DE2460255A1 - INSECTICIDES - Google Patents

Description

E. I. DU PONT DE NEMORS AND COMPANY 10th and Market Streets, Wilmington, Del. 19898, V.St.A.

SUBSCRIBED

l, 5-diphenyl-3-formazan carbonitriles and containing them

insecticides

The invention relates to substituted l, 5-diphenyl-3-formazanecarbonitrile, some of which are new, useful as insecticides and arachnicides.

Certain 1,5-diaryl-3-formazanecarbonitriles and their preparation were by Nasileva and Ermakova, Zh. Analite. Khim., 19, 1305 (196 * 0, Nineham, Chem. Reviews, 55, 355-483 (1955), Shawali and El-Galil, Tetrahedron, 27, 4305-4316 (197O, Zh. Organ, Khim., 2, 7O8-IO (1966), CA. 65, 8800 (1966); Zh. Org. Khim. 7, 1932-7 (I97I), CA. Jan-Jun 1972 - Chemical Substance Index and Henderson in U.S. Patent No. 3,541,107. However, their properties as insecticides were used and arachnicides as found according to the invention,

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not disclosed for the known compounds.

Insect control is essential for healthy grain growth important factor because insect infestation totally destroys or seriously affects nutrient sources for humans and animals can be; in addition, the maintenance of general health depends in part on proper insect control away. Therefore, there is a continuing need for new products with high activity or better selectivity to regulate the insect population, because with existing ones Products that cannot fully regulate insect populations. The general one depends in the same way Health partially depends on proper arachnid control.

According to the invention, compounds are described which are used for control or regulation of insects and / or arachnids are suitable. These compounds correspond to the general formula (i)

M = NC = N-NH- / Π \ > Formula I

X the trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, Pentafluoroethylthio-, Pentafluorthio-, Cyano-, Trifluormethy1-, Chlorine, bromine, fluorine or nitro group

Y hydrogen, a trifluoromethoxy, trifluorraethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoro

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ethoxy, pentafluoroethylthio, pentafluorothio, chlorine, fluorine, bromine, trifluoromethyl or alkyl group with 1 to k carbon atoms;

R _{1 is} hydrogen, a chlorine, bromine, fluorine or trifluoromethyl group;

R _{2 is} hydrogen, a chlorine, bromine, fluorine or trifluoromethyl group;
R, hydrogen, a chlorine, bromine, fluorine, trifluoromethyl or nitro group;

Z is hydrogen, a chlorine, bromine or fluorine group and Q is hydrogen, a chlorine, bromine or fluorine group, where
l) when Y is an alkyl group having 1 to k carbon atoms, X is a trifluoromethyl group;

2) when X is a 4 * -Broni or 4-fluoro group and R ₁ , Q and three. of the radicals R ₀ , Z, Y and R_ are hydrogen, the groups R ₀ , Z, Y or R ^. must be groups other than the 4-bromo or 4-fluoro group;

3) when X is nitro, R "is other than hydrogen; and
4), if X is halogen, at least one of the groups R ₁ , R ₀ ,

R-, Q, Z and Y are other than hydrogen; as well as the agriculturally suitable salts, preferably the Lithium, potassium and sodium salts.

Some of the compounds according to formula I are new. These connections correspond to the general formula (il):

CN ^Ra

N = N-C = N-NH

Formula II

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whereby

X is a trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, Pentafluoroethylthio, pentafluorothio, cyano, trifluoromethyl, Chlorine, bromine, fluorine or nitro group;

Y hydrogen, a trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, pentafluoroethylthio, pentafluorothio, chlorine, bromine, fluorine, Trifluoromethyl or an alkyl group with 1 to k carbon atoms;
R. hydrogen, a chlorine, bromine, fluorine or trifluoromethyl

group j
R "hydrogen, a chlorine, bromine, fluorine or trifluoromethyl

group;
R, hydrogen, a chlorine, bromine, fluorine or trifluoromethyl

or nitro group;

Z are hydrogen, a chlorine, bromine or fluorine group, where, if
l) X is a nitro group, at least one of the groups Y or R,

is a trifluoromethyl group;
2) when Y is an alkyl group with 1 to h carbon atoms,

X is a trifluoromethyl group;
3) when R 1 is nitro, X is trifluoromethyl;

and
4) when X is halogen, no more than three of the groups can

R., R ₀ , R_, Z and Y are hydrogen;

and their agriculturally suitable salts, preferably the lithium, potassium and sodium salts.

The following new compounds according to formula II are due particularly preferred for their high insecticidal activity:

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1,5-bis (4-trifluoromethylphenyl) -3-formazanecarbonitrile; 1,5-bis (3,4-dichlorophenyl) -3-f orraazanecarbonitrile; 1- ( ² I-TrIf luorniethylphenyl) -5-phenyl-3-f o nu a ζ an carbon it ril.j 1- (4-trifluorraethylphenyl) -5- ( ^/ i-chlorophenyl) -3-forraazanecarbonitrile; 1- (3-trifluoromethylphenyl) -5- (4-chlorophenyl) -3-forniazane carbonitrile; i- (3-trifluoromethylphenyl) -5- (3,5-dichlorophenyl) -3-formazanecarbonitrile;

1- ( ² I-trifluoromethylphenyl) -5- (3 »^ -dichiorphenyl) -3-formazanecarbonitrile;

1,5-bis (3,5-dichlorophenyl) -3-forraazanecarbonitrile; 1- ( ² I-Trifluoromethylphenyl) -; 5- (4-chlor- 3-trifluorraethylphenyl.) -3-formazanecarbonitrile

1- (4-trifluoromethylphenyl) -5- (2-chloro-5-trifluoromethylphenyl) -3-formazanecarbonitrile; .

1- ( ² I-trifluoromethylphenyl ) -5- (2,6-difluorophenyl) -3-formazanecarbonitrile;

1- ( ² I-trifluoromethylphenyl) -5- (3-nitrophenyl) -3-formazan-cartonitrile; 1- (4-trifluoromethylphenyl) -5- ( ² ^ nitrophenyl) -3-formazane carbonitrile; 1- (4-trifluoromethylphenyl) -5- (2, k, 6-trichiorphenyl) -3-formazanecarbonitrile;

1- ( ² I-trifluoromethylphenyl) -5- (3-trifluoromethylphenyl) -3-formazane carbonitrile;

1- (4-trifluoromethylphenyl) -5- (3-bromophenyl) -3-formazanecarbonitrile; 1- (4-trifluoromethylphenyl) -5- (4-bromophenyl) -3-formazanecarbonitrile; 1- (4-trifluoromethylphenyl) -5- (3-fluorophenyl) -3-formazanecarbonitrile;

1- (4-trifluoromethylphenyl) -5- (3-chlorophenyl) -3-formazanecarbonitrile; 1- (4-trifluoromethylphenyl) -5- (4-isopropylphenyl) -3-formazanecarbonitrile;
1,5-bis- (3j4-dichlorophenyl) -3-forraazane carbonitrile, potassium salt.

The invention also relates to a method of insect or Combating arachnids by using a compound according to formula I.

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and formulations with such a compound. Such formulations consist essentially of an inert one Diluent and / or a foam generator or surfactant Means and one, or more, according to the invention Links.

The action according to the invention can take place at the site of the infestation, on the area to be protected or on the insects or arachnids themselves.

The invention accordingly relates to certain substituted 1,5-diphenyl-3-formazanecarbonitrile compounds and their use for insect and / or arachnid control.

The compounds according to the invention correspond to the general ones Formula I.

(D

CN

-N = N-C = N- NH-

However, this formula also includes the tautomeric formulas Ia and Ib, as well as mixtures of these tautomers and the cis and trans or syn and anti isomers resulting from the double bonds result.

(la)

(Ib)

CN-H-N-CH-N

other

CN

-NH-N-C-N

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The same applies to the new compounds according to formula II, which are also covered by formula I.

In the same way, the agriculturally suitable ones are also suitable Salts of the compounds according to formula I are suitable. The lithium, potassium and sodium salts are preferred. The invention relates to Compounds used for insect and / or arachnid control. are suitable. These compounds correspond to formula I:

Formula I N / V. ι

N = N-C = N-NH-

In here is

"X is a trifluoromethoxy, trifluoromethylthio, -1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, pentafluoroethylthio, pentafluorothio, cyano, trifluoromethyl, chlorine, Bromine, fluorine or nitro group; Y hydrogen, a trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, pentafluoroethylthio, pentafluorothio, chlorine -, bromine, fluorine, trifluoromethyl or an alkyl group with 1 to k carbon atoms; R. hydrogen, a chlorine, bromine, fluorine or trifluoromethyl group

group;
R "hydrogen, a chlorine", bromine, fluorine or trifluoromethyl

group;
R_ hydrogen, a chlorine, bromine, fluorine, trifluoromethyl

or nitro group;

Z is hydrogen, a chlorine, bromine or fluorine group and Q is hydrogen, a chlorine, bromine or fluorine group,

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1) when Y is an alkyl group with 1 to k carbon atoms,

X is a trifluoromethyl group;
2) when X is a 4-bromo group or ^ -fluoro group and R., Q and three of the groups R ₉ , Z, Y and R_ are hydrogen, the remaining groups R ₉ , Z, Y and R, respectively, are something other than

are the 4-broja or 4-fluoro group; 3) when X is a nitro group, R must be something other than

Be hydrogen; and
h) if X is halogen, at least one of the groups R.,

R ", R_, Q, Y and Z are other than hydrogen; the invention also relates to those agriculturally suitable Salts of these compounds.

Because of their higher activity are the following compounds

according to formula I preferred, in the

X is a trifluoromethyl, chlorine, bromine, pentafluoroethoxy or

Nitro group j

Y is hydrogen, a trifluoromethyl, chlorine, bromine, fluorine or pentafluoroethoxy group or a branched alkyl group having 3 or h carbon atoms;

R. hydrogen, a chlorine, bromine or trifluoromethyl group; R “is hydrogen, a chlorine, bromine or trifluoromethyl group; R_ hydrogen j
Z hydrogen or chlorine and
Q are hydrogen or chlorine, where

1) when Y is a branched alkyl group having 3 or k carbon atoms, X is a trifluoromethyl group; 2) when X is halogen, not more than one of the groups R>, R ₀

and Y can be hydrogen;

3) when X is a nitro group, Y is other than hydrogen.

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Because of their high insecticidal activity within the compounds according to formula I, the compounds according to formula II are preferred,

in the

X is trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, pentafluoroethylthio, pentafluorothio, cyano, trifluoromethyl, chlorine, bromine , Fluorine or nitro group; Y hydrogen, trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, pentafluoroethylthio, pentafluorothio, chlorine, bromine, fluorine, trifluoromethyl - or an alkyl group with 1 to k carbon atoms;

R> hydrogen, a chlorine, bromine or trifluoroethyl group; R _{2 is} hydrogen, a chlorine, bromine or trifluoromethyl group; R, hydrogen, a chlorine, bromine, fluorine, trifluoromethyl

or nitro group;

Z are hydrogen, a chlorine, bromine or fluorine group, where l) when Y is an alkyl group with 1 to k carbon atoms,

X is a trifluoromethyl group;

2) when R_ is a nitro group, X must be a trifluoromethyl group be;

3) if X is a ² I-BrOIa or 4-fluoro group and R., R ", Z and one of the groups R ₉ and Y are hydrogen, the remaining groups R ₀ or Y are something other than a ² I-BrOm - or ^ -Fluorgruppe must be;
² O, when X is a nitro group, Y is a Trif is ^{luormethylgruppe.}

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More preferred because of their high insecticidal activity are the compounds according to formula II, if X is a trifluoromethyl, chlorine, bromine, pentafluoroethoxy or nitro group;

Y is hydrogen, trifluoromethyl, chlorine, bromine, fluorine, pentafluoroethoxy or branched alkyl group with 3 or h carbon atoms;

R> hydrogen, a chlorine, bromine or trifluoromethyl group: R ₀ hydrogen, a chlorine, bromine or trifluoromethyl group; R_ hydrogen and
Z are hydrogen;

where, (l) j when Y is a branched alkyl group with 3

or h is carbon atoms, X is trifluoromethyl group;

(2) when X is halogen, no more than one of R., R1 and Y can be hydrogen; (3)> when X is nitro group, Y is trifluoromethyl group.

For the same reasons, the compounds according to formula II are also preferred in which

X is a trifluoromethyl, chlorine, bromine or pentafluoroethoxy group;

Y hydrogen, a chlorine, bromine, fluorine, pentafluoroethoxy or branched alkyl group having 3 or 4 carbon atoms;

R. Hydrogen, chlorine or bromine; R _{2 is} hydrogen, chlorine or bromine; and R1 and Z are each hydrogen; whereby

l) when Y is a branched alkyl group having 3 or h carbon atoms, X is a trifluoromethyl group; 2) when X is halogen, no more than one of R., R and Y can be hydrogen;

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Also preferred are compounds according to formula II, in

the

X is chlorine, bromine or a pentafluoroethoxy group;

Y is hydrogen, chlorine-j bromine-j fluorine or a pentafluoroethoxy group ;

R _{1 is} hydrogen, chlorine or bromine;
R _{0 is} hydrogen, chlorine or bromine;
R_ and Z are each hydrogen; where, when X is halogen, no more than one of the groups R., R ₀ and Y can be hydrogen.

More preferred because of their even higher insecticidal activity are compounds according to formula II in X is a trifluoromethyl group;

Y is hydrogen, a trifluoromethyl group, chlorine or bromine; R _{1 is} hydrogen, chlorine or bromine;

Rp hydrogen, chlorine or bromine; R_ and Z are each hydrogen.

Because of their higher insecticidal activity and the ease of their preparation, compounds according to formula II are even more preferred if
X chlorine or bromine;

Y chlorine or bromine;

R _{1 is} hydrogen, chlorine or bromine; Rp chlorine or bromine; R_ and Z are each hydrogen.

Some of the compounds according to formula I are new. These connections correspond to formula II; their agriculturally suitable Salts are also new. The lithium, potassium and sodium salts are preferred.

^H CN ^Ra

I ₁ <£. ^ VN = NC = N-IiH

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The new compounds correspond to the formula II, in which X represents a trifluoromethoxy, Trifluormethylthiq-, I ^ 1,2,2-Tetrafluoräthoxy, 1,1,2,2-Tetrafluoräthylthio-, Pentafluoräthoxy-, Pentafluoräthylthio _r Pentafluorthio-, cyano, Trifluoromethyl, chlorine, bromine, fluorine or nitro group; Y hydrogen, a trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy ₇ 1,1,2,2-tetrafluoroethyl tlii ο-, pentafluoroethoxy, pentafluoroethylthio, pentafluorothio, chlorine, bromine, fluorine , Trifluoromethyl or alkyl group with 1 to k carbon atoms;
R.! Hydrogen, chlorine, bromine, fluorine or trifluoromethyl

group;
R ₂ hydrogen, chlorine, bromine, fluorine or trifluoromethyl

group;
R_ hydrogen, chlorine, bromine, fluorine, trifluoromethyl or

Nitro group;

Z is hydrogen, chlorine, bromine or fluorine, where
l) if X is a nitro group, at least one of the groups

Y or R_ must be trifluoromethyl; 2) when Y is an alkyl group having 1 to k carbon atoms

X is trifluoromethyl; 3) when R 1 is a nitro group, X is a trifluoromethyl group

is; and
4) if X is halogen, not more than 3 of the groups R., R ₂ ,

R ", Z and Y can be hydrogen;

and the agriculturally suitable salts of these compounds.

Also preferred are new compounds of the formula II in which

X is a Trifluorraethy1gruppe, chlorine, bromine, 4-pentafluoroethoxy- or nitro group;

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Υ hydrogen, trifluoromethyl group, chlorine, bromine, fluorine, 4-pentafluoroethoxy or branched alkyl group with 3 or 4 carbon atoms;
R _{1 is} hydrogen, chlorine or bromine;
Rp hydrogen, chlorine or bromine;
R_ and Z are both hydrogen, where l), when X is halogen, not more than one of the groups R-,

R ₂ and Y can be hydrogen;

2) when Y is a branched alkyl group having 3 or k carbon atoms, X is a trifluoromethyl group, and 3) when X is a nitro group, Y is a trifluoromethyl group.

New compounds are preferred according to formula II in which X is a trifluoromethyl group, chlorine, bromine or a * i-pentafluoroethoxy group;

Y is hydrogen, chlorine, bromine, fluorine, a 4-pentafluoroethoxy or branched alkyl group with 3 or h. Carbon atoms;

R. Hydrogen, chlorine or bromine;
Rp hydrogen, chlorine or bromine;
R1 and Z are both hydrogen, where l) when X is halogen, no more than one of the

Groups R., R ₀ and X are hydrogen;

2) when Y is a branched alkyl group having 3 or h carbon atoms, X is a trifluoromethyl group.

New compounds of the formula II in which X is chlorine, bromine or an h- pentafluoroethoxy group are preferred;

Y is hydrogen, chlorine, bromine, fluorine or a 4-pentafluoroethoxy group;

R _{1 is} hydrogen, chlorine or bromine; Rp hydrogen, chlorine or bromine; R, and Z are both hydrogen, where

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when X is halogen, not more than one of the groups R. and R and Y can be hydrogen.

More preferred because of their high activity and ease of preparation are the compounds of formula II, if X is a trifluoromethyl group;

Y is a trifluoromethyl group, hydrogen, chlorine or bromine; R _{1 is} hydrogen, chlorine or bromine; R _{2 is} hydrogen, chlorine or bromine; and R_ and Z are hydrogen.

Even more preferred because of the ease of their preparation are the new compounds according to formula II, in X chlorine or bromine;

Y chlorine or bromine;

R. Hydrogen, chlorine or bromine; R _{2 is} chlorine or bromine; and R, and Z are both hydrogen.

Representation method

JCN

Diazotization (yyy> £ N

ArNH ₀ ; £ ArN ₀ ⁺ S "* ^ 4— ► ArNHN = C

I Vo

T I

> ArN = NC = N-NHAr ¹

CN

-Ik-

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where T = OH, OR, NHR and R = H or an alkyl group with 1 to h carbon atoms and S = Cl, HSO ^, Hp ^P0 4 or other counterions which correspond to the acid used to prepare the amine salts.

The process for the preparation of 1,5-diphenyl-3-forinazanecarbonitrile are known. Symmetrically substituted 1,5-diphenyl-3-formazanecarbonitriles (Ar = Ar ') can be prepared by adding two moles of diazonium salt with one mole an active methylene compound having a cyano group and a carboxy, carboalkoxy or carboamido group will. The diazonium salt is made by diazotizing the appropriate aromatic amine. The intermediate, substituted Phenylhydrazone can be isolated; however, with symmetrical formazans it is usually more practical and more conveniently, two equivalents of the diazonium salt with one equivalent of the active methylene compound without isolation of the hydrazone to couple. The symmetrical formazans separate and are easy to isolate by filtration.

Unsymmetrical formazans (Ar ^ Ar ¹ ) are made from one mole of active methylene compound and two moles of diazonium salt, ArN ₀ ⁺ S "and Ar'N ₀ ⁺ S", where Ar / Ar 'is.,

Ole

The intermediate hydrazone of one of the diazonium salts can be prepared isolated, purified, redissolved and reacted with one mole of the other diazonium salt. The hydrazone does not need to be isolated. In this case, an equivalent of the diazonium salt with an equivalent of the active Methylene compound are reacted, and after a suitable increase the pH value, a second mole of the other diazonium

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salt unreleased while maintaining the desired pH will. The unsymmetrical formazans separate and are easily isolated by filtration.

In the procedures described in each case, the formazans have a purity of 90 % or higher after washing with water to remove the salts and can be used directly for regulating or controlling insects. The product can be further purified by crystallization from a suitable solvent system such as acetone, acetone-water, chloroform or acetonitrile.

The diazo be tierungen \ ^r orzugsweise carried out in a strongly acidic aqueous medium. In cases where the amine or diazonium salts are sparingly soluble in water, it is often desirable to use a combination of water and organic solvents. Water-miscible solvents such as alcohol, ether or organic acids, for example methanol, ethanol, tetrahydrofuran, dioxane, ethylene glycol and acetic acid are preferred. For some weakly basic amines, strong acids such as concentrated sulfuric acid, phosphoric acid or aqueous hydrochloric acid {hO Jc) are required and used. The Diazotierungstemperaturen may range from -20 to 100 C, preferably from 0 to 40 are ⁰ C.

Many nitrosating agents are known, for example nitrous acid, Nitrosylsulfuric acid, nitrogen tetroxide, alkyl nitriles and a variety of compounds that produce nitrous acid. Preferred nitrosating agents include nitrous acid and nitrogen tetroxide. An equivalent is preferred or a slight excess of a nitrosating agent

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per amine equivalent. The pressure is in the process according to the invention not a critical variable. Although pressures above and below atmospheric pressure can be used, it is more atmospheric Pressure preferred.

The coupling of diazonium salts and active methylene compounds is used in a conventional manner and preferably in aqueous Medium carried out. If the diazonium salts are poorly soluble in water, it is often desirable to use a combination of Use water and organic solvents. Water-miscible solvents such as alcohols and ethers are preferred or organic acids such as methanol, ethanol, tetrahydrofuran, dioxane, ethylene glycols and acetic acid.

The coupling between diazonium salts and the active methylene compounds takes place at pH values of 2 to 12. The intermediate hydrazone can be in the pH range from 2 to 6.5> preferably at 4 to 6, and then with a second one Mol Diazoniunisalz at a pH of 7 to 12, preferably 7.5 to 10, coupled. In the case of symmetrical formazans, it is more practical and convenient to mix two equivalents of diazonium salts with one equivalent of an active methylene compound in one pH from 7 to 12, preferably from 7.5 to 10, without isolation of the intermediate hydrazones, to couple. The pH of the reaction mixture can be adjusted by using suitable buffers such as potassium phosphate (monobasic) / potassium hydroxide or sodium acetate / sodium hydroxide or by simultaneous or subsequent Addition of a suitable base such as sodium hydroxide can be regulated.

The temperature of the coupling steps may range from -20 ° 100 ⁰ C, preferably 0 - 40 ⁰ C are.

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Two equivalents or a massive excess of the diazonium salt per equivalent of active methylene compound are preferred. The pressure is not critical in the process according to the invention Variable. There can be prints above and below atiaospheres pressure can be used, but atmospheric pressure is preferred.

The coupling of the diazonium salts and the active methylene compounds are carried out in a manner known per se and preferably in an aqueous medium. In those cases where the Diazonium salts are poorly soluble in water, it is often desirable to use a combination of water and organic solvents to use. Water-miscible solvents such as alcohols, ethers or organic acids are preferred, for example methanol, ethanol, tetrahydrofuran, dioxane, ethylene glycols and acetic acid.

If the substituted phenylhydrazones are isolated, the pH of the reaction mixture is kept at 2 to 6.5, preferably at h to 6.

An excess of active methylene compound can be used; however, a 1: 1 molar ratio or is preferred slight excess of active methylene compound, based on the diazonium salt, used.

The phenylhydrazones are normally insoluble in water; they can be isolated by filtration and in the subsequent Coupling step can be used directly. Alternatively, the product can be recrystallized in a suitable solvent system such as acetone, acetone / water, chloroform or acetonitrile can be further purified.

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In the second coupling step, the hydrazone or its Alkali metal salt in a suitable solvent system such as for example water, methanol, ethanol, tetrahydrofuran, Dioxane, ethylene glycol and their combinations dissolved and with an equivalent or slight excess of another diazonium salt implemented, the pH to 7 to 12, preferably 7.5 to 10, is regulated,

The temperature of the respective coupling steps may range from -20 to 100 ° C, preferably 0 to 40 ⁰ C, are.

The process variables and conditions are the same as described for the production of asymmetrical formazans became. However, the intermediate, substituted phenylhydrazone is not isolated. Rather, it becomes the pH raised to 7 to 12, preferably 7- »5 to 10; the Coupling is carried out directly with the other diazonium salt. Under these conditions, an excess of active methylene compound is preferably avoided.

The process for making 1,5-diphenyl-3-formazan carbonitriles can be discontinuous or continuous.

The invention is illustrated by the following examples, in which the preparation of the compounds according to formula I and formula II is described, explained in more detail. In all examples,. Cyanoacetamide Cyanoacetic acid or its ester be used. Part · = - and percentages are provided, provided there is not otherwise indicated, based on weight. Temperatures are given in degrees Celsius, unless otherwise stated.

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Example I.

A solution of 16.1 g (0.1 mol) of p-aminobenzotrifluoride in 30 ml of 12N acetic acid, diluted with 300 inl of water, is cooled to Q by adding crushed ice until the volume of the solution is 500 ml. Then a solution of 7> 0 g (0.1 Hol) sodium nitrite in 70 ml of water is added with stirring. A solution of 4.2 g (0.05 mol) of cyanoacetamide in 50 ml of water is then added; the mixture is introduced into 450 μl 1 molar NaH ₀ PO. buffer solution with a pH value of 7.5, an orange solid being formed within the solution. The pH of the solution is then adjusted to 7.5 by adding 100 ml of 10 sodium hydroxide. Carbon dioxide develops. The orange solid product is collected by filtration, the yield of crude product being quantitative. After recrystallization from acetone the product as l was (4-trifluoromethylphenyl) -3-formazancarbonitril 5-bis having a melting point of 232 - 234 ⁰ C identified.

example

To remove a small amount of an insoluble material, a solution of p-aminobenzotrifluoride (120.8 g; 0.75 mol, boiling point 117.5 ° θ / 6θ mm, n _ß ²⁵ 1.4815) in 12N HCl is diluted with 1167 ml of water and 333 ml of methanol, filtered. Crushed ice is added to the filtrate to cool the solution to 0 ° to 5 ° C. Sodium nitrite (52.5 g, 0.76 mol) in 100 ml of water is then quickly added and the solution stirred for 10 minutes at 0 to 5 ° C. The diazonium salt solution is slowly added to a stirred solution of cyanoacetamide (31.5 g> 0.37 mol) in a ca

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Lium phosphate (ionobasic / sodium hydroxide buffer (pH 8.65; 666 ml) was added, while at the same time aqueous 10 ^ iges sodium hydroxide is added at such a rate that that the pH ¥ ert is kept at 5.5 to 9.0.

After the addition was complete, the orange-red suspension was stirred for 10-20 minutes and filtered. The filter cake was washed free of salts with water and then dried; it was the orange-red solid 1, 5-bis (4-Trif luorraethylphenyl) -3-f örniazancarbonitril; - obtained (lhk g melting point 227 230 ⁰ C). Without further purification, this material showed excellent insect control properties.

When using the appropriately substituted aniline instead of p-aminobenzotrifluoride in one of the methods according to the example 1 or Example 2, the symmetrically substituted compounds of the formula I and II in Table I can be prepared will.

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Table I.

CN

N = N-C = N-N

R-

X R ₁ Y ^R 2 ^R 3 ζ'- "'■' m.p. ¹ I-HP ₂ CCP ₂ O- H .4-HF ₂ CCF ₂ O- H H H 198-201 ¹ I-CF ₃ S- H ¹ J-CP ₃ S- H H Ή 200-203 4-P ₅ C ₃ O- H 4-FC ₃ O- H H - H 210-212 ¹ JF ₅ S- H UF ₅ S- H H H 181-185 ¹ I-CF ₃ O- H A-CP ₃ O- H H · H 211 3-CP ₃ S- H 3-CF ₃ S- H H H . 141-1 ^ 5 3-P ₅ C ₂ O- H 3-P ₅ C ₂ O- H H H 136-139 3-HCP ₂ -CF ₂ -S- H 3-HCP ₂ CP ₂ -S- H H H 158-161 3-HP ₂ CP ₂ CO- H 3-HCF ₂ CF ₂ O- H H H 146-149 3-P ₅ S- H 3-F ₅ S- H H H 157-160

3-CP ₀ -

H 3-CF ₃ -

- 22 -

HHH 142-146 509836/1009

BA-8073-B

Table I (continued)

CN

N = N-C = N-N

X ^R l Y R ₂ ^H 3 Z M.p. 3-chloro 3-chloro H H H 231 3-CP ₃ ., - Cl 3-CF ₃ H-Cl H H 198-203 3-Cl 3-Cl 4-Cl H H

3-Cl

5-Cl 3-Cl

5-Cl H H 259-262

509836/10 0 9

BA-8073-B

Table I (continued)

CN

N = N-C = N-N

X R ₁ Y R ₂ R ₃ z 3-Br 4-Cl 3-Br Jl-Cl H H 3-Cl 4th-Br 3-Cl 4-Br H H 3-Br 4 -Br 3-Br 4-Br H H * 3-Br 5-Br 3-Br 5-Br H H 3-CF, 4 -Br 3-CF ₃ 4-Br H H 4-F ₅ CsS H UF ₅ C ₂ S H H H 4-ci 3-F 4-Cl 3-F H H 4-F 3-Br 4-F 3-Br H H

509836/1009

Table I (continued)

CN NH-N = O-N-N-

R.

Q-

cn
CD 4-Cl 2-Cl 6-Cl 4-Cl H 2-Cl 6-Cl CO
CO 4-Cl 2-Cl 5-Cl 4-Cl H 2-Cl 5-Cl co 2-CP ₃ 4-Cl H '2-CP ₃ 4-Cl H H I. £ 7> 4-Cl H 2-Cl 4-Cl H H 2-Cl ro
Ul CD 5-Cl 2-Cl H 5-Cl 2-Cl H H I. CD
CD ' 5-CP ₃ H - . 2-Cl '. 5-CP ₃ H H 2-Cl 5-CF ₃ H 2-P 5-CP ₃ . ■ H H 2-P 4-F 2-CP ₃ H 4-F H 2-CP ₃ H 3-NO ₂ 4-Cl. H H 4-Cl 3-NO ₂ H 3-CF ₃ 5-CP ₃ ' H 3-CP. 5-CP ₃ H H H 2-Cl 6-Cl H 2-Cl H 6-Cl 4-Br H
• 2-Br 4-Br H H 2-Br 5-Br. 2-Br H 5-Br 2-Br H H 4-Br H 2-Cl 4-Br H ' H 2-C1 4-F. H '2-P 4-F H H 2-P

M.p.

I32-I38 237-240 180-183 188-191 202-205 127-130 I54-I58 183-187 239-243 221-224

156-159 I83-I89 210-215 198-204

174-179

CD CD Ni

BA-8073-B

Table I (continued)

CN t

NH-N = C-N = N

X ^R l Q Y ^R 2 ^R 3 Z -Schmp. 2-CF ₃ H H 2-CF ₃ H H H 121-125 2-OCF ₃ H H 2-OCF ₃ H H H 111-115 3-F H H 3-F H H H 208-209 4-Cl
4-NO ₂ H
H H
H 4-Cl
H H
H H
4-NO ₂ H
H 242-245
219 (dec)

- 26 -

$ 0 9836/1009

Example 3

A solution of 9.3 g (0.1 mol) of aniline in 16.6 ml of 12N HCl, diluted with 150 ml of water, is cooled to 0 ° C. and a solution of 6.9 g of sodium nitrite in 50 ml of water is added diazotized. This solution is slowly poured onto a solution of 13.8 g (0.165 mol) cyanoazetaiaid and 15 g potassium acetate in 200 ml water. A yellow solid precipitate of CgHr-NHN = C (CN) CONH ₂ is formed Filter isolated and through

1) reflux with benzene and

2) Separation of the benzene / water azeotrope until none in the distillate Water appears more, dried.

The product is removed from the benzene suspension by filtration and characterized by IR spectrum.

A solution of k, 7 g (0.025 mole) C ^ H _e NHN = C (CN) C0NH ₂ in 25 ml In sodium hydroxide plus 25 ml of methanol is then prepared. Then a solution of 4.3 g (θ, 025 mol) of p-trifluorinethoxyaniline in 75 ml of In HCl is prepared, ^{cooled to 0} ° C. and diazotized by adding a solution of 1.75 g of sodium nitrite in 20 ml of water. This diazonium solution is poured into the stirred hydrazone solution; then 25 ml of In NaOH are added. An orange precipitate forms; the pH of the solution at this point is 7.6. The solid is removed by filtration; the filter cake is dissolved in chloroform. This solvent is removed. The residue is recrystallized from n-butyl chloride and leads to 3.0 g of light red crystals with a melting point of 183-184 ° C .; it is 1- (4-trifluoromethoxyphenyl) -5-phenyl-3-formazanecarbonitrile. .

- 27 τ

50 9 836/1009

BA-8073-BO

When using appropriately substituted anilines instead of aniline and p-trifluoromethoxvaniline in the sequence described of process steps or modifications known per se of these process steps, the asymmetrically substituted Compounds according to formula I and II listed in Table II are made.

- 28 -

509836/1009

BA-8073-B

Table II

CN

N = M-C = N-N

X "* Y H R ₂ ^R 3 Z Scnmp. 3-Cl 4-Cl * I-C1 H 2-Cl 6-Cl I55-I63 3-Cl 4-Cl * J-C1 H 2-Cl H I83-I87 3-Cl 4-Cl 3-Cl H 2-Cl 6-Cl 1ί | 0-150 3-CP ₃ 4-Cl H - 4-Cl H H 233-238 3-Cl 5-Cl H-Cl H H H 229-235 ή-CN H M-Cl - H H . H 26 Ii-2 6 7 1-Cl H H 2-Cl 6-Cl 210-215

3-Cl

ii-ci

H H 239-2 ^ 3

- 29 -

509836/1009

BA-8073-B

Table II (continued)

χ ^R l Y R ₂ ^R 3 Z Sehmp. 3-Cl 1-Cl 3-Cl 5-Cl H H 23-235 3-Cl ¹ I-Cl 3-F H H H 218-223 3-CP ₃ 1 »-C1 H-Cl H H H 235-2i | 0 3-Cl H-Cl H H 2-Cl H 170-175 3-Cl it-ci H H 2-CF ₃ H I5O-I56 ή-cn H 3-Cl . 5-Cl H H 247-253 3-Cl 5-Cl H-Cl H H H 2H0-245 3-Cl 5-Cl H H 2-Cl H _ 125-130 3-CP ₃ H H H H '176 4-CN H 3-CP ₃ H H H 250 3-CP ₃ H H H 2-P H 140-1 ^ 5 3-CF ₃ H H H 2-Cl H 130 3-CP ₃ H H-Cl H 2-Cl 6-Cl 181

3-Cl

H 2-CP ₃ H 92-102

509836/1009

BA-8O73-B Table II (continued) ο /, -> η ^ r i-

/ 4dUü: 55

χ "1 Y R ₂ ^R 3 Z M.p. ή-ci H H H 2-CF- • H 163-173 4-CN
* H H H 2-OF ₃ H I32-I37 3-Cl 5-Cl ' H H 2-CF ₃ H 168-178 4-CN H 3-Cl H H H 205-209 3-CF ₃ 1-C1 3-Cl H H H 225-229 3-Cl H 3-Cl 5-Cl H H 213-217 3-Cl H 3-Cl 4-Cl H H 209-213 3-CF ₃ H-Cl 1
4-isopropyl H H H 116-152 3-CF ₃ * t-Cl 3-Cl 5-Cl H H 190-195 4-CF ₃ 3-F H H H 200-201 4-CF ₃ H 3-Cl
• H H H 120-122 ^ i-CF ₃ H 1-isopropyl H H H 188-192 4-CF ₃ H H H 2-CF ₃ H 163-173 Jl-CF ₃ . H H H 2-F 6-tF

3-CF-H 4-Cl HH H 191-197

-31- 509836/1009

BA-8O73-B Table II (continued)

χ ^R l Y ^R 2 R ₃ Z M.p. 3-CFg H '3-Cl 5-Cl H H. 212 3-CFg \ H 3-Cl JJ-Cl H H · 209 3-CFg H 3-Cl H H H 198-204 3-CP H, 3-CPg H 2-Cl H .264 3-CPg H 3-CFg Jj-Cl H H . 166-172 3-CN H 3-CFg H H H 231-246 3-CPg H Jl-Br H H H 190-195 Jl-NO ₂ H 3-CPg H H H 185-196 3-CPg H . H H 2-P 6-F 105 3-CPg H 3-P H H H 175-178 4-CFg-, H H H H H 217-221 4-CFg H JJ-CHg H H H 246-247 4-CFg H JJ-Cl H H H 291-292 4-CF ₃ H 3-Cl 5-Cl H H 267-268

Jj-CP-H 4-Cl H 2-Cl 6-Cl 210

5 '

" ³² ~ 609836/1009

BA-8O73-B Table II (continued) 2 ^ 60255

X *1 Y ^R ? ^R 3 . . Z. M.p. 4-CF ₃ H ■ ^: 3-Cl 4-Cl H H - 211-213 Jl-CF ₃ H 3-CP ₃ 4-Cl H H' 198 Ji-CP ₃ H 5-CP ₃ H 2-Cl H 201 4-CP ₃ H 3-CP ₃ H H H 172 JI-CP ₃ H H H 2-NO ₂ H I6I-I62.5 3-NO ₂ H 4-CP ₃ H H H 187-190 JI-NO ₂ H 4-CP ₃ H H H 199-204 Jl-CP ₃ H H H 2-Br H 117 JI-CP ₃ H 3-Br H H • H 179-183 JI-CF ₃ H 4-Br H H H 243-243.5 Jl-CP ₃ H H H 2-P H 201-202.5 Jl-CN H 3-Cl 4-Cl H H 248-251

3-CP ₃ HHH ² ~ ^CP 3 ^{H 105}

- 33 -

50983 6/1009

BA-8O73-B

"Vf

Table II (continuation day)

X Ri Y R ₂ R ₃ Z ■ - 4-CF ₃
4 -CP 3
4-CF ₃
3-CP ₃
3-CF ₃
3-CF3
3-CP ₃
3-CN
4-CP ₃
3-CP ₃
4-CP ₃
3-CP3
3-CF3
4-CF 3 KKKKKKK KK K K K KK 3-Br
4-P
H
3-Br
H
4-Br
4-Cl
3-CP3
4-t-
Butyl
4-t-
Butyl
4 sec
Butyl
4 sec 4-Br
H
H
H
H
3-Br
3-Br
H
H
H
H
H
H
H H
H
2-Cl
H
2-Br
H
H
H
H
H
H
H
2-Cl
2-Cl H
H
H
H
H
H
H
H
H
H
H
H
6-Cl
6-Cl ΰ utyl
H
H

509836/1009

BA-8O73-B

Table II (continued)

CN _H

N = N-C-N-N

X Ri Y R ₂ R ₃ Z 3-CF ₃ H H H 2-Br 6-Βγ 4-CFj H H H 2-Βγ 6-Βγ 3-Cl 4-Cl 4-Br H H H 3-Cl 4-Cl 4-F H H H 3-Cl ί-Cl 3-Br H H H ή-CM H 4-CPa H H H 3-CN H 4-CF ₃ H H H

- 35 -

5098 3 6/1009

BA-8O73-B

2A60255

Table II (continued)

CN _H

NH = N-C = N-N

X Ri Y R ₂ R ₃ Z 3-CN H 3-Cl H H H 3-CF ₃ H-Cl 3-Br H H H 3-CF ₃ H-Cl H-Br H H H 3-Cl H-Cl H H . 2-F H 3-Cl H-Cl H H H H 3-Cl H-Cl 3-Br H-Br H H 3-Cl 5-Cl H-F H H H 3-CN H 3-Cl H-Cl H H 3-CN H 3-Cl H H H 3-Cl H H-Cl H 2-Cl 6-Cl H-CF O H H H H H

5098 3 6/1009

BA-8073-B

Table II (continued)

CN

X R, Q Y R ₂ R ₃ Z SehmT). ■ 3-CP ₃ H H H H 2-NO ₂ H 175d 4-CP ₃ H H 3-CP ₃ 5-CP ₃ H H 183-220 3-Cl H H H H 2-Cl H 155-8 3-Cl H H 4-Cl H H H 212-216 3-NO ₂ H H 3-Cl H H H 210-214 3-NO ₂ H H 3-Cl 5-Cl H H 217-223 3-Cl 4-Cl H H · H 2-NO ₂ H 168-173 3-NO ₂ H H 3-Cl 4-Cl H H 205-210 4-NO ₂ H H 3-Cl 4-Cl H H 239-245 4-NO ₂ H H 4-Cl H H H 245-250 3-NO ₂ H H 4-Cl H H H 252-257 4-ci H H 4-Cl H 2-Cl H I87-I92 4-Cl H H 4-Cl 6-Cl 2-Cl H 545-248 3-NO ₂ H H 4-Cl 6-Cl 2-Cl H 77-79

- 37 -

509836/1009

BA-8073-B

Table II (continued)

I ^x R, Q t R ₂ R ₃ Z j Schtnp. j
- r 1 A I.
4-NO ₂ H H 4-Cl 6-Cl 2-Cl ' H 73-75 H H 2-Cl H H 2-Cl 6-Cl 145-149 2-CF3 H H H H 2-Cl H 168-178 2-CF3 H H H H 3-NO ₂ H 155-165 4-CF3 H H H H 2-CF3 H 163-173 2-CF3 H H H H H H 125-130 3-CF ₃ H H 3-CF3 5-CF3 H H 168-200 3-CF ₃ H H H H H H 174-176 3-CF ₃ H H 4-F. H 2-CF ₃ H 134-138 3-CF ₃ H H 3-CF3 4-F H H 150-153 3-CF ₃ H H 3-CF3 H 2-F H 130-138 3-CF ₃ H H 3-CF ₃ 4- r H H 133-135

509836/1009

BA-8O73-B

Table II (continued)

X R ₁ Q Y R ₂ .R ₃ H Z Mp - 3-CF ₃ H H H 4-r 2-CF ₃ H H L32-I5O 3-CF ₃ H H . 5-CF ₃ H 2-r " H H L32-50 3-CF ₃ H H 4-CF ₃ H 2-NO ₂ H H LOI-IO7 -3-CF ₃ H H 2-CF ₃ H 4-NO ₂ H H ' 540-265 3-CF ₃ H H 3-CF ₃ 4-Cl H 5-Cl H I55-I68 3-NO ₂ H H 3-CF ₃ H H 4-Cl H 155-8 H 2-Cl H H H 2-F 4-Cl H 139-144 2-CN H H H H- 2-Cl H H I56-I6O 2-NO ₂ H H H 6-rCl 2-Cl H H' 191-195 2-CF H H K H 2-NO ₂ H I85-I9O 2-CN H H H H 2-NO ₂ H 197-199 2-F H H H H 2-NO ₂ H I77-I82 2-Cl H H H H 2-NO ₂ H 173-178 3-CN H H H H 2-NO ₂ H 172-175 3-CN H H H H 4-NO ₂ H 153 d. 2-CN ■ ' H ': ^H H H 3-NO ₉ H 132-136 2-CN H .. H H H ■ (Z. H L23 d. 3-Cl H H H H- 2-N0_ H L63 d. 3-Cl H H H H C. H L72 d. 3-CF ₃ 5-CF ₃ H 4-Cl H H I.85-2IO 3-CF ₃ H H 3-CH ₃ H H [L80-183 3-CF ₃ H H Jl-CH ₃ H H L97-2OO 3-CF ₃ H H 2-CK ₃ iJ-F H .58-165 3-CF ₃ H H 2-CH 5-F H .35-141 ^{2 |} ~ ^CF 3 H H 2-Cl 3-Cl ■. 6-Cl 4-CF H H 2-Cl 3-Cl 5-Cl 2-Cl 4-Cl 6-Cl 2-Cl 3-Cl 5-Cl 3-CF ₃ 5-CF ₃ H H H H 3-CF ₃ 5-CF ₃ - 3-Cl H- H

509836/1009

example

A solution of 3.5 g (0.01 mol) 1,5-bis (4-trifluoroethylphenyl) -3-f orinazancarbonitril in 150 nil methanol at 27 ° C is with 0.5 ^ g (0> 01 mol ) Sodium methoxide, dissolved in 15 ml of methanol, treated. After stirring for 15 minutes, the solution is evaporated and gives 1,5-t> is (4-trifluorinethylphenyl) -3-formazanecarbonitrile, sodium salt, with a melting point (decomposition) of 2k5 . According to the procedure in example h , other agriculturally suitable salts can be prepared by using or carrying out either metal alkoxides, metal hydroxides in suitable solvents or ion exchange processes known per se. This enables the following salts to be produced:

1,5-ois (^ trifluoromethylphenyl) -3-formazanecarbonitrile, Potassium salt, SehmP 217 ° (decomposition);

^ -TrIfluoromethylphenyl) -3-formazanecarbonitrile, lithium-

salt, mp 198-200 °;
1,5-Ms (3, 'i-Diehlophenyl) -3-formazancarboni tril, sodium salt,

Mp 29s - 301 ° (decomposition), with sintering at 130 °; 1,5-bis (3j4-dichlorophenyl) -3-formazanecarbonitrile, potassium salt,

M.p.> 300 °;

1,5-bis (3, Ί-dichlorophenyl) -3-formazanecarbonitrile, lithium salt; l- (3-trifluoromethylphenyl) -5 - (^ - chlorophenyl) -3-formazanecarbonitrile, Sodium salt, mp 233 ° (decomposition); l- (4-trifluoromethylphenyl) -5- (4-chlorophenyl) -3-formazanecarbonitrile, Potassium salt, mp 225 ° (decomposition); l - ('i-trifluoromethylphenyl) -5 - (^ - chlorophenyl) -3-formazanecarbonitrile, Lithiura salt.

509836/1009

Example 5

A solution from. 2.0 parts of 1, 5-bis (3, ^J i-dichlorophenyl) -3-f orm azancarbonitril in 50 parts of acetone plus 5.2 parts of 1, sodium hydroxide On "is stirred at room temperature for half an hour ge. The solution is to dryness and evaporated to afford <1,3-bis (3,4-dichlorophenyl) -3-formazancarbonitrilnatriumsalz having a melting point of 29S - 301 ° (dec.) under sintering at 130 ⁰ C.

Example 6

A column of 10 parts hexyl 101, a strongly acidic ion exchange resin (Fischer Scientific Co.) is treated with an excess of 10% potassium hydroxide. Then it is washed with distilled water until the solvent is neutral. A solution of 1.5 parts of 1,5-bis (3, ⁱ -dichlorophenyl) -3-formazanecarbonitrile sodium salt in 100 parts of acetone plus 100 parts of water is passed through the column. The column is then washed with an additional 100 parts of acetone plus 100 parts of acetone plus 100 parts of water. The combined solvents are evaporated to dryness and give 1,5-bis (3, ^ - dichlorophenyl) · 3-forniazanecarbonitrile potassium salt with a melting point of> 300.degree.

Suitable formulations of these compounds can be found in can be produced in a known way. These include dust powder, Granulates, solutions, suspensions, emulsions, wettable

_ 41. 509836/1009

BA-8073-B

bare powders, emulsifiable concentrates and the like. Many can be applied directly. Sprayable formulations can also be produced in suitable media and used in spray volumes of a few liters to a few 1,000 liters per hour, 000 m2. High strength compositions are used essentially as intermediates for further formulations. The formulations generally contain from about 1 to 99 percent by weight active compound and at least 0.1 to 20% of at least one surfactant and about 5 to 99% solid or liquid diluents. In particular, they contain these ingredients in the following approximate proportions:

Weight percent t

Active
Ingredients

Diluents

Surface-active agent (foaming agent, wetting agent)

Wettable
Powder, wettable powder

20-90

Oil suspensions
Emulsions, solutions (emulsifiable concentrates
including) 5-50

0-74

40-95

watery sus
pensions 10-50 40-84 Dust powder 1-25 70-99 Granules 1-95 5-99 very firm
Compositions 90-99 0-10

1-10

0-15

1-20

0-5 0-15

0-2

509836/1009

The active ingredients can be a compound of the present invention or mixtures of two or more of these compounds.

Depending on the intended use and the physical properties of the compound can be lower or higher concentrations of active compound may be present. Higher surfactant / wetting agent ratios Active compounds are sometimes desired and can be added by tank mixing or by incorporation into the formulation can be achieved.

Typical solid diluents are described in the Handbook of Insecticide Dust Diluents and Carriers, 2nd Edn., Dorland Books, CaIdwell, NJ. More absorptive diluents are preferred for wettable powders and the denser ones for dust powders. Typical liquid diluents and solvents are described in "Solvents Guide", 2nd. Ed., Interscience, New York, 1950. Solubilities below 0.1 % are preferred for suspension concentrates. Solution concentrates are preferably stable against phase separation at temperatures of ⁰ ° C. Surfactants or wetting agents are described in "McCutcheon's Detergents and Emulsifiers Annual", Allured Publ. Corp., Ridgewood, New Jersey and in "Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc., New York, 1964 as well as their recommended use is described. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and so on. The ingredients should preferably have been approved by the US Environmental Protection Agency for their intended use. Processes for producing such compositions are known per se. Solutions are made by simply mixing the ingredients. Fine solid compositions are made by blending and usually grinding

509836/1009

as in a hammer mill or in a jet mill. Suspensions are made by wet milling (See, for example, U.S. Patent 3,060,080). Granules can be produced by spraying the active material onto preformed granular carriers or by agglomerating techniques, as for example in "Agglomeration", Chemical Engineering, Dec. 4, 1967i page 1 ^ 7ff and "Perry's Chemical Engineer's Hand- ^ book ", 4th Edn., McGraw-Hill, N.Y., 1963, pages 8-59 * will.

"Further possibilities are given in U.S. Patents 3,576,83 ^ and 3,560 and shown in "Formulation", Chapter 6, Torgeson, Fungicides, Vol. I, Academic Press, N.Y., 1967.

The following examples are used to prepare the Compositions described. In these examples, the weight and percentage data relate to the weight, unless otherwise stated.

Example 7

Wettable powder

1,5-bis (4-trifluoromethylphenyl) -3-

formazan carbonitrile 80 %

Sodium alkyl naphthalene sulfonate $ 2

Sodium lignosulfonate 2 fo

synthetic, amorphous silica 3 %

Kaolinite 13 %

The ingredients are mixed, thoroughly hammer milled and then air milled, leaving particles with a diameter 10 microns or less. The product is remixed before packaging. 509836/1009

Ht

Example 8

granules

wettable powder even Example 7 10%

Attapulgite granules

(USS No. 20-40; 0.84-0.42mm) 90 %

A slurry of wettable powder containing 50 % solids is sprayed onto the surface of attapulgite granules in a double cone mixer. The granulate is dried and packaged.

Example 9 Dust powder

1- (3-trifluoromethylphenyl) -5- (4-chlorophenyl) τ

3-formazane carbonitrile 10 %

Attapulgite 10%

Talk 80 %

The active ingredient is mixed with the attapulgite and put in a hammer mill to a particle size of less than 200 microns in diameter. The ground concentrate is then mixed with talc powder until homogeneous.

509836/1009

Example 10

solution

1,5-bis (4-trifluoromethoxyphenyl) -3-

formazan carbonitrile 30 fo

Dimethylformamide 70 %

The ingredients are combined and stirred into a solution, which is suitable for the application of low volumes,

Example 11

Aqueous suspensions

1- (4-TrIfluoromethylphenyl) -5-phfinyl-3-formazanecarbonitrile 50%
Polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether 0.5 % disodium phosphate 1.0 $ monosodium phosphate 0.5% polyvinyl alcohol 1.0 pentachlorophenyl ' 0 _t h'% water 46.3 ^

The ingredients are combined into one in a sand mill Grind particle size less than 5 microns in diameter,

509836/1009

Example 12

High strength concentrates

Ij 5-bis ( ² I-TrIf luorraethylphenyl) -3-

formazane carbonitrile 98.5 %

Silica airgel 0.5 # ■

Synthetic, amorphous fine silica 1.0%

The ingredients are mixed and ground in a hammer mill to a concentrate of high strength, with the particles can be sieved through a sieve with 0.3 mm openings. This material can then be formulated in a number of ways.

The compounds according to the invention are used for regulating and controlling insects and arachnids, which are used in agriculture and harmful to public health. With them, harmful insects such as Lepidoptera, Coleoptera, Diptera, Hemiptera and Orthoptera and arachnids of the Acarina region can be influenced or controlled. This applies in particular to the following insects and arachnids: Mosquitos (Aedes aegypti and Culex pipiens), more southern Army worm (Prodenia eridania), cotton bollworm (Heliothis zea), cotton boll beetle (Anthonomous grandis), Mexican Bean beetle (Epilachna varivestis), house flies (Musca domestica), plant bug (Lygus lineolaria), crickets (Gryllus spp;), Colorado beetle (Leptinotarsa decimlineata), Kohlwurxrt (Pieris rapae), Earth flea (Epitrix cucumeris and others), eastern tent caterpillar (MaIacasoma americanum), beetroot armyworm (Spodoptera exigua), speckled cucumber beetle (Diabrotica undecimpunctata), Japanese beetle (Popillia japonica), and dog purposes (Dermacentor variabilis).

- kl - 509836 / 100-9 ■

The insects and arachnids are by the action of the invention Compounds in a suitable formulation at the infestation site in the area to be protected or through direct action on the pests fights. To control insects in agricultural crops, in general one or more of the compounds on the foliage or other parts of plants that are infested or that are being protected should, upset. The effective amounts to be used depend on the species to be controlled, their stage of life, The size and the place, the amount of rain, the season, the humidity and temperature as well as the type of application, the formulation and many other variables. Generally will 0.0p to 25 kg / ha for agricultural insect control required, whereby in general 0.1 to 5 kg / ha are sufficient. Preferred Amounts of the most preferred compounds when performed on a large scale are in the range of 1/4 to 1.5 kg / ha. Will used over a wide area, such as in the control of mosquito larvae, generally 1/50 is sufficient up to 10 kg / ha and preferably l / 25 to 0.5 kg / ha. Vermin that attack humans or animals, such as flies, can by direct application or action on the resting places, such as stable walls, etc., are applied. It's because of the activity If penetration of the insect's epidermis is necessary, it can be beneficial be to add an additive that supports or effects the penetration.

The compounds of the invention are generally in formulations with a carrier, which is usually oil or Water is used. The application can be in concentrated or dilute solutions or suspensions of the insecticide im Carrier take place. It can allow the application of lower volumes using suspensions containing 7> 5 $ of the ak-. tive ingredients are preferred, while equally dilute solutions or suspensions containing only 25 ppm when used of large volume is possible. Sn98? R / 10nQ

BA-8073-B

2 * 6.0255 HY

In certain circumstances it may be desirable to add certain additives such as activated charcoal or Panther Creek clay to the formulations to add to the benefit of the plant. Whether such additives are used depends on the sensitivity of the Plants, the amount of active ingredients, weather conditions and other factors.

The compounds according to the invention can be used with fungicides, Bactericides, acaricides, neraaticides, insecticides or others, biologically active compounds are mixed to the desired results with the least possible effort in time, effort and material to achieve. The amounts of these biologically active additives can each be 0.025 to 10 parts by weight, based on the compounds according to the invention, be. Such suitable agents are known to the person skilled in the art. Some are listed below:

Fungicides

Methyl 2-benzimidazole carbamate
Tetramethylthiuram disulfide (thiuram) n-dodecylguanidine acetate (dodine)
Manganäthylenbisdithiocarbamat (Maneb) 1 jh - Dichior-2,5-dimethoxybenzoe (Chloroneb) Methyl-1- (butylcarbamoyl) -2-benzimidazolecarbamat (Benomyl) N-Trichloromethylthiotetraliydrophthalimid (Captan) N-Trichloromethylthiophthalimid (Folio-methylthiophthal)

Bactericidal

Tribasic copper sulfate streptoinycin sulfate

- 49 - ■

509836/1009

^BA -. ⁸⁰⁷³ - ^B 2450255

SO

Acaricides

Senecio acid, ester with 2-sec-butyl-4t, 6-dinitrophenol ("Morocide") 6-methyl-1,3-dithiolo 2,3-B quinonolin-2-one ("Morestan") Ethyl - **, 4'-dichlordene zil ate (chlorobenzilate) 1,1-bis (p-chlorophenyl) -2,2,2-trichloroethane (ke1thane) bis (Pentachlor-2, - 'i-cyclopentadien-lyl) (Pentac) Tricyclohexyl trihydroxide (Plictran)

Nematicides

S-Me thy 1-1- (diine thy 1 earbam oy I) -N- (me thy lcarbamoyl oxy) thiof orinimidat

S-methyl-1-carbaaioy 1-N- (methyl carbamoyl oxy) -thiof ormiini da t

N-isopropylphosphoramidic acid, O-ethyl-O'-

4- (methylthio) -m-tolyl diester ("Nemacur")

insecticides

3-Hydroxy-N-niethylcrotonainid- (dimethy lphosphate) es ter (azodrine)

Methyl / carbamic acid, ester with 2,3-dihydro-2,2-diinethyl-7-benzofuranol (Furadan)

0-2, ^, 5-trichloro- (chloromethyl) benzyl phosphoric acid, 0 ', O'-dimethyl ester (Gardona)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, Dimethyl ester (malathion)

Phosphorothioic acid, 0, O-diniethyl, O-p-nitrophenyl ester (methyl parathion) Methyl carbamic acid, ester with naphthol (Sevin) Methyl 0- (methylearbamoyl) thiol acetohydroxamate (methomyl) N '- (-' i-Clilor-o-tolyI) -N, N-dimethylformainidine (Galecron)

0, O-diethy 1-0- (2-isopropyl - ^ - inetliyl-6-pyrimidy! Phosphorothioate (Diazinon)

- 50 -

509836/1009

BA-SO73-B

The following Examples 13 to Jk show the insecticidal properties of the compounds according to the invention. The determinations were made by observation.

Example 13

Groups of 25 newly hatched yellow fever mosquito larvae were made placed in 25 ml aliquots of water. The weighed quantities the compounds listed below were dissolved in acetone; Previously T certain amounts of these solutions were each added to the vessels with the mosquito larvae. Food for the larvae was also brought in periodically. The containers were checked daily and dead larvae and pupae were recorded. The results were recorded when the Mosquitos hatched and the remaining larvae or pupae were dead. For each compound, a dose of efficacy

ί κ. -ei.it-

curve and the EC value (concentration necessary to kill $ 50> mosquito larvae or pupae), expressed in ppm, was determined. The values are shown below:

CN

-N = N - C «N - HH -

4- C ₂ F ₄ HO-4-CF ₃ S-4-C ₂ F ₅ O-3-C ₂ F ₅ O-3-FsS-

¹ I- CF ₃ - ¹ J-OCF ₃ -11-CF ₃ O-

Value for k ECc ₀ Y ppm 4-C ₂ F ₄ HO- 0.45 4-CF ₃ S- 0.12 4-C ₂ FsO- 0.14 3-C ₂ FsO- Ο.56 3-F ₅ S- 0.5 4-F ₅ S- 0.15 4 — CF ₃ - . 0.02 4-OCF ₃ - 0.09 H O.Oö

509838/1009

BA-S073-B

example lh

Sl

Bean plants at the two-leaf stage were grown to drain sprayed with formulations of the specified compounds. These Formulations were prepared by dissolving 50 mg of compound in 10 ml of acetone and adding 1 ial of 1% methozol added and diluted to volume with Duponol water, 1: 3000 became. One hour after spraying, the leaves were removed and individually placed in covered Petri dishes with 10 southern Army worm larvae introduced. The evaluations with regard to the percentage kill and the percentage values of leaf damage were performed 1 and 2 days later.

H CN H

-N = N-C = N-NH

Compound spray concentrate entered ion £

valuation

1 day

2 days

^ ₀ kill % leaf fc kill % leaf damage

4-CF ₃ - 4-CF ₃ - 0, 05 95 0, 025 90 4-SCF ₃ - 4-SCF 3 "° ' 05 90 4-C ₂ F ^ H O- hC ₂ F, H0- 0.05 10 Untreated 0

2
2
H

kO
100

100 100 100 100 0

2 ο

it

100 100

* Duponol L - E.I. Du Pont de Nemours & Co., Wilmington, Delaware

509836/1009

BA-SO73-B

Example 15

Bean plants at the two-leaf stage were grown to drain with l, 5-bis (^ - Trifluormetliylphenyl) -3-formazanecarbonitrile in specified concentrations sprayed. Suspensions were made by dissolving 50 mg of the compound in 10 ml of acetone Kurds, and by adding 1 ml of l ^ ige Methocel 15 * and diluted to volume with Duponol water, 1: 3,000. Two days later the leaves were removed and individually in covered Petri Sohalen with 10 southern army urine larvae brought in. Ratings for percentage kill and percentage leaf damage became one Carried out one day later and are given below:

% Spray concentration

valuation fc kill

$ Leaf damage

0.05

untreated comparison

100
0

3 100

* Methocel 15 - Dow Chemical Company, M dland, Michigan

Example 16

Red kidney bean plants at the two-leaf stage were grown up to Drain with different concentrations of!, S-bisC ^ -trifluoromethoxyphenyl) -3-formazanecarbonitrile sprayed. Suspensions were made by dissolving 50 mg of the compound in 15 nil acetone,

- 53 -

5098 3 8/1009

BA-SO73-B

Add 1 ral of a 1% Methocel 15 solution and dilute to volume with a Duponol water solution, 1: 3,000. After the plants had dried, the leaves were removed and placed individually in covered Petri dishes with 10 southern army worm larvae. Reviews regarding the Percentage kill and leaf damage were performed daily for 3 days and are given below:

valuation

1 day

2 days

3 days

# Spray- % kill % leaf damage ^ Deterioration leaf-% Deterioration leaf concentration erosion erosion

0.05

30th

100 16

untreated

100

0 .100

100

Example 17

Cotton leaves, tobacco leaves, and corn leaves (corn ears) were made in 0.1 and 0.05% acetone solutions of 1,5-bis (4-trifluoromethoxyphenyl ) -3-f orinazancarbonitril immersed, - dried and then exposed to the larvae of the cotton bollworm. All Larvae in contact with the treated plant material came, were killed; the untreated leaves and plant parts in the control experiment were severely eaten.

50983 6/1009

BA-8O73-B

sr

Example 18

A number of plastic basins (200 L) were placed on a field arranged and filled with water to a depth of 15-20 cm. A wheat straw infusion was added to feed the mosquito larvae, as was a local egg mass Mosquito species (Culex pipiens). Naturally occurring mosquitos also deposited their eggs in the containers. Weighed amounts of 1, S-bis ^ -trif luorraethoxyphenyl) -3-formazancarbonitrile were dissolved in minimal amounts of acetone and introduced into the basin, so that concentrations of active Ingredient from 1.0 to 0.01 ppm. The mosquito larvae were completely combated at a level of 0.1 ppm.

Example 19

Bean leaf disks with a diameter of 4 cm from the Cotyledons were treated with acetone solutions of 1,5-bis (^ - trifluoromethylphenyl) -3-formazanecarbonitrile sprayed. The disks were placed individually in covered Petri dishes on moist pilter paper disks brought in together with 2 adult Mexican bean beetles. The evaluations were carried out a day later and are reproduced below:

valuation
% Spray concentration fo Mortification fo Leaf damage

ι loo 5

0.1 100 30

0.05 100 kO

- * ~ 509836/100 9 '51

BA-SO73-B

So

Example 20

House flies in cages (25 per cage) were given a l ^ ig Solution of 1,5-bis (4-trifluoromethyl-phenyl) -3-formazanecarbonitrile sprayed in acetone. After spraying, the flies were kept in a constant temperature room of 26.7 ° C at the Maintained constant relative humidity of 55%. After 20 Hours, all the treated flies were dead, while all the untreated flies were still alive in a comparison test.

Example 21

25 freshly hatched mosquito larvae were placed in 25 ml of distilled water in k glass vessels and 10 mg of food, consisting of 2 parts of liver powder and one part of fermentation yeast, were added. The compound in the 0.2 ml acetone was added to the vessels so that a final concentration of 0.5 resulted. 3 tests were carried out for each connection. The vessels were closed and left at 27-30 ^° C. with continuous exposure. Additional nutrition was added in the following way:

On day 3 20 mg; every following day replacement of the food consumed. The number of dead insects was recorded daily. The test was ended when all larvae were dead or had pupated. The test results were recorded without considering the mortality in the comparison vessels (these comparison glasses were designed to indicate if something was seriously wrong with a certain group of mosquito larvae; the mortality in the comparison glasses was usually 7% or less).

- 56 -

509 836/1009

BA-8O73-B

The following compounds were tested in a final concentration of 0.5 ppm against yellow fever raosquito larvae (Aedes aegypti) in the manner described; it was found that at least 90 fc of the larvae were killed.

- 57 -

• 5 09836/1009

BA-8073-B

CN

N = N-C = NNH

χ H. H H Y H 4-CFS H H H 4-CF S- H 4-C ₂ F ₅ O- H H H 4-C ₂ F ₅ O H 4-F.S- H 4-CF H 4-F ^ S- H 4-CF - H 4-CF H ■ H H (sodium
salt)
H 4-CF - H H H H H 4-CF 0- H 3-Cl H 4-CF 0- H 3-CF, - H 3-Cl H 4-Cl H 3-CF ₃ - H 5-Cl H 5-Cl H 3-CF ₃ - H 3-CF ₃ H H . H 3-CF - H 3-CF ₃ H 4-Cl H 4-CK H 4-CF - H H H 3-CF ₃ H 3-CF ₃ ' H H H 4-NO ₂ - H H H H H 4-CF - H 4-C1- H H H 4-CF ^ - H 3-C1- H H H 4-CF - H 3-CF ₃ H 4-Cl H 4-CF ₃ - H 5-CF ₃ Cl 4-Cl Cl 4-CF - H 4-C1- Cl H H 4-CF - H 4-Br- H H H 4-CF - H H F. H H 4-CF,
j? H H H H H 4-CF - H 3-CF ₃ H 3-F H 3-CF ₃ - 4-Cl 3-Cl H 4-Cl H 3-Cl 4-Cl 3-Cl H 4-Cl 3-ci 5-Cl 5-Cl

509836/1009

BA-8O73-B "5k 3-Cl H. Y Z 10 09 X H 3-CF ₃ H 4-Cl H 3-Cl H H Cl H H 3-CF ₃ H 3-Br Br H H 4-CF H 3-CF ₃ H H H 4-CF H 3-Cl H 4-Cl H 3-Cl H 3-CF ₃ . H H H 4-CN H 4-Cl H 5-CF ₃ H 3-CF ₃ H H Cl H Cl 3-CF ₃ H 3-Cl H 4 -! - C ₃ H ₇ H 4-CF H H H H H 4-CF, H H H 4-CF H 4-NO ₂ H 3-Cl H 4-CF, H 3-NO ₂ H 3-Cl H 5-Cl H 4-CN H 4-Cl H 5-Cl H 3-NO ₂ 5-ci 4-Cl H H H 3-Cl H H H 5-Cl H 4-Cl 5-Cl 3-Cl H 3-F H 4-Cl 5-Cl 3-CF ₃ H . 5-Cl H 4-Cl 5-Cl 3-Cl H 4-Cl H 3-Cl H 3-Cl H 4-Cl H 3-NO ₂ H H H 4-Cl H 4-NO ₂ 4r-Cl 4-Cl Cl H Cl 3-Cl H 4-Cl H H H 4-CN 4-Cl 4-Cl Cl ' H H 3-Cl 4-Cl 3-CF ₃ Cl H Cl 3-Cl 4-Cl 3-Cl H 4-Cl H 3-Cl H H H 4-Cl - H 4-CN 5-Cl H H H H 3-Cl H H 4-Cl H • 3-CF3- 509836 /

BA-8O73-B

The following compounds were tested against yellow fever mosquito larvae (Aedes aegypti) in the described tea at a final concentration of 0.5 ppm; at least 50 % of the larvae were killed.

OUV N = N-C = N-

2-Cl2-Cl2-Cl2-CF-2-Cl 3-CF, 2-CF, 2-Cl

4-NO, 2-Ν0 _Λ

3-CF,

3-Cl

4-Cl 4-Cl 4-Cl 4-Cl 5-Cl 6-F 4-F 4 -Br H H 6-Cl

Ί-Cl

ä 6-Cl

5-Cl

H.

2-Cl

2-Cl

2-Cl

2-CF-

2-Cl '

3-CF,

2-CF_

2-Cl

4-Cl

3-CF,

4-Cl

4-Cl

4-Cl

4-Cl

5-Cl

6-F

4-F

4-Br

-NO

5-Cl

6-Cl

6-Cl

5-Cl

H.

..H H Ή H H H H H

H (sodium salt)

H Η

- 60 -

509836/1009

BÄ-8073-B

Example 22

Red liver bean plants in the two-leaf stage were grown up to Sprayed drain with formulations with a concentration of 0.05 of the listed 3-formazan carbonitriles. Suspensions were prepared by adding 50 mg of the compounds in 50 ml aliquots Acetone were dissolved by adding 1 ml of a l ^ igen Methocel Solution was added and by diluting to volume with a Duponol water solution, 1: 3000. After drying The leaves were removed from the plants and placed individually in covered Petri dishes at the same time as 10 southern armyworm larvae brought in. The evaluations were made for each compound after 3 days; the values are given below :

- 61 -

5098 3 6/1009

BA-8O73-B

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509836/1009

m ο,

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2Ä60255

BA-8073-B

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509836/1009

B4-8O73-B

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509836/1009

BA-8O73-B (continued)

© moo © omoooooooomo σ * co © ο co © οοοοοοοοοοοσ ^ οο

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509836/1009

BA-8O73-B (continued)

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509836/1009

3-CF ₃ 4-Cl 4-Cl 3-Cl H . H 2-CF ₃ 4-Cl H 3-Cl H H 4-CN 4-Cl 3-Cl. H H .H 3-Cl H S-Cl H

100 oo ο -j

100

100

100

4-NO,

3-NQ ₅

4-Cl

3-CF,

4-Cl

cn
ο
co ₄ . _CF

4-CF,

2-NO,

4-Cl

4-Cl

4-Cl

4-Cl

4-Cl

4-Cl

4-CF ₃

4-CF ₃

3-Cl

3-Cl

3-CF "

2-Cl 4-Cl 3-Cl

• H H H

H
H
H
H
3-Cl

H
H

H
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H
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H H H H H

H H

H H

H H

100

100 ^

85 pounds

(D

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H (potassium salt) 100

H (potassium salt), 100

H (potassium salt) iQO

H (potassium salt) IOO

H 100

H 100

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CD Ό 'K)

BA-8073-B

(Continuation)

2A60255

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4- 68 - 509836/1009

BA-8073-B

(β

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BA-S073-B
Example 25

Soya bean plants in the true two-leaf stage were sprayed with an aqueous suspension of 1,5-bis (4-trifluoromethyl) -3-formazanecarbonitrile at a concentration of 0.03% until they had dripped off. The formulation used contained activated carbon in addition to the other normal formulation ingredients. The plants grew under light in the laboratory for 8 days and were in excellent condition with lush dark green foliage. The leaves were then removed and placed in petri dishes (3 / dish) along with 10 southern army worm larvae approximately 1.2 cm in length. One day later it was found that all larvae in the control experiment were alive without treatment, while all those exposed to the treated leaves were dead.

example 2k

Test units were prepared each containing 10 Lygus bugs collected from a field in Delaware. Two of these units were sprayed with acetone solutions containing 1,5-bis (- ^; i-trifluoromethylphenyl) -3-formazancarboniti'il at concentrations of 0.01 % and two with pure acetone (comparison test). The insects were placed in a room of constant temperature and constant humidity and provided with drinking water. The test results after three days are given below;

ffiSpray concentration test number ^ kill

0.01 1 100

2 100

Comparative experiment 1 20

2 20

- 70 -

509836/1009

BA-8O73-B

B is ρ ie 1 25

Red kidney bean plants that were about two weeks old were until drained with a 0.05 / kigen S.uspension of 1,5-bis (Ί-Trifluormetlrylphenyl) -3-formazancarbonitril sprayed, After drying, they were put into one with 10 gray crickets Cage introduced. Two days later, most of the foliage was there of the comparative plants consumed, and most of the crickets lived and ate. All crickets made with the treated Plants locked in were dead so the plants could grow unmolested.

Example 26

Leaf disks with a diameter of 4.2 cm were made from the Cut out cotyledons from bean plants. The leaves were in an acetone solution of 1,5-bis (4-trifluoromethyl-3-formazanecarbonitrile immersed at a concentration of 0.1% and then dried. The treated disks were each placed in Petri dishes with 10 speckled cucumber beetles. All beetles in the comparison experiment lived after one day, while all beetles exposed to the treated leaf disks were dead.

Example 27

20 corn earworm larvae, which were individually raised on an artificial standard food in 30 ecm cups ■, were

- 71 -

509836/100 «

BA-SO73-B

flat with an acetone solution of 1,5-UiS (^ - TrIfluorraethylphenyl) -3-formazanecarbonitrile treated. The larvae were treated by adding 1 microliter of a solution containing one microgram of compound on the back of each Insect was applied. Two days later, all 20 treated larvae were dead, while the 20 untreated larvae all lived and grew rapidly.

Example 28

Red liver bean plants in the two-leaf stadiura were sprayed in a group of three with a 0.015% suspension of 1,5-bis (4t-trifluoromethylphenyl) -3-foririazancarbonitrile in water. The leaves were removed individually from the plants and placed in covered Petri dishes together with 10 beet armyworm larvae, which were 8 days old and each weighed about 13 mg. The insect culture was a standard laboratory culture from Tucson, Arizona. Two days later, all of the insects feeding on the treated leaves were dead. 95 % of the insects feeding on the untreated leaves lived and grew rapidly.

Example 29

A flowering crab apple tree in Mendenhall, Pennsylvania grows, and with eastern tent caterpillar, (eastern tent caterpillar) was infected, was with an aqueous suspension of a wettable powder formulation of 1,5-bis (* i-trifluoromethyl) -3-formazanecarbonitrile a concentration of 320 ppm active ingredient

- 72 509836/10 0 9

ΒΛ-8Ο73-Β

dience "- the larvae were at the time of spraying about 1.5 em long. Many dead caterpillars were found five days later no more living caterpillars in the nest or on the leaves or twigs. Caterpillars on an identical but untreated old tree, who saw near were big and strong and had a large part of the foliage destroyed.

Example 30

Discs with a diameter of h cm were cut from the leaves of a linden tree and lightly washed with acetone solutions of 1,5-his ('i-trifluoromethylphenyl) -3-formazanecarbonitrile (A), 1- (3,5-dichlorophenyl) -5 ~ (3-trifluoromethylphenyl) -3-fonaazancarbonitril (B) and 1,5-bis (3, ^{i-dichlorophenyl)} -3 ~ f sprayed orinazancarbonitril (C). The disks were each placed on moistened filter paper in Petri dishes together with 2 Japanese beetles each. The evaluations were carried out kS hours later; the results given below show excellent "effects of the compounds;"

Compound concentration of % kill (^ S hours) active ingredient (£ ·)

A '0.01 100

B 0.01 100

C 0.01 100

Comparative experiment - 0

- 73 -

509836/1009

BA-SO73-B

T he s piel 31

Bauamol! Plants approximately 25 cm high were sprayed with an aqueous suspension of 1,5-bis ('i-trifluoromethylphenyl) -3-forniazanearbonitrile at a concentration of 50 ppm until they ran off. Two days later, each test plant was challenged with 10 cotton boll beetles. Three days later, 100,000 of the beetles were dead on the treated plants, while only 50,000 were dead on the untreated plants. The treated plants were hardly eaten, while the untreated plants were considerably damaged.

Example 32

Acetonic solutions of 1,5-bis (4 ~ trifluoromethylphenyl) -3 ~ formazanocarbonitrile (A) and 1,5-bis (3> ^z t-dichlorophenyl) -3- ^ formazanoarbonitrile (B), each in concentrations of 100 ppm , were sprayed into vessels (6.5 cm × 6.5 cm) and closures in order to deposit a thin film of solution on them. After drying, 5 dog uses are placed in each jar; then the vessels are closed. The values after 2 days are given below:

Compound Concentration % kill active ingredient (ppm) __

A 100 100

B 100 100

Comparative ⁱ

attempt - 0

- 74 -509836/1009

BA-SO73-B

B ei vs ρ ie 1 55

Experiments were made in a cabbage plantation in Newark, Delaware with 1,5-bis (Ί-trifluorinethylphenyl) -5-f orruazancarbonitril (A) and 1- (^ - chloroplienyl) -5- (3-trifluoriiiethylplienyl) -3-formazanecarbonitrile (B) performed. There were four test fields νση 7 meters long. The plants were released in late spring and weekly after insects were present sprayed. In the untreated areas, strong populations of imported cabbage worm and earth fleas developed. The data recorded on August 15, 1974t will be reproduced below and show the excellent effect of the agent on both types of insect.

link concentration
(active) ppm fc effect
Imported
Cabbage worm Earth flea A. 320 99 92 B. 320 99 90 Comparative
attempt 0 0 (93% indicated
eat it
Foliage) (30% of the outside
ren leaves
and 50% of the
Head leaves
damaged)

Example J> k '

Potato leaves, about h cmχ 3 cm, were removed from a plant and lightly treated with an acetone solution of 1,5-bis- (A-trifluorraethylphenyl) -3-forraazane carbonitrile at a con-

- 75 -. 509836/1009

BAD ORJGINAL

BA-SO73-B

concentration of $ 0.01 ■ active ingredient sprayed. After drying, the sprayed leaves were each placed on moistened filter paper in Petri dishes together with 2 CoI orado potatoes per shell. After 2h hours vurdo found that all of the beetle on the treated Blältern were dead, while the were healthy on untreated leaves and the leaves arranty further ten.

¹ - 76 -

509 8 36/1009 BAD ORIGINAL

Claims (1)

Pat ent X is a trifluoromethoxy-j trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, pentaf lxxoräthylthio, pentafluorothio, Cyano, trifluoromethyl group, chlorine, bromine, fluorine or a nitro group Y hydrogen, trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy-j pentafluoroethylthio, pentafluorothio group, chlorine, bromine, fluorine, a trifluoromethyl or alkyl group with 1 to k carbon atoms; . Hydrogen, chlorine, bromine, fluorine or a trifluoromethyl group; * Hydrogen, chlorine, bromine, fluorine or a trifluoromethyl group; - 77 - 5098 3 6/1009 BA ~ 8O73-B R »hydrogen, chlorine, bromine, fluorine, a trifluoriaethyl- or nitro group; Z are hydrogen, chlorine, bromine or fluorine, where l) if X is a nitro group, at least one of the Groups Y or R- be a trifluoromethyl group got to; 2) when Y is an alkyl group of 1 to h carbon atoms, X is a trifluoromethyl group; 3) when R_ is a nitro group, X is a trifluoromethyl group is; and 4) when X is halogen, no more than three of the groups R., R ₀ , R 1, Z and Y can be hydrogen; 1 d J and the agriculturally suitable salts of these Links. 2. Lithium, potassium or sodium salts of the compound Claim 1. Compound according to claim 1, in which according to formula X a trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, Pentafluoroethylthio, pentafluorothio, Cyano, trifluoromethyl group, chlorine, bromine, fluorine or a nitro group; Y hydrogen, trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, pentafluoroethylthio, pentafluorothio, chlorine, bromine, fluorine, a trifluoromethyl or Alkyl group having 1 to h carbon atoms; - 78 - 5098 3 6/1009 BA-8O73-B. R. Hydrogen, chlorine, bromine, fluorine or a trifluoromethyl group; R _{2 is} hydrogen, chlorine, bromine, fluorine or a trifluoromethyl group; R_ hydrogen, chlorine, bromine, fluorine, a trifluoromethyl or nitro group; Z are hydrogen, chlorine, bromine or fluorine, where I) "when X is a nitro group, at least one of the Groups Y or R_ be a trifluoromethyl group, got to; 2) when Y is an alkyl group, X is a trifluoromethyl group of 1 to * k carbon atoms; 3) when R 1 is a nitro group, X is a trifluoromethyl group is; and h) if. X is halogen, no more than three of the groups R., R ₂ , R_, Z and Y can be hydrogen. k. A compound according to claim 1, wherein X is a trifluoromethyl group, chlorine, bromine, a 4-pen.ta- fluoroethoxy or nitro group; Y is hydrogen, a trifluoromethyl, 4-pentafluorathoxy or branched alkyl group having 3 or h carbon atoms, chlorine, bromine or fluorine; R- hydrogen, chlorine or bromine;
R_ is hydrogen, chlorine or bromine and R- and Z are each hydrogen, where 1) if. X is halogen, no more than one of the groups R., R ₂ and Y can be hydrogen; 2) when Y is a branched alkyl chain of three or four carbon atoms, X is trifluoromethyl; - 79 - 509836/1009 BA-8O73-B 2ο 3) when X is a nitro group, Y is a trifluoromethyl group is; and the agriculturally suitable salts of these Links. Lithium, potassium or sodium salts of the compounds according to claim k. A compound according to claim k _t wherein X is a trifluoromethyl, 4-pentafluoroethoxy or Nitro group, chlorine, bromine; Y hydrogen, trifluoromethyl group, chlorine, bromine, Fluorine, 4-pentafluoroethoxy or branched alkyl group with 3 or 4 carbon atoms; R. Hydrogen, chlorine or bromine; H “hydrogen, chlorine or bromine; R_ and Z are each hydrogen, where 1) when X is halogen, no more than one of the groups. R., R "and Y can be hydrogen; 2) when Y is a branched alkyl group of 3 or k carbon atoms, X must be a trifluoromethyl group; 3) when X is a nitro group, Y is a trifluoromethyl group is. 7. A compound according to claim 4, wherein X is a trifluoromethyl group, chlorine, bromine or a k- pentafluoroethoxy group and - 80 509836/1009 BA-8O73-B Y are hydrogen, chlorine, bromine, fluorine, a 4-pentafluoroethoxy or branched alkyl group with 3 or h carbon atoms; as the agriculturally suitable salts of these Links. 8. Lithium, potassium or sodium salts of the compounds according to claim 7. Compounds according to claim 4, wherein X is a trifluoromethyl group, chlorine, bromine or a 4-pentafluoroethoxy group; and Y hydrogen, chlorine, bromine, fluorine, a 4t-pentafluoroethoxy or branched alkyl group with 3 or h are carbon atoms. 10. A compound according to claim 7 »wherein X is chlorine, bromine or a 4-pentafluoroethoxy group and Y hydrogen, chlorine, bromine, fluorine or a 4-penta are fluoroethoxy group; as the agriculturally suitable. Salts of these compounds . 11. Lithium, potassium and sodium salts of the compounds according to claim 10. - 81 - 50983 6/1009 BA-8O73-B ti 12. A compound according to claim 7, wherein X is chlorine, bromine or a 4-pentafluorathoxy group; and Y is hydrogen, chlorine, bromine, fluorine or a 4-pen.ta-fluorathoxy group. 13. A compound according to claim 4, wherein X is a trifluoromethyl group and Y is a trifluoromethyl group, hydrogen, chlorine or Are bromine; and "the lithium, potassium and sodium salts of these Links. A compound according to claim k, wherein X is a trifluoromethyl group and Y is a trifluoromethyl group, hydrogen, chlorine or bromine. 15. A compound according to claim 7, wherein X is chlorine or bromine;
Y chlorine or bromine; and R "are chlorine or bromine; and the lithium, potassium or sodium salts of these compounds. 16. A compound according to claim 7 »wherein X is chlorine or bromine; ' - 82 - 509836/1009 BA-8O73-B Y chlorine or bromine; and R _{2 are} chlorine or bromine. 17. 1,5- »fris (4-Tr if luorme thylphenyl) -3-f orinazan carbon i tril. 18. 1,5-ois (3 »^ - dichlorophenyl) -3-formazanecarbonitrile. 19. 1- (4-Trifluoromethylphonyl) -5-phenyl-3-formazanecarbonitrile, 20 l- (4-trifluoromethylphenyl) -5- ⁽ⁱ i-chloro-phenyl) -3- formazane carbonitrile. 21. 1— (3-trifluorme thy lphenylJ-S - ^ - chlorophenyl) -3-form azancarbonitrile. 22. 1- (3-trifluoromethylphenyl) -5- (3 »5-dichlorophenyl) -3- formazane carbonitrile. 23. 1- (4-Trifluoromethylphenyl) -5- (3,4-dichlorophenyl) -3- formazane carbonitrile. 2k, 1,5-bis (3,5-dichlorophenyl) -3-formazane carbonitrile. 25. lr (4-trifluoromethylphenyl) -5- (4-chloro-.3-trifluorme ethylphenyl) -3-formazancarbonitrile. - 83 - 509836/1009 BA-8O73-B 26. 1- (4-Trifluoromethylphenyl) -5 ~ (2-chloro-5-trifluoromethyl- ph, enyl) -3-formazane carbonitrile. 27. l- {4-Tri fluorine thy lphenyl) -5- (2,6-difluorophenyl) -3- formazane carbonitrile. 28. 1- (4-Trifluoromethylphenyl) -5 ~ (3-ni troph.en.yl) -3-formazan carbonitrile. 29. 1- (4-Tri fluorine thylphenyl) -5- (4-ni tr ο phenyl) -3-formniazane carbonitrile. 30. 1- (4-trifluoromethylphenyl) -5- (3-fluorophenyl) -3-formazan carbonitrile. 31. 1- (4-Trifluoroinethylphenyl) -5- (3-chlorophenyl) -3-formazan carbonitrile. 32. 1- (4-Trifluoromethylphenyl) -5-t4-isoprQpylphenyl) -3- formazane carbonitrile. 33. i_ (4-trifluoromethylphenyl) -5- (2,4,6-trichlorophenyl) -3- formazancarbonltrile. 34. 1- (4-Trifluoromethylphenyl) -5- (3-trifluoromethylphenyl) -3 formazane carbonitrile. - 84 - 509836/1009 BA-8O73-B 35. 1- (4-Trifluoromethylpheuyl) -5-0- ^bromo P ^heij y ¹ ) "3" ^form ". Azanecarbonitrile. azancarbonitrile. 37. 1,5-bis (3, ^ - dichlorophenyl) -3-formazanearbonitrile, Potassium salt. 38. Composition for combating insects and arachnids, characterized in that it is essentially from an inert diluent and / or a surface-active one Agent and an effective amount of a compound of the formula CN Ii = N-C-N-NH- ordered in the 509836/1009 BA _r 8O75-B o / X is a trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, pentafluoroethylthio, pentafluorothio, Cyano, trifluoromethyl, nitro, chlorine, bromine, fluorine; Y hydrogen, trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, Pentafluoroethoxy, pentafluoroethylthio, Pentaf luorthio group, chlorine, bromine, fluorine, trifluoromethyl or an alkyl group having 1 to 4 carbon atoms; R. Hydrogen, chlorine, bromine, fluorine or a trifluoromethyl group; R _{2 is} hydrogen, chlorine, bromine, fluorine or a trifluoromethyl group; R, hydrogen, chlorine, bromine, fluorine, a trifluoromethyl or nitro group; Z is hydrogen, chlorine, bromine or fluorine and Q is hydrogen, chlorine, bromine or fluorine, where 1) when Y is an alkyl group having 1 to h carbon atoms, X is a trifluoroethyl group; 2) if X is a 4-bromo or 4-fluoro group and R., Q and three of the groups R ₀ , Z, Y and R are hydrogen, the remaining groups R ₂ , Y, R_ and Z are something other than 4 Are -bromo or 4-fluoro groups; 3) when X is a nitro group, R_ something other than Is hydrogen; · and h) when X is halogen, at least one of the groups R., R ₂ , R_ and Q, Y and Z must be something other than hydrogen; and the agriculturally suitable salts of these Links. 509836/1009 - 86 - JB & -8O73-B 39 · Composition according to claim 38, characterized in that it contains the lithium, potassium or sodium salts. Composition according to claim 38, characterized in that that it contains compounds of the formula given, in the X is a trifluorraethoxy, trifluoromiethylthio, 1,1,2,2-tetrafiuorethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, pentafluoroethylthio, pentafluorothio, cyano, trifluoromethyl group, chlorine, bromine, fluorine or a nitro group; Y is hydrogen, a trifluoromethoxy, trifluoromethylthio , 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, pentafluoroethoxy, pentafluoroethylthio, pentafluorotloro group, chlorine, bromine, fluorine, a trifluoroethylthio group - Or alkyl group with 1 to 4 carbon atoms; R ₁ Va ^ seratoff, chlorine, bromine, fluorine or a trifluoromethyl group; ^ B ₂ hydrogen, chlorine, bromine, fluorine or a trifluoromethyl group; R_ hydrogen, chlorine, bromine, fluorine, a trifluoromethyl or nitro group j Z is hydrogen, chlorine, bromine or fluorine and Q are hydrogen, chlorine, bromine or fluorine, where 1) when Y is an alkyl group with 1 to H Is carbon atoms, X is trifluoromethyl group; 2), if X is a 4-bromo or 4-fluoro group and R., Q and two of the radicals.R ₂ , Z, Y and R_ are hydrogen, the remaining of the groups R ₂ , Y, R- and Z are something different must be than the 4-bromo or 4-fluoro group; 509Ö36 / 1009 BA-8O73-B 3) when X is a nitro group, R_ something other than Is hydrogen;
4) when X is halogen, at least one of the groups IL, R ₀ , R ", Q, Y and Z is something other than hydrogen must be. kl, composition according to claim 38, characterized in that it contains compounds of the formula indicated in which
X is a trifluoromethyl group, chlorine, bromine, a penta fluoroethoxy or nitro group;
Y hydrogen, a trifluoromethyl group, chlorine, bromine ^ fluorine, a pentafluoroethoxy or branched alkyl group with 3 or k carbon atoms; R. Hydrogen, chlorine, bromine or trifluoromethyl group; R _{2 is} hydrogen, chlorine, bromine or a trifluoromethyl * · group; R, hydrogenj Z hydrogen or chlorine and Q are hydrogen or chlorine, where 1) when Y is a branched alkyl group with 3 or 4 carbon atoms X is trifluoromethyl; 2) when X is halogen, no more than one of the Groups R., R "and Y are hydrogen; and 3) when X is a nitro group, R_ is different as hydrogen; and the agriculturally suitable salts of these Links. Ί2. Composition according to claim 11, characterized in that that it contains the lithium, potassium or sodium salts. 509836/1009 BA-8O73-B 43 · Composition according to claim 38, characterized in that it contains compounds of the formula indicated in which
X is a trifluoromethyl group, chlorine, bromine, a penta fluoroethoxy or nitro group; Y hydrogen, a trifluoroethyl group, chlorine, bromine, Fluorine or a pentafluoroethoxy or branched alkyl group with 3 - ^ carbon atoms; R. Hydrogen, chlorine, bromine or a trifluoromethyl group; R _{2 is} hydrogen, chlorine, bromine or a trifluoromethyl group; R, hydrogen; Z hydrogen or chlorine; and Q are hydrogen or chlorine, where 1), if Y is a branched alkyl group with 3 or 4 Koh is carbon atoms, X is a trifluoroethyl group; 2) when X is halogen, no more than one of the groups R ₁ , R ₂ and Y can be hydrogen and 3) when X is a nitro group, R_ is something other than hydrogen. 44. Composition according to claim 38 for combating insects. -. 45 · Composition according to claim 39 for combating Insects. 46. Composition according to claim 40 for combating Insects. 47. Composition according to claim I41 for combating Insects. 509836 / 100ä - 89 - BA-8O73-B So 48. Composition according to claim 42 for combating insects. 49. Composition according to claim 43 for combating of insects. 50. Composition according to claim 38 for combating of arachnids. 51 · Composition according to claim 39 for combating arachnids. 52. Composition according to claim 40 for combating arachnids. 53 · Composition according to claim 4l for combating of arachnids. 54. Composition according to claim 42 for combating of arachnids. 55 · Composition according to claim 43 for combating of arachnids. 56. Composition according to claim 44, characterized in that that they are a compound of the formula CN " ³
ι N = N-C = N-NH R ₂ contains, in the 509836/1009 - 90 - BA-8O73-B X is a trifluoromethoxy, trifluorraethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio ₇ , pentafluoroethoxy, pentafluoroethylthio, pentafluorothio, cyano, trifluoromethyl group, chlorine, bromine, fluorine or a nitro group; Y hydrogen, a trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, Pentafluoroethoxy, pentafluoroethylthio, Pentafluorothio group, chlorine, bromine, fluorine, a trifluoromethyl or alkyl group with 1. to Carbon atoms; R. Hydrogen, chlorine, bromine or a trifluoromethyl group; R. "Hydrogen, chlorine, bromine or a trifluoromethyl group; R_ hydrogen, chlorine, bromine, fluorine, trifluoromethyl or nitro group; Z are hydrogen, chlorine, bromine or fluorine, where. 1) when Y is an alkyl group having 1 to 4 carbon atoms X is trifluoromethyl; 2) when R 1 is nitro, X is trifluoromethyl; 3), if X is a 4-bromo or 4-fluoro group and R., R ", Z and one of the groups R "and Y is hydrogen, the remaining of the groups R1 and Y must be something other than a 4- or 4-fluoro group; 4) when X is a nitro group, Y is a trifluoromethyl group is; and the agriculturally suitable salts of these Links. 509836/1009 BA-8O73-B 57 · Composition according to claim 56, characterized in that that it contains the lithium, potassium or sodium salts of these compounds. 58. Composition according to claim Jjil, characterized in that that it contains compounds of the formula given, in the X is a trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, Pentafluoroethoxy, pentafluoroethylthio, pentafluorothio-j Cyano, trifluoromethyl group, chlorine, bromine, fluorine or a nitro group; Y hydrogen, trifluoromethoxy, trifluoromethylthio, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-tetrafluoroethylthio, Pentafluoroethoxy, pentafluoroethylthio, Pentafluorothio group, chlorine, bromine, fluorine, a trifluoromethyl or an alkyl group having 1 to 4 carbon atoms ; R. Hydrogen, chlorine, bromine or a trifluoromethyl group; . Rp hydrogen, chlorine, bromine or a trifluoromethyl group;
R_ hydrogen, chlorine, bromine, fluorine, trifluoromethyl or nitro group; Z are hydrogen, chlorine, bromine or fluorine, where 1) when Y is an alkyl group having 1 to 4 carbon atoms X is trifluoromethyl; 2) when R 1 is a nitro group, X is a trifluoromethyl group is; 3) »if X is a 4-bromo or 4-fluoro group and R., Z and two of the groups R _n and Y and R ^ are hydrogen, the remaining groups of R ₂ , Y and R_ are something other than 4-bromine or must be 4-fluoro groups; 509836/1009 BA-8O73-B k) t when X is a nitro group, Y is a trifluoromethyl group. . 59 · Composition according to claim 56, characterized in that that it contains compounds of the formula given, in the X is a trifluoromethyl group, chlorine, bromine, a pentafluoroethoxy or nitro group; Y is hydrogen, trifluoromethyl group, chlorine, bromine, fluorine or a pentafluoroethoxy or branched alkyl group with 3 or k carbon atoms; R_ hydrogen and Z are hydrogen, where, if X is halogen, not more than one of the groups R., R ₂ and Y can be hydrogen; and the agriculturally suitable salts of these Links. 60. Composition according to claim 59 »characterized in that that it contains the lithium, potassium or sodium salts of these compounds. 61. Composition according to claim 56, characterized in that that they have compounds of the specified. Contains formula in the X is a trifluoromethyl group, chlorine, bromine or pentafluoroethoxy or nitro group; Y is hydrogen, a trifluoromethyl group, chlorine, bromine, fluorine or a pentafluoroethoxy or branched alkyl group with 3 or _r 4 carbon atoms; R, hydrogen and
Z are hydrogen, where, if X is halogen, no more than one of the groups R ₁ , R ₂ and Y can be hydrogen. "■: 509836/1009 BA-8O73-B 62. Composition according to claim 59 » characterized in that it contains compounds of the formula in which X is a trifluoromethyl group, chlorine, bromine or a Pentafluoroethoxy group; Y is hydrogen, chlorine, bromine, fluorine, a pentafluoroethoxy or branched alkyl group with 3 or h carbon atoms; R _{1 is} hydrogen, chlorine or bromine; R _{2 are} hydrogen, chlorine, or bromine; and the agriculturally suitable salts of these Links. 63. Composition according to claim 62, characterized in that it contains the lithium, potassium or sodium salts this contains compounds. 64. Composition according to claim 59a, characterized in that that it contains compounds of the formula given, in the X is a trifluoromethyl group, chlorine, bromine or a pentafluoroethoxy group; Y is hydrogen, chlorine, bromine, fluorine, pentafluoroethoxy or branched alkyl group with 3 or h carbon atoms; R _{1 is} hydrogen, chlorine or bromine; Rp are hydrogen, chlorine or bromine. 65. Composition according to claim 62, characterized in that it contains compounds of the formula given contains, in the 509836/1009 - 9/1 - BA-8O73-B X chlorine, bromine or a pentafluoroethoxy group and Y is hydrogen, chlorine, bromine, fluorine or a pentafluoroethoxy group are; and / or the lithium, potassium or sodium salts of these compounds. 66. Composition according to claim 6 ¹ I, characterized in that it contains compounds of the formula indicated in which
X chlorine, bromine or a pentafluoroethoxy group and Y is hydrogen, chlorine, bromine, fluorine or a pentafluoroethoxy group are. 67 · Composition according to claim 59 *, characterized in that it contains compounds of the formula indicated in which
X is a trifluorraethyl group, Y is a trifluoromethyl group, hydrogen, chlorine or Bromine; Usually hydrogen, chlorine or bromine
R “are hydrogen, chlorine, or bromine; and / or the lithium, potassium or sodium salts of these compounds. 68. Composition according to claim 6l, characterized in that it contains compounds of the formula given in which ^v X is a trifluoromethyl group, Y is a trifluoromethyl group, hydrogen, chlorine, bromine, Usually hydrogen, chlorine or bromine R _{2 are} hydrogen, chlorine or bromine. 509836/1009 - 95 - BA-8O73-B 69 · The method according to claim 65, characterized in that it contains compounds of the formula indicated in which
X chlorine or bromine, Y is chlorine or bromine and R _{2 is} chlorine or bromine; and / or the lithium, potassium or sodium salts of these compounds. 70. Composition according to claim 66, characterized in that that it contains compounds of the general formula in which X chlorine, or bromine, Y chlorine or bromine, R "are chlorine or bromine. 71. Composition according to claim 4 * 1, characterized by a content of 1,5-bis ( ² I-trifluoromethylphenyl) -3-formazanecarbonitrile. 72. Composition according to claim 44, characterized by a content of l, 5-bls (3 » ^/ t-dichlorophenyl) -3-formazanecarbonitrile. 73 · Composition according to claim 44, characterized due to the content of 1- (4-trifluoromethylphenyl) -5-phenyl-3-formazanecarbonitrile. 74. Composition according to claim 44, characterized by the content of 1- (4-trifluoromethylphenyl) -5- (4-chlorophenyl) -3-formazane carbonitrile. 509836/1009 - 96 - BA-8U73-B 75. Composition according to claim ² J ¹ I, characterized by the content of 1- (3-trifluoromethylphenyl) -5- (4-chlorophenyl) -3-formazanecarbonitrile. 76. Composition according to claim 44, characterized by the content of 1- (3-trifluoromethylphenyl) -5- (3,5-dichlorophenyl) -3-iOi "raazancarbonitril. 77. Composition according to claim 44, characterized by the content of 1- (4-trifluoromethylphenyl) -5- (3,4-dichlorophenyl) -3-formazan carbonitrile. 78. Composition according to claim 44, characterized due to the content of 1,5-ois (3,5-dichlorophenyl) -3-formazanecarbonitrile. 79 · Composition according to claim 44, characterized due to the content of l- (4-trifluoromethylphenyl) -5- (4-chloro-3-trifluoromethylphenyl) -3-forraazanecarbonitrile, 80. Composition according to claim 44, characterized by content of! - (^ - trifluoromethylphenylJ-S-CS-chloro-5-trifluoromethylphenyl) -3-formazanecarbonitrile, 81. Composition according to claim 44, characterized by the content of. 1- (4-Trifluoromethylphenyl) -5- (2,6-difluorophenyl) -3-formazane carbonitrile. 82. Composition according to claim 44, characterized in that it contains 1- (4-trifluoromethylphenyl) -5- (3-nitrophenyl) -3-formazanecarbonitrile. 5 09836/1009 BA-8O73-B 83 · Composition according to claim 44, characterized by the content of 1- (4-trifluoromethylphenyl) -5 - (^ - nitrophenyl) -3-formazane carbonitrile. 84. Composition according to claim 44, characterized due to the content of 1- (4-trifluoromethylphenyl) -5- (3-fluorophenyl) -3-formazanecarbonitrile. 85. Composition according to claim 44, characterized due to the content of 1- (4-trifluoromethylphenyl) -5- (3-chlorophenyl) -3-formazanecarbonitrile. 86. Composition according to claim 44, characterized by a content of 1- (4-trifluoromethylphenyl) -5- (4-isopropylphenyl) -3-formazanecarbonitrile. 87 · Composition according to claim 44, characterized due to the content of l- (4-trifluoromethylphenyl) -5- (2,4, trichlorophenyl) -3-formazancarbonitrile. 88. Composition according to claim 44, characterized in that it contains 1- (4-trifluoromethylphenyl) -5- (3-trifluoromethylphenyl) -3-formazanecarbonitrile. 89. Composition according to claim 44, characterized due to the content of 1- (4-trifluoromethylphenyl) -5- (3-bromophenyl) -3-formazanecarbonitrile. 90. Composition according to claim 44, characterized due to the content of 1- (4-trifluoromethylphenyl) -5- (4-bromophenyl) -3-formazanecarbonitrile. SQ9836 / 1009 - often - BA-8O73-B 91. Composition according to claim ^ ₉ characterized by a content of 1,5-bis (3,4-Di chi orphenyl) -3-forniazancarbonitril, potassium salt. 509836/1009 - 99 -