CS198217B2 - Insecticide and process for preparing effective components - Google Patents

Abstract

The insecticide according to the invention contains a novel thiadiazolylbenzamide of the formula I <IMAGE> in which the substituents are as defined in Claim 1, and an inert carrier.

Description

The present invention relates. . and a process for preparing a series of novel N- (1,3,4-thiazol-2-yl) benzamides containing a 'phenyl,' naphthyl or heteroaryl group at the 5-position of the thiadiazoil ring and a 2,6-substitution on the benzene ring. These compounds are useful as insecticides.

Insect control is one of the main problems of agricultural chemical research, which is continuing intensively. Insects of various species endanger crops of all types and *. It also causes' unhealthy conditions and contamination by food contamination. Insect damage is incalculable and the control of harmful insects necessarily has a high priority. .....

Recently, research into new and improved insecticides has been accelerated by removing old insecticides that leave residues.

The compounds of formula I are novel. Some of them 'known in the literature' are. however, of interest, for example, Ce-balo, U.S. Pat. No. 3,726,892 discloses the herbicidal effect of 1,3,4-thiadiazol-2-ylureas.

Rao, Indian J. Chem. No. 8,509-13 (1970) discloses the synthesis of 2-amino-1,3,4-thiadiazoles, which are intermediates for the compounds of the present invention.

Wellinga. and Mulder, U.S. Patent No. 3,748,356 discloses the herbicidal effect of N-benzoyl-N '-phenyl ureas.

The present invention relates to the field of agricultural chemistry and to the field of the present invention are prepared novel thiadiazolylbenzamides of the general formula I

where

R 0, R ¹ and R ² are each independently hydrogen, chlorine or bromine, with at least one of R 0, R ¹ and R ² being chlorine or bromine,

X is an oxygen or sulfur atom,

R ³ and R ⁴ are each independently hydrogen, chlorine, bromine or methyl, wherein R ³ is hydrogen when X is oxygen,. and either.

1) R ⁵ and R ⁷ are hydrogen, one of R ⁸ and R ⁸ is hydrogen and the other of R ⁸ and R ⁸ is hydrogen, chlorine, methoxy, bromine, iodine, fluorine, trifluoromethyl, methyl , hydroxy}, phenyl or phenyl monosubstituted with bromine, chlorine or fluorine; or

2) R ⁸ and R ⁷ are hydrogen and R ⁸ and R ⁸ are independently chlorine, fluorine, bromine or

3) R ⁸ and R ⁸ are hydrogen and R ⁷ and R ⁸ are independently chlorine, fluorine, bromine or trifluoromethyl,

4) R ⁷ and R ⁸ are hydrogen and R ⁸ and R ⁸ are independently chlorine, fluorine or bromine; or

5) R ⁷ , R ⁸ and R ⁸ are hydrogen and R ⁸ is chlorine, fluorine or bromine; or R ⁸ , R ⁷ and R ⁸ are hydrogen and R ⁸ is acetamido, nitro, amino or cyano,

_Rio drank _SOU j is _{independently} hydrogen, chlorine, fluorine, bromine, methyl or methoxy, wherein

1) one of R ¹⁰ and R ¹¹ can be hydrogen if the other is only methoxy,

2) at least one of R ¹⁰ and R ¹¹ must be methyl or methoxy, unless

(a) R ⁸ is not hydrogen and R ⁸ , R ⁷ and R ⁸ is hydrogen; or

b) R ⁸ and R ⁸ are hydrogen and one or both of R ⁷ and R ⁸ are trifluoromethyl;

3) neither R ⁸ nor R ⁸ are phenyl, acetamido, methďxyl, nitro, aminosku- · full, cyano or substituted phenyl unless both ^R18 and R ^u is methoxy,

4) two of R ^7, R ⁸ and R ⁸ are hydrogen unless both ^R10 and ^Rn are methyl or methoxy,

5) both R ¹⁰ and R ¹¹ are methoxy or methyl when R is pyrldyl, naphthyl, furyl or thienyl,

6) both R ¹⁰ and R ¹¹ are methoxy when R is benzothiazolyl, benzoxazolyl, benzothlenyl, benzofuryl, isoxazolyl, quinolyl or thiazolyl by acylating 2-amino-5-R-substituted

1,3,4-Thladiazole II

R ** R ² *

R is as defined in formula I, except that R is not aminophenyl or acetamidophenyl, a benzoyl halide of formula III wherein:

/? ^<0 hX-C

к um.

hal is chlorine or bromine and r 10 _and r 11 are as defined in formula I, and optionally reducing a compound of formula I wherein R ® is nitro to form a compound wherein R ® is amino and optionally acylating the compound of formula I, wherein R ® is amino to form a compound wherein R ® is acetamido.

The present invention relates to an insecticidal composition which is characterized in that it contains a compound of the above general formula (I) as active ingredient.

In the present invention, all amounts are measured by the metric system and temperatures are given in degrees Celsius. «All ratios, and percentages are by weight. The term halogen denotes fluorine, chlorine, bromine and iodine.

A number of certain classes and types of compounds of Formula I form preferred groups. A particularly preferred group of compounds are those of formula (V)

wherein R15 _and R16 _S0U j is _{independently} hydrogen, chlorine or bromine, wherein at least one of R ¹⁵ and R ¹⁶ is chlorine or bromine,

X is an oxygen or sulfur atom,

R ² <> is hydrogen, chlorine, bromine or methyl, and either

1) R ²² and R ²³ are hydrogen and one of R ²⁷ and R ²⁵ is hydrogen and the other of R ²⁴ and R ²⁵ is hydrogen. chlorine, bromine, or fluorine or trifluoromethyl, methyl, hydroxyl, phenyl or phenyl monosubstituted with bromine, chlorine or fluorine; or

2) R ²² and R ²³ are hydrogen and R ²⁴ and R ²⁵ are independently chlorine, fluorine or bromine; or

3) R ²² and R ²⁴ are hydrogen and R ²³ and R ²⁵ independently of one another are fluorine, chlorine, bromine or trifluoromethyl; or

4) R ²³ and R ²⁵ are hydrogen and R ²² and R ²⁴ are independently chlorine, fluorine or bromine; or

5) R ²³ , R ²⁴ and R ²⁵ are hydrogen and R ²² is chlorine, fluorine or bromine;

R ¹³ and R ¹⁴ are, independently of one another, hydrogen, chlorine, fluorine, bromine, methyl or methoxy;

1) one of R ¹³ and R ¹⁴ may be hydrogen if and only if the other is methoxy,

2) at least one of R ¹³ and R ¹⁴ must be methyl or methoxy, unless

(a) R ²⁴ is not hydrogen and R ²² , R ²³ and R ²⁵ are hydrogen; or

b) R ²² and R ²⁴ are hydrogen atoms and one or both of R ²³ and R ²⁵ are trifluoromethyl,

(3) neither R ²⁴ nor R ²⁵ are phenyl or substituted phenyl, unless R ¹³ and R ¹⁴ are methoxy;

4) two of R ²³ , R ^24, and R ²⁵ are hydrogen, unless both R ¹³ and R ¹⁴ are methyl or methoxy;

5) R ¹³ and R ¹⁴ are both metho-

V-217 xyls if R is pyridyl, naphthyl, furyl or thienyl.

Within the above group, a more preferred group includes compounds wherein R ¹² is

and a further preferred group includes compounds wherein both R ¹³ and R ¹⁴ are methoxy. It will be understood that a variety of other different types or groups of compounds useful in the preparation of the insecticide compositions of the present invention are also prepared by the process of the present invention. For example, the following preferred groups of compounds have been contemplated. Each numbered sub-paragraph below describes an independent group of compounds, in each group the variable substituents having the general meaning given in Formula I unless stated above. In the subsections below, each general meaning such as phenyl also includes substituted forms of said groups.

Compounds where:

1) R is phenyl

2) R is phenyl or pyridyl,

3) is pyridyl, thienyl, furyl, benzothienyl, benzofuryl, benzothiazolyl, oxoxazolyl, isoixazolyl, quinolyl or thiazolyl;

4) R is phenyl or naphthyl,

5) R is pyridyl, benzothiazolyl, benzoxazolyl, isoxazolyl, quinolyl or thiazolyl,

6) R is thienyl, furyl, benzoxazolyl, benzothiazolyl, benzothienyl, benzofuryl, isoxazolyl, quinolyl or thiazolyl,

7) one of R ⁸ and R ⁸ is hydrogen and the other is halogen or trifluoromethyl;

8) R ⁸ and R ® are independently chlorine, fluorine or bromine,

9) R ⁷ and R ⁹ are independently chloro, fluoro, bromo or trifluoromethyl,

10) one of R ⁸ and R ⁸ is hydrogen, and the other is halogen, trifluoromethyl, methyl or methoxy,

11) ^R10 and ^R11 is methoxy,

12) R ¹⁰ and R ¹¹ are each independently methyl or methoxy;

13) R ¹⁰ and R ¹¹ are independently chloro, fluoro or bromo.

Compounds of subparagraph 11 above, wherein:

14) R is phenyl,

1´5) R is phenyl or · pyridyl,

16) R is pyridyl, thienyl, furyl, benzothienyl, benzofuryl, benzothiazolyl, benzoxazolyl, isoixazolyl, quinolyl or thiazolyl,

17) R is phenyl or naphthyl,

18) R is pyridyl, benzothiazolyl, benzoxazolyl, isoxazolyl, quinolyl or thiazolyl,

19) R is thienyl, furyl, benzoxazolyl, benzothiazolyl, benzothienyl, benzofuryl, isoxazolyl, quinolyl or thiazolyl,

20) one of R ⁸ and R ⁸ is hydrogen and the other is halogen or trifluoromethyl;

21) ^R8 R® and are independently chlorine, fluorine or bromine,

22) R ⁷ and R ® are independently chloro, fluoro, bromo or trifluoromethyl,

23) one of R ⁸ and R ⁹ is hydrogen and the other is halogen, trifluoromethyl, or methoxy.

The compounds of subparagraph 12 above, wherein:

24) R is phenyl,

25) R is phenyl or pyridyl,

26) R is pyridyl, thienyl, furyl, benzothienyl, benzofuryl, benzothiazolyl, benzoxazolyl, isoxazolyl, quinolyl or thiazolyl,

27) R is phenyl or naphthyl,

28) R is pyridyl, benzothiazolyl, benzoxiazolyl, isoixazolyl, quinolyl or thiazolyl,

29) R is thienyl, furyl, benzaxazolyl, benzothiazolyl, benzothienyl, benzofuryl, isoxazolyl, quinolyl or thiazolyl,

30) one of R ⁸ and R ⁹ is hydrogen and the other is halogen or trifluoromethyl,

31) R® and ^R8 are independently chlorine, fluorine or bromine,

32) R ⁷ and R ⁹ are independently chlorine, fluorine, bromine or trifluoromethyl,

33) one of R ⁸ and R ⁸ is hydrogen and the other is halogen, trifluoromethyl, methyl or methoxy.

Compounds of subparagraph 13 above, wherein:

34) R is phenyl,

35) R is phenyl or pyridyl,

36) R is pyridyl, thienyl, furyl, benzothienyl, benzofuryl, benzothiazolyl, benzoxazolyl, isoxazolyl, quinolyl or thiazolyl,

37) R is phenyl or naphthyl,

38) R is pyridyl, benzothiazolyl, benzoxazolyl, isoxazolyl, quinolyl or thiazolyl,

39) R is thienyl, furyl, benzoxazolyl, benzothiazolyl, benzothienyl, benzofuryl, isoxazolyl, quinolyl or thiazolyl, one of R ⁸ and R ⁸ is hydrogen and the other is halogen or trifluoromethyl,

41) R ⁸ and R ⁸ are independently chlorine, fluorine or bromine,

42) R ⁷ and R ⁷ are independently chloro, fluoro, bromo or trifluoromethyl,

43) one of R ⁸ and R ⁹ is hydrogen and the other is halogen, trifluoromethyl, methyl or methoxy.

While the above formulas clearly describe compounds of Formula I, they are

9 8217 The following typical examples are given to ensure full clarity for agricultural chemists.

N- [5- (6-chloro-3-pyridyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (4-chloro-3-pyridyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (4-, 5-dibromo-3-pyridyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethylbenzamide,

N- [5- (5-bromo-p-pyridyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (4-chloro-2-pyridyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethylbenzamide,

N- [5- (5-bromo-3-chloro-2-pyridyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (3,4,5-trichloro-2-pyridyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (3-furyl) -1,3,4-thladiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- [5-chloro-2-furyl] -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (5-bromo-3-thienyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethoxybenzamide,

N- (5- (5-methyl-2-thienyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide,

N- [5- (3-chloro-1-naphthyl) -1,3,4-thladlazol-2-yl] -2,6-dimethoxybenzamide,

N- (5- (2-bromo-1-naphthyl) -1,3,4-thiadlazol-2-yl) -2,6-dimethoxybenzamide,

N- [5- (4-fluoro-2-naphthyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (3-Trifluoromethyl-2-naphthyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (4-chlorophenyl) -1,3,4-thiadiazol-2-yl] -2-bromo-6-fluorobenzamide,

N- [5- (3-bromophenyl) -1,3,4-thiadiazol-2-yl] -2-fluoro-6-methylbenzamide,

N- [5- (3-iodophenyl) -1,3,4-thiadiazol-2-yl] -2-fluoro-6-methoxybenzamide,

N- [5- (3-methylphenyl) -1,3,4-thiadiazol-2-yl] -2-chloro-6-methylbenzamide,

N- [5- (3-hydroxyphenyl) -1,3,4-thiadiazol-2-yl] -2-bromo-6-methylbenzamide,

N- [5- (3-phenylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N - {5- [3- (3-fluorophenyl) phenyl] -1,3,4-thiadiazol-2-yl) -2,8-dimethoxybenzamide,

N- (5- [4- (3-bromophenyl) phenyl] -1 '3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide,

N- <5- [4- (2-chlorophenyl) phenyl] -1,3,4-thladiazol-2-yl) -2,6-dimethoxybenzamide,

N- (5- [3- (4-chlorophenyl) phenyl] -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide,

N- [5- (3,4-dibromophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethylbenzamide,

N- [5- (3-bromo-4-fluorophenyl) -1,3,4-thiadiazol-2-yl] -2-methoxy-6-methylbenzamide,

N- [5- (3,4-difluorophenyl) -1,3,4-thladiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (3,5-difluorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethylbenzamide,

N- [5- (3,5-dibromophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (3-chloro-5-trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (3-bromo-5-phenylphenyl) -1,3,4-thiadiazol-2-yl] -2-methoxy-6-methylbenzamide,

N- (5- (2,4-dibromophenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethylbenzamide,

N- [5- (4-fluorophenyl) -1,3,4-thiadlazol-2-yl] -2,6-difluorobenzamide,

N- [5- (2-bromo-4-fluorophenyl-1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide,

N- [5- (4-bromo-2-chlorophenyl) -1,3,4-thiadiazol-2-yl] -2-methoxybenzamide,

N- (5- [5-chloro-2-benzo (b) thienyl] -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide,

N- [5- (2-benzothiazolyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (2-chlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimetholxybenzamide,

N- [5- (2-quinolyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethoxybenzamide,

N- [6- (3-quinolyl) -1,3,4-thladlazol-2-yl] -2,6-dimethoxybenzamide,

N - ['5- (4-trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dichlorobenzamide,

N- [5- (2-bromophenyl) -1,3,4-thiadiazol-2-yl] -2-methoxy-6-methylbenzamide,

· - [· 5- (β-Chloro-1-naphthyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (5-fluoro-2-naphthyl) -1,3,4-thladlazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (7-Trifluoromethyl-4-naphthyl) 1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide,

N- [5- (4,5,6-Trichloro-3-pyridyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- (5- [6-bromo-2-benzo (b) thlenyl] -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide,

N- (5- _[4-methyl-2 - _b enzo (b Jthieny 1) - 13.4 · -thladiazol-2-yl) -2,6-dimethoxybenzamide,

N- (5- [5-chloro-2-benzo (b) -benzylamino-2-thiadiazol-2-yl) -2,6-dimethoxybenzamide,

N- (5- [7-methyl-2-benzo (b) furyl] -1,3,4-thladlazol-2-yl) -2,6-dimethoxybenzamide,

N- [5-bromo-4,6-dlc] Мог-З-ругШу! -1,3,4-thiadiazol-2-yl] -2,6-dimethylbenzamide;

N- [5- (3,4,5-Tribram-2-pyridyl) -1,3,4-thiazol-2-yl] -2-methoxy-.beta.-methylbenzamide,

N- [5- (3-bromo-4,6-dichloro-2-pyridyl) -1,3,4-thiadiazol-2-yl] -2, 6-dimethoxybenzamide,

N- [5- (4-methyl-2-thlenyl) -1,3,4-thladiazol-2-yl] -2,6-dimethylbenzamide,

N- [5- (4-bromo-5-methyl-2-thlenyl) -1,3,4-thladlazol-2-yl] -2-methoxy-6-methylbenzamide,

N- [S- (4,5-dlchloro-2-thienyl) -1,3,4-thladlazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (2-benzoxazolyl) -1,3,4-th! Ladlazo ^and L-2-yl] -2,8-dimethoxybenzamide,

N (5- [2-benzo (b) thlenyl] -1,3,4-thladiazol-2-yl) -2,6-dimethoxybenzamide,

N- (5- [2-benzo (b) furyl) -1,3,4-thladiazol-2-yl) 2,6-dimethoxybenzamide,

N- [5- (5-isoxazolyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethoxybenzamide,

Preferred compounds of formula I are:

N- [5- (4-chlorophenyl-l, ^3,4tth! Thiadiazol-2-yl] -2,6-dimethylbenzamide

N- [5- (4-chlorophenyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (4-fluorophenyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethylbenzamide,

N- [5- (4-Trifluoromethylphenyl) -1,3,4-thiazol-4-yl] -2,6-dimethylbenzamide,

N- [5- (4-fluorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethaxybenzamide,

N- [5- (3-trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (3-chlorophenyl) -1,3,4] imidazol-2-yl] -2,6-dimethoxybenzamide, and

N- (5- [3,5-bis- (trifluoromethyl) phenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide,

N- [5- (4-Trifluoromethylphenyl) -1,3,4-thladlazol-2-yl] -2,6-dimethoxybenzamide.

N- {5- (2-thlazcilyl) -1,3,4-thladiazol-2-yl] -2,6-dimethoxybenzamide,

N- [5- (4-iodophenyl) -1,3,4-thldiazol-2-yl] -2-chloro-6-methoxybenzamide,

N- [5-. (4-iodophenyl) -1,3,4-thladiazol-2-yl] -2,6-dichlorobenzamide,

N- [5- (3-iodophenyl) -1,3,4-thiadlazol-2-yl] -2-bromo-6-methylbenzamide,

N- [5- (5-trifluoromethyl-4-naphthyl) -1,3,4-thacliazin-2-yl-2,6-dimethylbenzamide,

N- [5- (4-chloro-1-naphthyl) -1,3,4-thiadiazol-2-yl] -2-methoxy-6-methylbenzamide,

N- [5- (2-furyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethyibenzamide,

N- [5- (5-bromo-3-furyl) -1,3,4-thiadlazol-2-yl] -2-methoxy-6-methyl-benzamide,

The compounds of formula (I) are prepared by methods known or analogous to known procedures. All compounds are readily prepared by acylation of the 2-amino-5-R-substituted 1,3,4-thiadiazoles of formula II

A — N κΛ, *νη * dl) where

R is as defined above. in formula II, with benzoyl halide. common. of formula III

wherein hal is chlorine or bromine and ^R10 and ^u are as defined in formula I, and optionally reducing a compound of formula I wherein R ⁸ is nitro to give a compound wherein R ⁸ is amino, and further · optionally acylating the compound wherein R ⁸ is an amino group to form a compound wherein R ⁸ is acetamido.

The acylation step is carried out in the presence of a base in a reaction solvent such as tetrahydrofuran, dimethylformamide, dimethylsulfoxide or diethyl ether. The preferred base is sodium hydride, although organic bases such as pyridine, triethylamine and triethanol amine as well as inorganic bases including sodium hydroxide, potassium carbonate and lithium bicarbonate may be used.

The reaction temperature range is from about -10 ° C to about 50 ° C, preferably from about 0 ° C to about 25 ° C.

Aminothiadiazoles as intermediates are prepared by reactions known in the art. They are generally prepared by either oxidative cyclization of thiosemicarbazone, preferably ferric chloride, or dehydration cyclization of thiosemicarbazide with a strong acid. See, for example, Rao, supra and Cebalo, supra.

Compounds having an amino or acetamido group on phenyl R are preferably prepared by first preparing the corresponding nitrosubstituted compound and then reducing the nitro group by hydrogenation using a hydrogenation catalyst, preferably a noble metal catalyst to form an amino-substituted compound. The amino group is then acylated with acetic anhydride or acetyl halide to form the acetamidubstituted compound.

As is known to organic chemists, all of the starting compounds used in the preparation of the compounds of formula I are obtainable by known methods.

The following examples describe the syntheses of typical compounds and the following preparations describe the syntheses of typical starting compounds. In all examples, compounds were identified by NMR analysis, elemental microanalysis, and in some cases by infrared and mass spectroscopy.

The following preparation describes a typical preparation of the starting thiadiazole by oxidative cyclization with ferric chloride.

Preparation 1

2-Amino-5- (4-pyridyl) -1,3,4-thiadiazole

9.0 g of thiosemicarbazone 4-pyridylaldehyde are added to 450 ml of ethanol and 54 g of ferric chloride hepcahydrate are added. The mixture was stirred at boiling for one hour, cooled and the solvent removed in vacuo. The residue is mixed with 40 ml of cold concentrated hydrochloric acid and allowed to stand overnight in the freezer. The mixture is then filtered, the solids are washed with three 15 ml portions of concentrated hydrochloric acid and dissolved in water. The pH of the mixture was adjusted to 8.0 by addition of sodium hydroxide, and the mixture was filtered again. The solids were washed with ethanol. The wash was evaporated to dryness and the residue was crystallized from acetone. The combined yield was 1.3 g of 234-238 ° C.

Calculated:

O / o C 47.18, o / o H 3.39, o / o N 31.44;

Found:

O / o C 47.02,% H 3.45, θ / ο N 31.39.

The following preparations illustrate the preparation of the starting compounds by dehydration cyclization with methanesulfonic acid and sulfuric acid.

Preparation2

2-Amino-5- (4-chlorophenyl) -1,3,4-thiadiazole g of 1- (4-chlorobenzoyl) thiosemicarbazide was slowly added with stirring to 330 g of methanesulfonic acid while maintaining the temperature below 35 ° C. After stirring for 5 hours after the addition is complete, it is poured into a liter of ice water, the pH of the mixture is adjusted to 7.5 with ammonium hydroxide, and the precipitated solids are filtered off and dried, and the solids are recrystallized from ethanol. g of 2-amino-5- (4-chlorophenyl) -1,3,4-thiadiazole, which was identified by NMR analysis.

Calculated:

% C 45.39,% H 2.86,% N 19.85;

Found:

% C, 45.61;% H, 3.12;% N, 19.70.

Preparation 3

2-Amino-5- (4-chlorophenyl) -1,3,4-thiadiazole

4.78 g of 1- (4-chlorobenzoyl) thiosemicarbazide are slowly added to 48 g of concentrated sulfuric acid at room temperature. During the addition, the temperature rises by about · 10 ° C. The mixture was stirred at room temperature for 6 hours after the addition was complete. The reaction mixture was then poured into ice, basified with ammonium hydroxide to pH 7.5 and filtered. The dried solids were recrystallized from ethanol to give 2.4 g of 2-amino-5- (4-chlorophenyl) -1,3,4-thiadiazole, m.p. 221 ° C.

Calculated:

% C 45.39,% H 2.86,% N 19.85;

Found:

O / o C, 45.28; "/ H of 2.63, 0 / N ₀ 20.02.

The following examples illustrate typical amino acid thiadiazoles to give compounds of the present invention.

Example 1

N- [5- (4-Chloro-phenyl) -1,3,4-thiadiazol-2-yl] -2,6-dichloro-benzamide

4 g of 2-amino-5- (4-chlorophenyl) -1,3,4-thiadiazole in 200 ml of tetrahydrofuran were added at room temperature with cooling and stirring to 1.85 g of 50% sodium hydride in oil. The cooling jacket is removed and the reaction mixture is stirred for 15 minutes, then 4.8 g of 2,6-dichlorobenzoyl chloride are added dropwise. The mixture was stirred for an additional hour and the excess sodium hydride was quenched by the addition of water. The solvent was evaporated and the residue was suspended in water and acidified with hydrochloric acid. The solids were removed from the acidic solution by filtration, dried and crystallized from ethyl acetate to give 4 g of N- [5- (4-chlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dichlorobenzamide mp above 260 degrees Celsius.

Calculated:

% C 46.84,% H 2.10,% N 10.92;

Found:

% C, 46.60;% H, 1.90;% N, 10.75.

Example 2

N- [5- (3-Hydroxyphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide

To 1.9 g of 2-amino-5- (3-hydroxyphenyl) -1,3,4-thiadiazole in 100 ml of pyridine was added 2.2 g of 2,6-dimethoxybenzoyil chloride. The reaction mixture was stirred under cooling for three hours to maintain the temperature below 30 ° C. The volatiles were removed in vacuo and the residue diluted with water. The aqueous mixture was stirred for three hours and the solids were collected and crystallized from acetone to give 1.3 g of N- [5- (3-hydroxyphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, 1.1. Mp 243-245 ° C.

Calculated:

% C 57.13,% H 4.23,% N 11.76; Found:

% C, 57.38;% H, 4.36;% N, 12.01.

The synthesis of the following examples of the compounds S6 is carried out according to the procedure of Examples 1 and 2. In each example above, the substituents of the aminothiadiazoles and the benzoyl halide are apparent from the product name. Examples of compounds are first named and then the table shows the amounts of reaction components, melting points, yields and elemental analyzes of the products.

He attaches

N- [5- (2,4-Dichlorophenyl) -1,3,4-thiadiazol-yl] -

2,6-dimethoixybenzamide.

Example 5

N- [5- (4-Hydroxyphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide.

Example

N- [5- (3,5-Dichloro-phenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxy-benzamide.

Example 7

N- [5- (3-Fluorophenyl) -1,3,4-thiadiazol-2-yl] -. -2,6-dimethoxybenzamide.

Example 8

N- [5- (4-Pyridyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide.

Examples

N- [5- (4-Cyanophenyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethoxybenzamide.

He did

N- (5- [3,5-bls (Trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide.

Example 11

N- [5- (2-Fluorophenyl) -1,3,4-thiadiazol-2-yl] -. -2,6-dimethoxybenzamide.

Example 12

N- (5-Phenyl-1,3,4-thiadiazol-2-yl) -2,6-dl-chlorobenzamide.

Example 13

N- [5- (4-Trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dichlorobenzamide.

Example 14

N- [5- (4-Chloro-phenyl) -1,3,4-thiadiazol-2-yl] -2-chloro-6-methyl-benzamide.

Example 15

N- [5- (4-Chlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-difluorobenzamide.

Example 16

N- [5- (4-Chlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethylbenzamide.

Example 3

N- [5- (1-Naphthyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide.

Example. 17

N '- [5- (4-Bromophenyl) halo-4-thiazolazol-Z-yl} -2,6-dichlorobenzamide.

Example 18

N- [5- (4-Fluorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dichlorobenzamide.

nUiH 1?

N- [5- (4-Chloro-phenyl) -1,34-thiathiazol-2-yl] -2,6-dimethoxy-benzamide.

Example 20

N- [5- (N-Dichloro-phenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethyl-benzamide.

Example 21

N- (-5- (4-fluorophenyl) -1,34-thiophthiazolidol-42-yl) -2,6-dimethylbenzamide.

Example. 22nd

N- [5- (4-Trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethylbenzamide.

Example 23

N- (5- (4-Biphenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethylbenzamide.

Example 1 a d 2 4

N- (5-Phenyl-1,3,4-thiadiaz (ol-2-yl) -2,6-di-phenylbenzamide).

Example 25

N- [5- (4-Fluoro-phenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide.

Example 2 6

N- [5-12-Thienyl] -1,4,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide.

Example 27

N- [5- (2-chloro) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide.

Example 28

N- [5- (4-Methylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide.

Example 29

N- [5- (4-Phenylphenyl) -1,3,4-thiadiazole ^; 1-2-yl] -2,6-dimethoxybenzamide.

Example 30 '

N- [5- (3-Trifluoromethylphenyl) -1,3,4-thiadia-. zol-2-yl] -2,6-dimethylethoxybenzamide.

Example 31

N- [5- (3-Chloro-methyl) -1,3,4-phthiadiazin-2-yl] -2,6-dimethyl-benzamide.

Examples of P 32 zol- ² - ^yl | -2, ^i! - ^<il ine ^IL ox ^{y and} lienzaml.

Example 33

N- (5-Phenyl-1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide.

Example 3 4

N- [5- (4-Chlorophenyl) -1H-bladlazol-4-yl} -2-methoxybenzamide.

Example 1 a d 3 5 - · ..

N- [5- (3-Trifluoromethylphenyl) -1,3,4-thiadiadal-2-yl] -2,6-dimethylbenzamide.

Example 36

N- (5- [4-chlorophenyl] phenyl] -1,3,4-hiadiazol-2-yl) -2,6-dimethoxybenzamide.

Example 37

N- (5- [4-Fluorophenyl] phenyl] <1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide.

Example 38

N- [5- (4-Bromophenyl) -1,3,4'-thiadiazol-2-yl] -2,6-dimethoxy-benzamide.

Example 39

N- (5- [3,5-bis (η 1 6,6-yl) phenyl] -1,3,4-biadiazol-2-yl) -2,6-dimethoxybenzamide

Example 1 and d - 4 0

N- (5- (2-Naphthyl) -1,3,4-thiadiazol-2-yl) -2,8-dimethoxy-benzamide.

Example 41

N- [5- (3,4-Dichlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-di-ethoxy-benzamide.

Example 4 2

N- [5-. (3-Hydroxy-phenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxy-benzamide.

Example 4 3

N- (5- (4-Methyloxylenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide.

Example 4 4

-2, § - dm &lt;

'i

Example 45

N- [5- (3-chloro- _6- piperidin) -1,3,4-thiadlazol-2-yl] -2,6-dimethylbenzamide.

Example 4 6

N- [5- (2-Naphthyl) -1,3,4-thiaziazol-2-yl] -2,6-dimethylbenzamide.

Example, 4 7

N- (5- [3,5-bis (Trifluoromethyl) phenyl] -1,1,3,4, -thladlazol-2-yl) -2,6-dimethylbenzamide.

Example, 4 8

N- [5- (3-Thienyl) -1,3,4-thladiazol-2-yl] -2,6-dimethoxybenzamide. ·

Example, 49,

N- [5- (3-Furyl) -1,3,4-thladlazol-2-yl] -2,6-dimethoxybenzamide.

EXAMPLE 5 N- [s- (s-Bromo-s-ynyl ₎ -I) d4,4-imidHiol-s-yl] -S, 3-dimethoxyoxybenzamide.

Example 51

N- [5- (4-iodophenyl) -1,3,4-thladlazol-2-yl] -2,6-dimethoxybenzamide.

Example 52

N- [5- (5-Bromo-3-pyridyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethoxybenzamide.

Example 53 a

N- [5- (5-Chloro-2-hienyl) -1,3,4-thladlazol-2-yl] -2,6-dimethoxybenzamide.

Example 54 *

N- [5- (3-Isoxazolyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethoxybenzamide.

example no. Aminothiadiazole 8 Benzoyl chloride 8 Product g Mp ° C · o / o 'C % H % N 3 2.3 2.2 2,0 209—210 64.24 4.58 10.88 4 2.5 2.2 2.3 > 260 49.56 3.17 10.30 5 2,0 2.3 1.5 > 260 57.38 4.45 11.55 8 2.5 2.2 2.5 249—251 49.89 3.25 10.49. .. 7 2,0 2.2 2.3 216—218 57,00 ‘ 4.07 11.75 8 1.3 1.6 1.5 241—243 55.89 4,11 16.06 9 2,0 2.2 1,8 > 260 58.82 3.85 15.09 10 3.2 2.2 2.1 '236—237 48.01 2.81 9.07 11 2,0 2.2 1.6 248—249 57.12 3.74 11.77 12 3.5 4,5 3.0 232—237 51.22 2.59 11.99 13 .2,3 2.4 2.3 > 260 45.96 1.90 9.96 14 2,0 2,0 2.5 258—260 52.61 2.91 11.58 15 Dec 2,0 2,0 0.8 > 260 50.97 2.57 11.86 16 2,0 2,0 1,8 247—249 59.42 4.22 11.94 17 2.4 2.4 2.8 > 260 42.27 2.13 9.58 18 2,0 2.4 1,8 254—256 47.84 4.55 11.24 19 Dec 2.1 2.3 2.6 238—240 54.12 4.07 11.11 20 May 2.4 2,0 1.9 > 260 54.35 3.66 11.16 21 2,0 2,0 1.7 231—233 62.16 4.52 12.70 22nd 2.3 2,0 1.9 240—242 57.19 4.04 11.30 '23 2.4 2,0 0.5  250—252 52.23 3.80 11.11 24  2.7 3.0 2.8 248—250 65.72 4.77 13.28 25 2,0 2.3 1.9 248—251 57.11 3.95 11.53 26 2,0 2.4 2.6 256—259 52.06 3.92 11.74 27 Mar: 2,0 2.6 1.6 233—235 54.39 4.12 12.52 28 2.6 3.1 3.1 228—230 60.63 4.77 11.66 29 2.5 2.3 2.4 236—239 66.02 4.92 10.39 30 2.7 2.9 2.8 183—185 52.59 3.43 10.49 31 2.5 2.9 1.3 213—214 54.60 4.02 11.38 32 2.4 2.2 3.0 217—220 52.56 3.37 10.37 33 1,8 2.2 2,0 253—255 60.09 4,77 ' 11.99 34 2.1 1.9 2.3 -214—216 55.4C 3.63 11.91. 35 2.4 2,0 1,8 > 260 57.10 3.82 11.19 36 3.3 2.4 1.9 259—261 55.45 3.53 8.84 37 2.9 2.4 1.0 259—261 61.02 3.84 9.36 38 - 2,6 2.2 2.4 240—243 48.36 3.55 10.29 39 * 1.6 1.1 1.4 255—257 63.08 4.19 10.00 40 2.3 2.2 2.2 230—232 64.43 4.66 11.01 41 2.5 2.2 2.5 255-257 50.04 3.24 10.25 42 1.9 2.2 1.3 243—245 57.38 4.36 12.01 43 2.5 2,0 2.4 239-241 58.29 4.88 11.46 44 2.7 2.9 1,8 - > 260 53.07 3.51 14.36 45 - 2,1 1.9 2,0 > 260 59.24 4.27 12.17 46 2.3 1.9 1.3 235—237 69.91 4.95 11.43 47 3.1 1,8 2,0 230—232 51.16 2.68 9.36 48 1,8 2.2 1.6 > 260 52.13 3.82 12.06 49 1.7 2.2 2.1 255—257 54.23 4.22 12.44 50 1.5 1.3 1.7 207—209 43.72 3.10 10.18 51 1.7 1.3 2.7 180—182 43.85 3.12 8.85 52 2.6 2.2 2.6 259—261 45.89 3.21 13.02 53 1.0 1.1 1.5 259—260 47.46 3.36 11.14 54 0.5 0.6 0.3 228—229 50.39 3.85 16.62

The following examples illustrate the preparation of amino and acetamido-substituted compounds. .....

Example 55

N- [. (4-Aminophenyl) -1,3,4-thiadiazo-1-2-yl] -2,6-dimethoxybenzamide

3.6 g of the nitrophenyl compound prepared in Example -44 is hydrogenated in tetrahydrofuran in the presence of 5% palladium on carbon as. - a catalyst. After hydrogenation is carried out. solvent. It is evaporated to dryness in vacuo and the residue is recrystallized from ethyl acetate. The catalyst was washed with ethanol and dimethylformamide and the solvent was evaporated to dryness. The residue is then recrystallized from ethyl acetate and 1.8 g of the combined recrystallized products are obtained. g of N- [(4-aminophenyl) -1,3,4-thiadiazo.l-2-yl-2,6-dimethoxybenzamide mp 232-234 C. ^Q.

Calculated

P / o C 57.30% -H 4.49% -N 15.73.

Found% C 56.95,% H-4.67,% N 15.41

Example 56.

N- [5- (4-Acetamidophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide

0.5 g of the product of Example 55 is dissolved. 20 ml of pyridine and 0.2 ml of acetic anhydride in 5 ml of tetrahydrofuran are added (the reaction mixture is cooled to keep the temperature below -35 ° C). After the addition was complete, the mixture was stirred for 16 hours at room temperature and evaporated to dryness under vacuum. The residue is recrystallized from ethyl acetate to give 0.25 g of N- [5- (4-ac-etamidophenyl) -1,3,4-thladiazol-2-yl] -2,6 -dimethoxybenzamide, mp 211-213 ° C.

Calculate>

% - C -57.42,% H, 4.31,% N, 14.10

Found:% -C 57.70,% H 4.61,% N 13.80.

The compounds of formula I were tested on living insects to determine the extent of their insecticidal activity. Typical experiments and results obtained are shown in the following tests.

In many cases . repeated tests were performed using one application rate and the results of these tests were averaged. The blanks in the table data below indicate that no tests were performed at the indicated application rate. The compounds' were - identified - by the numbers of the examples.

Testi

Epilachna varivestis and Spodopt-era eridania j

Each test compound was adjusted so that 10 mg of the compound was dissolved in 1 ml of a solvent consisting of a 1: 1 mixture of anhydrous ethanol and acetone containing 23 g of Toximul R and 13 g of Toximul-S per ml. 1 liter. (Toximul R and S are trademarks of a mixture of sulfonate nonionic surfactants produced by Stepan Chemical Co., Northfield, Illinois). Each sample is then dispersed in 9 ml of water to prepare a concentration of 1000 ppm of test compound. This dispersion is then diluted with water and optionally lower concentrations are prepared. Disperse - are evenly sprayed on 'ten-day' plants; the beans and plants are allowed to dry.

The leaves were removed from the plant and wrapped with cotton wool soaked in water. The two leaves were placed in each of a 100 mm plastic petri dish - and each of them was loaded with 5 second or third instar larvae of Epilachna varivestis or 5 - second instar larvae of Spodoptera eridania. Three dishes were used for each test compound. The plates were left for 4 days at 25 ° C with 51% relative humidity, after which the first evaluation of insecticidal activity was carried out. Some of the trays 'were left for another three days, when' another assessment was made.

Insecticidal efficacy was evaluated according to the following scale, comparing controls with 'solvents' and untreated controls.

= no dead 'larva =' 1 to - 7 dead larvae = 8 to 14 dead larvae = 15 dead larvae

The following table shows the results of typical compound tests.

1 »ftЭГТ

Example Compound No. Amount ppm Table 1 Epilachna varivestis Spodoptera erida ^ La 4 days 7 days 4 days 7 days 1 Í0OO 0 1 ..... 3 3 100 ALIGN! 0 0 . 1 1 3 1000 1 2 2; 2 100 ALIGN! 0 1 0 1 . 4 1000 1 2 2 2 100 ALIGN! 1 1 1 0 5 1000 1 2 0 0 100 ALIGN! 1 2 0 0 6 1000 0 0 3; 3 100 ALIGN! 0 0 2 3 50 1 2 25 0 2 7 1000 1 2 : 3 100 ALIGN! 0 2 2 2 8 1000 ' 2 3 2 ‘ 3 100 ALIGN! 0 0 0 0 9 1000 0 0 2 2 100 ALIGN! 0 0 0 O 10 1000 1 1 3 3 100 ALIGN! 0 1 3 3 50 1 1 3 3 25 2 2 2 3 10 1 1 2 2 5 0 1 1 3 11 1000 2 3 3 2 100 ALIGN! 1 2 1 0 50 1 2 0 0 25 1 2 0; 0 12 1000 0 0 3 2 100 ALIGN! 0 0 0 13 1000 0 0 3 3 100 ALIGN! 0 0 1 1 14 1000 1 2 3 3 100 ALIGN! 1 1 2 2 15 Dec 1900 0 0 2 3 100 ALIGN! 0 0 0 0 16 1000 2 2 3 3 100 ALIGN! 1 2 2 3 50 2 3 1 2 25 1 2 and and 17 1000 0 0 2 2 100 ALIGN! 0 0 0 0 18 1000 0 0 3 3 100 ALIGN! 0 0 1 1 19 Dec 1000 2 3 3 3 100 ALIGN! 2 2 3 3 50 2 2 2 3 25 2 2 and 2 10 1 2 0 1 20 May 1Q00 1 1 0 3 100 ALIGN! 0 0 0 0 21 1000 1 2 3 3 100 ALIGN! 2 2 2 3 50 2 3 2 2 25 2 3 1 2 20 May 1 3 1 2 10 1 2 and 1 22nd 1000 2 3 3 3 100 ALIGN! 1 2 2 2 50 0 1 and 2 25 0 1 O 1

Example Compound No. Quantity PPm Epilachna varivestis Spodoptera eridania 4 days 7 days 4 days 7 days 23 1000 2 2 3 3 100 ALIGN! 1 2 2 2 50 1 2 1 2 25 1 1 0 0 24 1000 1 2 2 3 100 ALIGN! 1 2 0 0 25 1000 2 3 3 3 100 ALIGN! 1 2 3 3 50 1 2 2 2 25 0 2 1 2 26 1000 1 0 3 2 100 ALIGN! 0 0 0 0 27 Mar: 1000 2 2 2 2 100 ALIGN! 1 2 0 1 28 1000 1 3 2 2 100 ALIGN! 0 2 0 0 29 1000 0 0 3 3 100 ALIGN! 0 0 2 2 30 1000 2 2 3 3 100 ALIGN! 2 2 2 3 50 · 2 2 2 2 25 2 2 2 3 '10 1 2 2 2 with 1 2 2.5 1 1 31 1000 2 3 2 3 100 ALIGN! 2 2 2 2. 50 1 2 25 1 1 32 1000 2 3 3 3 100 ALIGN! 2 2 3 3 50 3 3 3 3 25 3 3 10 2 3 33 1000 2 3 3 3 100 ALIGN! 0 1 0 0 34 1000 0 1 3 3 100 ALIGN! 0 0 0 0 35 1000 2 2 2 2 100 ALIGN! 0 0 0 0 36 1000 0 0 2 3 100 ALIGN! 0 0 0 0 37 1000 0 0 3 3 100 ALIGN! 0 0 1 2 38 1000 0 2 1 3 100 ALIGN! 1 2 3 3 50 1 3 1 2 25 1 2 2 2 39 1000 0 0 3 3 100 1 1 2 2 50 0 1 2 2 25 0 1 0 · 1 40 1000 0 and 2 1 100 ALIGN! 1 1 1 0 41 1000 1 1 3 3 100 ALIGN! 0 0 1 1 42 1000 1 2 0 0 100 ALIGN! 0 0 0 0 43 1000 2 0 2 0 100 ALIGN! 0 0 0 0 44 1000 2 0 2 0 100 ALIGN! 0 0 0 0

Compound · according to example no. Quantity PPm Epilachna varivestis Spodoptera · eridania 4 days 7 days 4 days 7 days 45 1000 2 0 • 1 0 100 ALIGN! 0 0. 0 0 46 1000 1 0 1 0 100 ALIGN! 0 0 0 0 47 1000 1 2 3 3 100 ALIGN! 0 0 3 3 48 1000 1 3 0 0 100 ALIGN! 0 0 0 0 . 49 1000 1 1 2 2 100 ALIGN! .0 0 0 0 50 1000 3 3 2 3 100 ALIGN! 1 - 2 3 3 51 1000 3 3 3 3 100 ALIGN! 2 3 2 2 50 3 2 1 1 10 1 2 1 1 52 1000 0 1 ' 2 2 100 ALIGN! 0 0 0 1 53 1000 1 1 2 3 100 ALIGN! 0 0 1 1 54 1000 1 3 100 ALIGN! 0 0 55 1000 2 0 0 0 100 ALIGN! 0 0 0 0 56 1000 1 0 1 0 100 ALIGN! 0 0 0 0

1.93317

Test 2

Adult development test. Epilachna varivestis from pupa

This assay is performed to determine the ability of the compounds. hinder 'adult development of Epilachna varivestis from pupae.

The compounds were. Adjusted as described in Test 1 above. Bean plants are treated. as described. in Test 1 and the leaves of the treated plants are used for the third larvae. Instaru Epilachna varivestis. For each dish. are used. larvae. If necessary, add new leaves and. The larvae are kept up to the dome, for about 3 to. 5 days. The pupae are then placed in clean Petri dishes. After 7 to 10 days, the number of hatched adults is counted and the percentage calculated. hatch control compared to untreated control and solvents. as a control. . For various tests he was. different number used. the larvae bowls in each case all the bowls were connected. for. determination of control percentage. ',.

Table 2

Compound Concentration% Control

No. ppm

16 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 19 Dec 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 21 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 22nd 100 ALIGN! 100 ALIGN! 50 48 25 3 10 11 25 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 30 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 31 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 32 100 ALIGN! 93 50 50 25 65 10 50

Test .3

Life test. cycle Epilachna varivestis

This test was performed according to Test 1 except that the larvae were used in the last phase of the third instar. The larvae were evaluated after three days to determine the larvicidal effect and the number of developed adults was determined by complete counting. pupation and development of adults in untreated controls.

T a - b.ulk a - 3

Compound No. Amount PPm '% larval control % - control of adult development 1. 1000 60 12 100 ALIGN! 70 0 50 60 0 25 50 0

Testi

Life cycle test of Epilachna varivestis

This test was carried out according to the method described immediately above, except that second instar larvae were used and the results were evaluated on 3rd, 8th and 21st.

day after treatment. The first two assessments show a larvicidal effect, since the larvae have not yet started to pupate. On the twenty-first day, adults hatched from the chrysalis were counted. In any case, the results below indicate the percentage of control compared to the control experiment.

Table 4

Compound No. Quantity PPm 3. dán Percentage 'of control Day 8 21. den 1 1000 0 20 May 100 ALIGN! 12 1000 0 0 42 13 1000 0 6 100 ALIGN! 14 1000 0 100 ALIGN! 100 ALIGN! 19 Dec 1000 11 100 ALIGN! 100 ALIGN! 100 ALIGN! 22nd 100 ALIGN! 100 ALIGN! 10 0 '60 100 ALIGN! · '. ·  · I · · - 0 0 71

Test 5

Test for Phormia regina

Each test compound is treated by dissolving 4 mg in 0.4 ml of acetone and mixing it with 40 g of homogenized bovine liver to give a concentration of 100 ppm, lower concentrations of compounds are prepared using an acetone solution containing appropriate quantities of the compound .

The processed liver is divided into two - 250 ml plastic flasks and each dose - is infected with two-day larvae of Phormia regina. The liver is placed on a layer of wood shavings and overlaid with another batch of shavings. All flasks, including the solvent flasks and the untreated control, are brought together in a room with a controlled temperature and humidity until the pupil is in the hood. All pupae are then removed, - placed 'in' 'clean' petri dishes - from plastic and kept in them until they hatch - adult flies from the control pupae.

The number - the pupae of the flask - is calculated at the time these are placed in the Petri dishes. - The number of adults hatched per dish is also calculated and the percentage of control (adults) is given in Table 5 below.

This test demonstrates the efficacy of typical compounds on Pho-ria regina.

% - checks. . .

adults

Uf

Table 5

Compound. . - - -č.

Amount ppm

16. 100 ALIGN! 0 10 0 1 0 19 Dec 100 ALIGN! 100 ALIGN! 10 15 Dec 1 0 • 21 - .. - - - - - -. 100 ALIGN! 45 • ··,. ·. · 10 0 ·. · · .. '' .. 1 - - · - ': »·. : 1 · -.22 '' - · - in i; 100 ALIGN! 25 10 O . 1. .. 0 25 100 ALIGN! 100 ALIGN! 10 . ·. ;.: / ·· «- :: / - u 1, · / '451 1 0 30 100 2 ^ (L 10 0 1. 0 31 ........... 100 ALIGN! ’10 10 0 1 0 32: 100 ALIGN! 25 10 0 1 - 0

Test 6

Larvalic test of Gallérla mellonella

This test was performed to determine the effect. certain 'compounds to' Gallerlamellonella, a bee hive parasite.

The compound - amount sufficient for the desired concentration is dissolved in 5. ml of acetone and mixed. s - -49 · g -diet. composed of g baby oat porridge, 10.6 ml of honey. and 8.0 ml glycerin, 5.3 ml water and 0.5 ml. - liquid vitamins. Acetone · is allowed to evaporate and the treated food is divided into. three - Petri dishes and. five larvae of the second - and third instar are added to each; The plates are kept under controllable conditions for seven days and the percentage of larval control compared to controls is determined.

* ·

Table 6

........ Quantity PPm % control 19 Dec 500 0 100 ALIGN! 0 50 0 25 ' 0 12.5 . :. 0 16 500 '100 100 ALIGN! 100 ALIGN! ..... 50 100 ALIGN! 25 13 12.5 '0 21 500 100 ALIGN! 100 ALIGN! 100 ALIGN! 50 0 '25 0 12.5 ·: ..... '0 22nd 500 100 ALIGN! and 100 ALIGN! 100 ALIGN! 50 86 25 13 12.5 .....-> 0 25 500 100 ALIGN! 100 ALIGN! 100 ALIGN! 50. 13 25 0 12.5 0 30 500 100 · 100 ALIGN! 100 ALIGN! 50 0 25 0 20 May 0 12.5 13 10 0 5 0 2.5 0 31 500 0 100 ALIGN! 0 50 0 25 0 12.5 0 32 500 100 ALIGN! > 100 ALIGN! 13 50 0 , 25 0 20 May 7 12.5 0 10 0 5 . 0 2.5 0

за

Test 7

Sterile lysis test for Epilachna varivestls

This test is carried out by leaving the adults of Epilachna varivestis on bean plants treated with a dispersion of 1000 ppm of a typical compound of formula I. Adults are left on these plants until the females start laying eggs, the tufts of eggs from 20 to 30 eggs are removed. and incubate. None of the plants' grown egg eggs treated with the compound of Example 30 hatch. The compound completely sterilizes shot pellets fed to treated leaves.

Test 8

Test for Lepidoptera in the field of Brussels sprouts

Compounds of Formula I are tested against Lepidoptera pests in the Brussels sprouts field. The Brussels sprouts are transplanted to field plots and treatment begins about four weeks after transplanting.

The compounds listed in the table below are made into wettable powders and dispersed in water to the concentrations given below, spraying about 1000 liters per hectare.

The compounds are applied three times at seven-day intervals and the insect-attacking plants are counted on the seventh day after the third application.

The insect control obtained using the compound is described in the table below as a percentage of insect reduction compared to the number of insects attacking untreated control plants.

Brussels sprouts are preferably attacked by two species of Pieris rapae and Trichoplusia ni. Control of these two species is shown in the table below as a control of all Lepidoptera species.

Compound No. Amount kg / ha Pieris rapae Percentage of Trichoplusia ni control total Lepidoptera 10 0.14 91 72 83 0.28 100 ALIGN! 31 72 0.56 100 ALIGN! 66 86 1.1 100 ALIGN! 79 92 16 0.14 40 0 11 0.28 49 52 50 0.56 72 17 50 1.1 91. 45 72 19 Dec 0.14 49 24 39 0.28 77 38 61 0.56 67 45 58 1.1 91 52 75 30 0.14 44 17 33 0.28 77 59 69 0.56 95 24 67 1.1 91 59 78 32 0.14 95 72 86 0.28 86 52 72 0.56 95 72 86 1.1 100 ALIGN! 31 72

T e s t 9

Test for Pieris rapae on Brussels sprouts

This test is carried out according to the method described in Test 8, except that the compounds are administered only two times instead of three times. The only insect observed in this test was Pieris rapae.

32

Compound No. Amount kg / ha percent control

10 0.28 97 0.56 97 1.1 100 ALIGN! 2.2 '100 16 0.28 65 0.56 81 1.1 94 2.2 97 19 Dec 0.28 66 0.56 81 1.1 - - - 97 2.2 97 30 0.28 75 0.56 88 1.1 97 2.2 97 32 0.28 97 0.56 100 ALIGN! 1.1 100 ALIGN! 2.2 100 ALIGN!

The following test was carried out according to the above (carbonyl) -2,6-difluorobenzamide. The results of the described tests, which were tested at various concentrations, are given below, my insecticide Dimilin, N- (4-chlorophenylamine) Amount of ppm Epilachna varivestls Spodoptera erldania days 7 days 4 days 7 days

1000 . _ _: _ i _ o ~

1000 2 9

100 00

100 10

The above data indicate a potent insecticidal effect of the compounds of Formula I. Thus, it will be apparent to entomologists that the compounds are widely useful. to control insects of various orders that adversely affect humanity and its. economic. business.

For example, the compounds are useful for the control of Coleoptera such as. Anthonomus grandis, Crambus callginosellus, Oulema melanopus, Leptinotarsa decemlineata, Hypera postica, Anthrenus scrophularie, Tribodium confusum, Lyctidae species, Agriotes species, Sitophilus -oryzae, Nodonota puncticollis and Conotrachelus neruphar; Diptera like 8 are Musea domestlca, Stomexys calcitrans,

Haematobla irritans, Phormla regina, Hotymya brasslcae - and Psila rosae; Lepldoptera such as Laspeyresla pomonella, Euxoa species, Plodia interpunctella, Tartricidae species, Heliothis zea, Ostrinia nubilaiis, Hellula rogatalls, Trlchoplusia ni, Thyridopteryx epheme-aeformis, Malacosoma americanum and Spodoptera frugiper; and Orthoptera such as Blatella germanica and Periplaneta americana.

The compounds are useful for reducing the insect population by applying an insect, a tidally effective amount of one of the compounds to the substance that the insect receives with food.

Insects can ingest the compound by applying the compound to any substance the insect eats. For example, insect infesting plants are easily controlled by. the compound is applied to the parts of the plant that eat the insects, especially the leaves. Insects that attack and eat textiles, - paper, - wooden - products, etc. is readily controlled by applying the compound to these products. Compounds - se. - can - equally effectively - use for - protection of stored grain - and seeds.

It should be noted that the compounds prevent the formation of the following stages of development - the insects that have eaten these compounds. For example, if an adult - insects - eats these compounds, adults are predominantly unaffected but lay-sterile eggs. If the larvae consume these compounds, it will die without converting to the next larval stage. The last-stage larvae that consume the compounds are pupae, but die in the form of pupae.

Entomologists are aware that it is not a problem if the compound of formula I does not necessarily result in the eradication of all insect populations.

In some cases, of course, the entire population. -the dead. In other cases, a portion of the insect is killed - and the other survives the compound treatment. The size of the part of the population that dies depends on - the type of insect, the type of compound used, the amount applied, the life of the insect, - the weather and - other factors known to entomologists.

Thus, the term "reduction of insect population" is understood to mean a reduction in the number of living insect organisms, which in some but not all cases. The size of the reduction of the insect population caused by the compound depends, of course, on the applied amount - the compound. In all cases, at least an insecticidally effective amount must be used. The term "insecticidally effective amount" is used to describe an amount sufficient to measurably reduce the treated insect population. Insecticide. effective amounts range from 1000 ppm to 1000 ppm.

The amount of insecticide applied is commonly expressed as the concentration of insecticide in the dispersion in which it is present. se -aplikuje. The amount applied is measured in this manner because it is advantageous to apply a sufficient amount of dispersion to cover the leaves or other substances to be treated with a thin layer of dispersion. The amount of dispersion to be applied depends on the surface area of the substance to be treated and the amount of the substance depends on its concentration in the dispersion.

Dispersions in which the compounds are applied are prepared from typical insecticidal compositions, but which are novel because they contain the novel compounds of the present invention.

Most widely used are aqueous dispersions prepared by mixing small amounts of concentrated insecticidal mixtures with an appropriate amount of water to obtain the desired concentration of the compound. These concentrated water dispersible compositions containing generally from 5 to 90 percent of the compound are normally in the form of emulsifiable concentrates or wettable powders.

Wettable powders contain a perfect mixture of the active compound in an inert carrier, which is a mixture of a fine inert powder and a surfactant. The concentration of active compound is typically from about 10 percent. up to about 90 percent by weight.

The inert powder is commonly - selected - from attapulgite clays, montmorillonite clays and diatomaceous clays or. . purified - silicates. - - Effective surface-active substances contained in an amount of ⁶ - 0.5 ^I0 / o to 10 -% - relative to -prášek wettable, for example - the sulfonated lignins, the condensed naftalensulfonáty.naftalensulfonáty, alkylbenzenesulfonates, alkylsulfonates and nonionic surface active agents, such as ethylene oxide adducts to alkylphenol.

Typical emulsifiable compound concentrates include conventional concentrations of compounds, such as 50-500 g / liter of liquid, equivalent to 5% to 50%, dissolved in an inert carrier that is a mixture of a water-immiscible organic solvent and emulsifiers.

Useful organic solvents include aromatic compounds, especially xylenes and kerosene fractions, especially high boiling naphthalene and olefinic kerosene fractions, such as heavy aromatic naphtha. Other organic solvents such as terpenic solvents including resin derivatives and complex alcohols such as 2-ethoxyethanol can also be used. Suitable emulsifiers for emulsifiable concentrates are selected from the same types and concentrations as those used for wettable powders.

It is also practical to apply the compounds. in the form of solutions in an appropriate organic solvent; conventionally in fine petroleum oil, such as oil sprays, which are widely used in agricultural chemistry.

Further, the compounds may be applied as mixtures in the form of dusts and aerosol preparations. Dusts contain the compound - in finely powdered form - dispersed in a powdered inert carrier. The carrier is commonly a clay such as - pyrophyllite, bentonite - or volcanic-deposit or montmorillonite. Dusts typically contain compound concentrations ranging from about 0.1% to about 10%.

The aerosol formulations comprise a compound of formula (I) dissolved in an inert carrier, which is a propellant mixture, enclosed in a pressure vessel from which the mixture is dispersed by a spray nozzle. Propellant mixtures are either low boiling halogenated hydrocarbons which can be mixed with organic solvents or aqueous suspensions pressurized with inert gases or gaseous hydrocarbons.

Claims (2)

1) one of R ¹³ and R ¹⁴ can 19 8-217 are a hydrogen atom, if and only if the other is methoxy, 2) at least one of R ¹³ and R ¹⁴ must be methyl or methoxy, unless (a) R 21 is not hydrogen and R ²² , R ²³ and R 25 are hydrogen; or b) R 22 and R ²⁴ is -hydrogen atoms and one or both R23 and R @ ² are 5-trifluoromethyl, 3) neither R ²¹ nor R ²⁵ are phenyl or substituted phenyl, unless both R ¹³ and R 14 are methoxy; 4) two of R ^23, R24 and R25 are hydrogen unless both ^R13 and R are methyl or ^by methoxy, 5) R ¹³ and R ¹¹ are both metho- 4 xyly when R represents pyridyl, naphthyl, furyl or thienyl, wherein the acylating 2-amino-5-R1 ^{2-substituted} 1,3,4-thiadiazole of the formula VI Y —Unh _k (VI) wherein R42 is as defined in formula V, by reaction with a benzoyl halide of formula - VII V * by reaction with a benzoyl halide -obecného Formula III wherein Hal, R ⁴⁰ and R ^u are as defined in point -7 - and optionally - reducing -compound of the formula I, - wherein R ⁸ is a nitro group to give a compound wherein R8 is amino and further optionally acylating the compound wherein R ⁸ is an amind group to form a compound wherein R 8 is acetamido. 10. The process of item 9, for preparing a compound of formula I, wherein R 10 and R 11 are as defined for formula I, and R is R ^f R ⁶ (VII) in which - Hal is chlorine or bromine and R, ⁿ and R14 are as defined for formula V. 9. The process of item 7 for the preparation of compounds of formula I wherein R ^w and R ⁿ are as defined in item 7 and R is wherein R 0, R 1, -R ² , R ⁶ , R ⁷ , R 8. and R9 are as defined in item 7, characterized in that a compound of formula II (II) wherein R is as defined above, wherein R ⁸ is not amindskupina or acetamiddskupina wherein ^R8, R7, R8, and - R9 are as defined for wherein R6, R7, r8, and - R9 are as defined above, wherein R8 is not an amine or acetamide group, by reaction with an oenzoyl halide of the formula O wherein Hal, R ¹⁰ and ^R - have the meanings given in point 7 and optionally reducing a compound of formula I wherein R 8 is a nitro group to give a compound wherein R8 is amino, and further optionally acylating the compound wherein R8 is amindskuůina to give compound wherein R ⁸ 'is acetamido. 11. The method of item 7 for preparing Nt - [5- (4-chlorophenyl) te, 3,4-thiadiazol-2-yl] -2,6-dimethylbenzamide, characterized by acylating 2-amino-5- (4-chlorophenyl) -1,3,4-thiadiazole 2 6-dimethylbenzoyl chloride. 12. The method of item 7 for the preparation of N [5- (4-fluorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethylbenzamide, characterized in that 2-amino-5-] is acylated 4-fluorophenyl-1,3,4] thialiazole 2,6-dimethylbenzoyl chloride. 13. The method of item 7, for preparing N- - [5- (4-Trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl) - ε-dimethylbenzamide, characterized in that 2-amino-5- (4-trifluoromethylphenyl) -1 is acylated 3,4-thiadiazole with 2,6-dimethylbenzoyl chloride. . 14. The method of item 7 for preparing N- - [5- (4-chlorophenyl) 11,3,4-thiadiazol-2-yl] - 12,6-dimethoxybenzamide, characterized in that it is acylated. 2-amino-5- (4-chlorophenyl) 11,3,41-thiadiazole 2,6-dimethoxybenzoyl chloride. 15. The method of item 7 for the preparation of N- - [5- (4-fluorophenyl) -1,3,4-thiadiazol-2-yl] - 12.6-Dimethoxybenzamide, characterized in that it is - acylated with 2-amino-5- (4-fluorophenyl) -1,3,4-thiadlazole with 2,6-dimethoxybenzoyl chloride. 16. Method. according to item 7 for the preparation of N- (5- (3-trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide, characterized in that 2-amino-5- ( 3-trifluoromethylphenyl) -1,3,4-thiadiazole with 2,6-dimethoxybenzoyl chloride. 17. The method of item 7 for preparing N- (5- (3-chlorophenyl) -1,3,4-thiadiazol-2lyl) - 12.6-Dimethoxybenzamide, characterized in that it is acylated with 2-amino-5- (3-chlorophenyl) -1,3,4H-hiadiazole with 2,6-dimethoxybenzoyl chloride. 18. The process of clause 7 - preparing N- [5- (4-trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl] 1,2,6-dimethoxybenzamide, characterized in that it is acylated with 2- amino-5- (4-trifluoromethylphenyl) -1,3,4-thiadiazole with 2,6-dimethoxybenzoyl chloride. 19. The method of item 7 for preparing N- - (5- (3,5-bis' (trifluoromethylphenyl) -1,4,44,8-diazol-2-yl) 1,2,6-dimethoxybenzamide, characterized in that it is acylated with 2-amino-5- [3,5] bis (trifluoromethyl) phenyl '] -1,3,4-diadiazole 1) R ²² and R ²³ are hydrogen, one of R ²⁴ and R ²⁵ is hydrogen and the other is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, methyl, hydroxyl, phenyl or phenyl monosubstituted with bromine, chlorine or or fluorine 2) R ²² and R ²³ are hydrogen and R ²⁴ and R ^2S independently of one another are chlorine, fluorine or bromine; or 3) R ²² and R ²⁴ are hydrogen and R ²³ and R ²⁵ are independently chlorine, fluorine, bromine or trifluoromethyl; or 4) R ²³ and R ²⁵ are hydrogen and R ²² and R ²⁴ are independently chlorine, fluorine or bromine; or 5) R ^23, R ²⁴ and R ²⁵ are hydrogen and R ²² is chlorine, fluorine or bromine, R13 _and R14 j _{SOU to SO} It runs independently hydrogen, chlorine, fluorine, bromine, methyl or methoxy, wherein 1) one of R ¹⁰ and R ¹¹ can be hydrogen if and only if the other is methoxy, 2) at least one of R ¹⁰ and R ¹¹ must be methyl or methoxy, unless (a) R ⁸ is not hydrogen and R ⁸ , R ⁷ and R ® are hydrogen atoms; or b) R ⁸ and R ⁸ are hydrogen and one or both R ⁷ and R® are trifluoromethyl, 3) neither R ⁸ nor R® are phenyl, acetamido, methoxy, nitro, amino, cyano or substituted phenyl unless both ^R10 and R ^u is methoxy, 4) two of R ^7, R ⁸ and R® are hydrogen unless R ¹ ® and ^R11 are methyl or methoxy, 5) both R ¹⁰ and R ¹¹ are methoxy or methyl when R is pyrldyl, naphthyl, furyl or thienyl, 6), both R ¹⁰ and R ^u are methoxy when R represents benzothiazolyl, benzoxazolyl, benzothienyl, benzofuryl, lsoxazolyl, quinolyl or thiazolyl, wherein said acylating 2-Amino-5-R-substituted 1,3,4-thiadiazole of formula II N-N (II) wherein R is as defined in formula I, except that R is not aminophenyl or acetamidophenyl, by reaction with a benzoyl halide of formula III wherein hal is chlorine or bromine and R ¹⁰ and R ¹¹ are as defined in formula I, at a temperature of from -10 ° C to 50 ° C, and optionally reducing a compound of formula I wherein R ⁸ is nitro to form a compound wherein R ⁸ is amino and further optionally acylating the compound wherein R ⁸ is amino to form compounds wherein R ⁸ is acetamido. 8. The process of item 9, for preparing compounds of formula V wherein R ¹⁵ and R ¹⁸ are independently hydrogen, chlorine or bromine, wherein at least one of R ¹⁵ and R ¹⁸ is chlorine or bromine, X is an oxygen or sulfur atom, R ²⁰ is hydrogen, chlorine, bromine or methyl, and either 1) R 6 'and R 7 are hydrogen atoms, one of R 8 and R ⁹ is hydrogen and the other is hydrogen, chlorine, methoxy or bromine, iodine, fluorine, trifluoromethyl, methyl, hydroxyl, phenyl or phenyl monosubstituted with bromine , chlorine or fluorine; or 2) R 6 and R 7 are hydrogen and R 8 and R ⁹ are independently chlorine, fluorine or bromine; or 3) R ⁶ and R 8 are hydrogen and R 7 and R 9 are independently of one another. chlorine, fluorine, bromine or trifluoromethyl; or 4) R 7 and R ⁹ are hydrogen and R 6 and R 8 are independently of each other fluorine, chlorine or bromine atoms; or 5] R ⁷ , R ⁸ and R ⁹ are hydrogen and R ⁸ is chlorine, fluorine or bromine, or 6) R ^6, and R ⁷ are hydrogen R® and ^R8] e acetamido, nitro, amino or cyano, R¹⁰ _{and R¹¹} uj _S o _{U SO} bg independently hydrogen, chlorine, fluorine, bromine, methyl or methoxy , whereas 1) one of R ¹³ and R ¹¹ may be hydrogen if and only if the other is methoxy; 2) at least one of the substituents R 13 and R 14 must be methyl or methoxy, unless (a) R 24 is not hydrogen and R 22, R 23 and R 25 are hydrogen or b) R 22 and R 24 are hydrogen atoms and one or both of R 23 and R 25 are trifluoromethyl, 3) neither R 24 nor R 25 are phenyl or substituted phenyl, unless both R 13 and R ¹⁴ are methoxy; 4) two of R 23, R 24 and R 23; R25 are hydrogen atoms, except · RH and R ^M are each methyl or · methoíxyl, 3) both R 13 and R ^u are methoxy when R represents pyridyl, naphthyl, furyl or thienyl. 3. An insecticidal composition according to claim 1, wherein the active ingredient is a compound of formula (I) wherein R is R15 and R1® Are 'independently of one another · · hydrogen, chlorine or bromine · wherein' at least one of the substituents R 15 and R 1 ⁸ is Cl or Br ·, X is an oxygen or sulfur atom, RR ^f where R ⁶ , R ⁷ , R ⁸ and R 9 are as defined in point 1. * 4. An insecticidal composition according to claim 3, wherein the active ingredient is a compound of formula (I) wherein R10 and R11 are each independently methyl or methoxy. 5. An insecticidal composition according to claim 1, characterized in that it contains one of the following compounds as active ingredient: N- [5- (4-chlorophenyl-1,3,4-thiadiazol-2-yl)] -2,6-dimethylbenzamide, N- [5- (4-fluorophenyl) -1,3,4-thiadiazol-2-yl)] -2,6-dimethylbenzamide, N- [5- (4-Trifluoromethylphenyl) -1,3,4-thiadiazol-4-yl] -2,6-dimethylbenzamide. 6. An insecticidal composition according to claim 1, which comprises as an active ingredient any of the following: N- [5- (4-chlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, N- [5- (4-fluorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, N- [5- (3-Trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, N- [5- (3-chlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, N- [5- [4-Trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide. 7. A process thiadiazolylbenzamidů, effective according to claim 1 of formula I, or wherein R °, R 1 and R ² are independently hydrogen, chlorine or bromine, wherein at least one of R °, R1 and R2 is chlorine or bromine, X is an oxygen or sulfur atom, R 3 and R ⁴ are each independently hydrogen, chlorine, bromine or methyl, wherein R 3 is hydrogen when X is an oxygen atom, and either 1) R2 ² and R 23 are hydrogen atoms, one of R 24 and R 25 is hydrogen and the other is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, methyl, hydroxyl, phenyl or phenyl monosubstituted by bromine, chlorine or fluorine; or 2) R ²² and R ²³ are hydrogen and R ²⁴ and R ²⁵ are independently chloro, fluoro or bromo; or 3) R 22 and R 24 are hydrogen and R 23 and R 25 are independently chlorine, fluorine, bromine or trifluoromethyl; or 4) R23 and R25 are hydrogen and R22 and R24 independently of one another are chlorine, fluorine or bromine; or 5) R23, R24 and R25 · j _S ou hydrogen and R22 is chlorine, fluorine or bromine, R 13 and R 14 are independently hydrogen, chlorine, fluorine, bromine, methyl or methoxy; whereas 1) one of R ¹⁰ and R ¹¹ may be hydrogen, if and only if the other is methoxy, 2) at least one of R ¹⁰ and R ¹¹ must be methyl or methoxy, unless a] R ⁸ is not a hydrogen atom and R ⁶ , R ⁷ and R ⁹ are hydrogen or b) R ⁶ and R ⁸ are hydrogen and one or both of R ⁷ and R ⁹ are trifluoromethyl, 3) neither R ⁸ nor R ⁹ are phenyl, acetamido, methoxy, nitro, amino- A94217-pin, cyano or substituted phenyl, unless both R ¹⁰ and R ¹¹ are methoxy, 4) two of R ^7, R 8 and R 9 are hydrogen unless R 1 ° and R ^u are methyl or methoxy substituents · _t 5) both R 10 and R 11 are methoxy or methyl when R is pyridyl, naphthyl, furyl or thlenyl, 6) both R10 and ^Rn are methoxy when R represents benzothiazolyl, benzoxazolyl, benzothienyl ·, 'benzofuryl, isoxazolyl, quinolyl or thlazolyl · together with an inert carrier. 2. An insecticidal composition according to claim 1, wherein the active ingredient is a compound of the formula (V): EMI3.1 wherein: R 20 is hydrogen, chlorine, bromine or methyl and either 1) R ⁸ and R ⁷ are hydrogen atoms, one of R ⁸ and R ⁹ is hydrogen and the other is hydrogen, chlorine, methoxy, bromine, iodine, fluorine, trifluoromethyl, methyl, hydroxyl, phenyl or phenyl monosubstituted by an atom bromine, chlorine or fluorine; or 2) R ⁶ and R ⁷ are hydrogen and R ⁸ and R ⁹ are independently chlorine, fluorine or bromine; or 3) R ⁸ and R ⁸ are hydrogen, R ⁷ and R ⁹ are independently chlorine, fluorine, bromine or trifluoromethyl; or 4) R ⁷ and R ⁹ are hydrogen and R ⁸ and R ⁸ are independently chlorine, fluorine or bromine; or 5) R ⁷ , R ⁸ and R ⁹ are hydrogen and R ⁶ is chloro, fluoro or bromo; or 6) R ^8, R ⁷ and R ⁹ are hydrogen and R ⁸ is an acetamido, nitro, amino or cyano, Rio _and Rii. _S0ll j _{independently} represent hydrogen, chlorine, fluorine, bromine, methyl or methoxy, wherein What is claimed is: 1. An insecticidal composition comprising, as active ingredient, a compound of formula (I) wherein: R 0, R ¹ and R ³ are each independently hydrogen, chlorine or bromine, with at least one of R 0, R ¹ and R ² being chlorine or bromine, X is an oxygen or sulfur atom, R ³ and R ⁴ are each independently hydrogen, chlorine, bromine or methyl, wherein R ³ and R ⁴ are each independently hydrogen, chloro, bromo or methyl; R ³ is a hydrogen atom when X is an oxygen atom, and either 2,6-dimethbeybenzoyl chloride. severography, n. p., plant 7, - Most