropionyl-3'-nitro-5'-tri-fluoromethyl-o-phenylenediamine, m.p., 161-63C.

Nl-Trifluoroacetyl-N2-methoxycarbonyl-4'-trifluoromethyl-6'-nitro-o-phenylenediamine, m.p., 129-30C.
Nl-Pentadecafluorooctanoyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, m.p., 111-13C.

Nl-Trifluoroacetyl-N2-benzoyl-3'-trifluoro- - ' methyl-5'-nitro-o-phenylenediamine.
Nl-Trifluoroacetyl-N2-naphthoyl-4'-trifluoro-methyl-6'-nitro-_-phenylenediamine.
N -Trifluoroacetyl-N2-trichloroacetyl-3'-nitro-5'-(methylsulfonyl)-o-phenylenediamine.
Nl-Pentadecafluorooctanoyl-N2-acetyl-4'-(methylsulfonyl)-o-phenylenediamine.
N1,N2-Bis(heptafluorobutyryl)-4'-(methyl-8ulfonyl)-o-phenylenediamine.
Nl-Trifluoroacetyl-N2-acryloyl-4'-(methyl-sulfonyl)-o-phenylenediamine.
Nl-Trifluoroacetyl-N2-propioloyl-4'-(methyl-sulfonyl)-o-phenylenediamine.
Nl-Trifluoroacetyl-N2-benzoyl-4'-(ethyl-sulfonyl)-6'-nitro-o-phenylenediamine.
~; Nl-Pentaf1uoropropionyl-N2-naphthoyl-4'-~; (methylsulfonyI)-o-phenylenediamine.
Nl-Difluoroacetyl-N2-metho~ycarbonyl-4 ' -:
~ (methylsulfonyl)-o-phenylenediamine.
: :~
.

.

10~04S9 Nl-Heptafluorobutyryl-N2-p-toluoyl-4'-(methylsulfonyl)-6'-nitro-o-phenylenediamine.

- Nl-Trifluoroacetyl-N2-benzoyl-4',5'-dichloro--E~hen~lenediamine.
Nl-Trifluoroacetyl-N2-naphthoyl-4'-nitro-o-phenylenediamine.
Nl-Trifluoroacetyl-N2-furoyl-5'-(methyl-sulfonyl)-o-phenylenediamine, m.p., 185-87C.
Nl-Difluoroacetyl-N2-furoyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine.
Nl-Chlorodifluoroacetyl-N2-furoyl-4',5'-dichloro-o-phenylenediamine.
Nl-(2,2,3,3-Tetrafluoropropionyl)-N2-methoxy-carbonyl -6'-nitro-4'-trifluoromethyl-o-phenylenediamine, m.p., 129-30C.

~ 1-(2,2,3,3-Tetrafluoropropionyl)-3'-nitro-5'-trifluoromethyl-o-phenylenediamine.
Nl-(2,2,3,3-Tetrafluoropropionyl)-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, m.p., 144-45C., prepared by reacting 2,2,3,3-tetrafluoropropionyl bromide with 3-nitro-5-trifluoromethyl-_-phenylene-diamine.

Nl-Pentafluoropropionyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine, m.p., 161-53C., prepared by reactlng pentafluoropropionyl bromide with 3-nitro-5-trifluoromethyl-o-phenylenediamine.

Claims (25)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN
EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED
AS FOLLOWS:

1. A compound selected from the group consisting of the compounds of the formulae:

I.
II . and III. wherein R°0 is a 2,2-difluoroalkanoyl radical of the formula , in which Y is hydrogen, chlorine, fluorine, difluoromethyl, perfluoroalkyl of C1-C6, or a radical of the formula in which each Z independently is hydrogen or halogen and n is 0 or 1;
R1 is hydrogen, a radical of the formula , in which Y1 is C1-C4 alkyl or phenyl, benzoyl, furoyl, naphthoyl, or substituted benzoyl of the formula in which each Z' independently is halo or nitro, Z" is C1-C4 alkyl or C1-C4 alkoxy, p is 0, 1, or 2, q is 0 or 1, and the sum of p and q is 1-3;
R2 is R°, R1, C1-C8 alkanoyl, C3-C4 alkenoyl, C3-C 4 alkynoyl, halogenated C2-C4 alkanoyl bearing on any position or positions one or more halogen atoms, each independently selected, subject to the limitation that the alpha position bear at least one substituent moiety selected from the group consisting of hydrogen and halogen of atomic weight from 35 to 127, both inclusive;
each R3 independently is halogen;
R4 is nitro;
R5 is trifluoromethyl, difluoromethyl, or difluorochloromethyl, and in compounds of formula (II), R4 and R5 are meta to one another;

R6 is C1-C4 alkylsulfonyl and is located at the 4 or 5 position, and any R4 group is meta to R6;
m is from 0-4;
n is 0 or 1; and in compounds of formula (I), the sum of m and n is an integer of from 1 to 4;
subject to the further limitation that where R1 or R2 is hydrogen, the ring position ortho to the -NH-R1 or -NH-R2 group bears one of the designated R3, R4 or R5 moieties.

2. A compound of Claim 1 which is of formula (I).

3. N1-Trifluoroacetyl-3'-nitro-5'-chloro-o-phenylenediamine.

4. N1-Trifluoroacetyl-3',4',5',6'-tetrachloro-o-phenylenediamine.

5. N1-Trifluoroacetyl-N2-(2,4-dichloro-6-methoxybenzoyl)-6'-nitro-o-phenylenediamine.

6. A compound of Claim 1 which is of formula (II).

7. N1-Trifluoroacetyl-3'-nitro-5'-trirfluoro-methyl-o-phenylenediamine.

8. N1-(2,2,3,3-Tetrafluoropropionyl)-3'-nitro-5'- trifluoromethyl -o-phenylenediamine.

9. N1-Trifluoroacetyl-3'-trirfluoromethyl-5'-nitro-o-phenylenediamine.

10. N1-Chlorodifluoroacetyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine.

11. N1-Trifluoroacetyl-N2-benzoyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine.

12. N1-Trifluoroacetyl-N2-naphthoyl-6'-nitro-4'-trifluoromethyl-o-phenylenediamine.

13. N1-Trifluoroacetyl-N2-(p-n-butoxybenzoyl)-4'-trifluoromethyl-6'-nitro-o-phenylenediamine.

14. N1-Trifluoroacetyl-N2- (p-nitrobenzoyl)-4'-trifluoromethyl-6'-nitro-o-phenylenediamine.

15. N1-Heptafluorobutyryl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine.

16. N1-Pentafluoropropionyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine.

17. N1-Trifluoroacetyl-N2-methoxycarbonyl-4'-trifluoromethyl-6'-nitro-o-phenylenediamine.

18. N1-Pentadecafluorooctanoyl-3'-nitro-5'-trifluoromethyl-o-phenylenediamine.

19. N1-(2,2,3,3-Tetrafluoropropionyl)-N2-methoxycarbonyl-6'-nitro-4'-trifluoromethyl-o-phenylene-diamine.

20. N1- Pentafluoropropionyl -3'-nitro-5'-trifluoromethyl -o-phenylenediamine.

21. A compound of Claim 1 which is of formula (III).

22. N1,N2-Bis(trifluoroacetyl)-5'-(methyl-sulfonyl)-o-phenylenediamine.

23. N1-Trifluoroacetyl-N2-acetyl-4'-(methyl-su1fonyl)-o-phenylenediamine.

24. N1-Trifluoroacetyl-N2-furoyl-5'-(methyl-sulfonyl)-o-phenylenediamine.

25. A process for the preparation of a compound selected from the group consisting of the compounds of the formulae:

I.
II.

and III.

wherein the various symbols are defined as in Claim 1, which comprises reacting a compound selected from the group consisting of the compounds of the formulae:

VII.

VIII.

IX. wherein the various symbols are defined as in Claim 1, with an acylating agent of the formula IV. wherein Y is defined as in Claim 1, or the active derivative thereof.