CS198218B2 - Method of producing thiadiazolylbenzamides - Google Patents

Description

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

Insect control is one of the major problems of agricultural chemical research that is continuing intensively. Insects of various species endanger crops of all types and also cause unhealthy conditions and contamination of food contamination. The damage caused by insects 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. However, some of these, known from the literature, are of interest, for example Cebal, U.S. Pat. No. 3,726,892 discloses the herbicidal effect of 1,3,4-thiadiazol-2-yl-ureas.

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.

Welling and Muldpr, U.S. Patent No. 3,748,356 discloses the herbicidal and insecticidal effect of N-benzoyl-N'-phenylureas.

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

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 an oxygen atom, and either

1) R ⁶ and R ⁷ are hydrogen atoms, one of R ⁶ and R ⁹ is hydrogen and the other of R ⁶ and R ⁹ is hydrogen, chlorine, methoxy, bromine, iodine, fluorine, trifluoromethyl, methyl, hydroxyl, phenyl or phenyl monosubstituted with bromine, chlorine or fluorine; or

2) R® and R ⁷ are hydrogen and R® and ^R9 are independently hydrogen, chlorine, fluorine or bromine atom or

3] R ® and R ® are hydrogen and R ⁷ and R ⁹ are independently chlorine, fluorine, bromine or trifluoromethyl, or

4) R ⁷ and R ⁹ are hydrogen and R ® and R ® are independently chlorine, fluorine or bromine; or

5) R ⁷ , R ® and R ⁹ is hydrogen and R ® is chlorine, fluorine or bromine; or

8) R ®, R ⁷ and R ⁹ are hydrogen and R ® is an acetamido, nitro, amino or cyano group,

R ¹⁰ and R ¹¹ are, independently of one another, hydrogen, chlorine, fluorine, bromine, methyl or methoxy;

1) one of the substituents R ¹⁰ and R ¹¹ may be hydrogen if the other is only methoxy, _x 2 J at least one of the substituents R ¹⁰ and R ¹¹ must be methyl or methoxyl, unless

a] R® is not hydrogen, and R®, R ⁷ and R ⁹ is hydrogen or bi R® R® and are hydrogen atoms, and one or both R ⁷ and R ⁹ are trlfluormethyly,

3) neither R ® nor R ⁹ are phenyl, acetamido, methoxy, nitro, amino, cyano or substituted phenyl, unless both R ¹⁰ and R ¹¹ are methoxy.

4) two of R ^7, R® and ^R9 are hydrogen unless both ^R10 and R are methyl or ^by methoxy,

5) R ¹⁰ and R ¹¹ are both metho198218

With xyls or methyls when R is pyridyl, naphthyl, furyl or. thienyl, 6), both R ¹⁰ and ^R are methoxy when R represents benzothiazolyl, benzoxazolyl, benzothienyl, benzofuryl, isoxazoyl, quinolyl or thiazolyl, such that the cyclized compound of formula II

wherein ^R10 and ^u are as defined for formula I and X is a group of formula

O

II

R = C-NH- or

R - CH = N - wherein R is as defined in formula I, except for aminophenyl or acetamidophenyl, using a dehydrating agent when X is

R — C — NH—

O, or using an oxidizing agent ,, when X is -R-CH-N-, and optionally reducing a compound of formula I wherein R ⁸ is a nitro group to give a compound wherein R ⁸ is amino, and further optionally acylating a compound of formula I wherein R ⁸ is an amino group to produce a compound wherein R ⁸ is acetamido.

The compounds of formula I are useful as insecticidal active ingredients.

In the present invention, all amounts are measured by a 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 write j _S Q _{u to S} each independently hydrogen, chlorine or bromine atom, 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 or bromine or methyl, and either

1) R ²² and R ²³ are hydrogen and one of R ²⁴ 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 a bromine, chlorine or fluorine atom; 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 are independently of each other a fluorine, chlorine, bromine or trifluoromethyl atom; 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 _{having at SOU} j bg independently hydrogen, chlorine, fluorine, bromine, methyl or methoxy, wherein

(1) one of R ¹³ and R ⁴⁴ may be hydrogen if and only if the other is methoxy;

(2) at least one of R ⁴³ and R ¹⁴ must be methyl or methoxy, unless R ²⁴ is also hydrogen and R ²² , R ²³ and R ²⁵ are hydrogen; or

b) R ²² and R ²¹ 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;

R) R ¹³ and R ¹⁴ are both methoxy when 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 ⁴⁴ are methoxyls.

It will be understood that a number of other different types or groups of compounds useful in the preparation of insecticidal compositions 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 otherwise stated above. In the subsections below, each general meaning, such as phenyl, includes such substituted forms of said groups.

Compounds where:

1) R is phenyl

2) R is phenyl or pyridyl,

3) R is pyridyl, thienyl, furyl, benzothienyl, benzofuryl, benzothiazolyl, benzoxazolyl, isoxazolyl, 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 ⁹ is hydrogen and the other is halogen or trifluoromethyl,

8) R 8 and R ⁹ are independently chlorine, fluorine or bromine;

9) R ⁷ and R ⁹ 'are independently atoin of chlorine, fluorine, bromine or trifluoromethyl,

10) one of R 8 and R ⁹ is hydrogen and the other is halogen, trifluoromethyl, methyl or methoixyl;

11) R ⁴⁰ and R ⁴¹ is methoxy, '

12) R ¹⁰ and R ⁴¹ are 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,

15) R is phenyl or pyridyl,

16) R is pyridyl, thienyl, furyl, benzothienyl, benzofuryl, benzothiazolyl, benzoxazolyl, isoxazolyl, 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 ⁹ is hydrogen and the other is halogen or trifluoromethyl;

21) R (R) and R ( ⁹⁾ independently of one another are chlorine, fluorine or bromine,

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

23) one of R 8 and R ⁹ is hydrogen and the other is halogen, trifluoromethyl, methyl 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, benzothlenyl, benzofuryl, benzothiazolyl, benzoxazolyl, isoxazolyl, chiholyl or thiazolyl,

27) R is phenyl or naphthyl; 28) R is pyridyl, benzothiazolyl, benzoxazolyl, isoxazolyl, quinolyl or thiazolyl,

29) R is thienyl, furyl, benzoxazolyl, 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 R ⁹ are independently chlorine, fluorine or bromine,

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

(33) one of R @ ⁹ and R @ ⁹ 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,

40) one of R 8 and R ⁹ is hydrogen and the other is halogen or trifluoromethyl;

41) R ⁸ and R ⁹ are independently chloro, fluoro or bromo, 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 the compounds of formula I, the following typical examples are provided to provide full clarity to 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-dimethoxyberisamide,

N- [15- (4,5-dibromo-3-pyridyl) -1,3,44-thiadiazol-2-yl] -2,6-dimethylbenzamide,

N- [5- (5-bromo-2-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-12-yl] -2,6-dimethoxybenzamide,

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

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

N- [5- (5-methyl-2'-thienyl) -1,3,4-thiadiazazol-2-yl] -2,6-dimethoxybenzamide,

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

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

N- [5- (4-fluoro-2-naphthyl) -1,3,4-thiadiazol-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-thiadiazazol-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,

42) R ⁷ and R ® are independently an atom

N- [5- (3-methylphenyl) -1,3,4-thiadlazol-2H-yl] -2-chloro-8-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] -2,6-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-thiadiazol-2-yl] -2,6-dimethoxybenzamide,

N-15- [13- (4-chlorophenyl) phenyl] -1,3,4-thladiazol-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-thiadlazol-2-yl] -2,6-dimethoxybenzamide,

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

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

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

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

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

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

N- [5- (2-bromo-4-fluorophenyl) -1,3,4-thladiazol-2-yl] -2,8-dimethoxybenzamide,

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

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

N- [5- (2-bromophenyl) -1,3,4-thladiazol-2-yl) -2-methoxy-6-methylbenzanide,

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

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

N * [5- (7-trifluoromethyl-1-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-thromo-4,8-dichloro-3-pyridyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethylbenzamide,

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

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

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

N- [5- (4-bromo-5-methyl-2-thienyl) -1,3,4-thladiazol-2-yl] -2-methoxy-6-methylbenzamide;

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

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

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

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

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

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

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

N- [α- (4-iodophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dichlorobenzamide,

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

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

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

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

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

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

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

Preferred compounds of formula I are:

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

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

N- (5- (4-fluorophenyl) -1,3,4-thladiazol-2-yl) -2,6-dimethylbenzamide,

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

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

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

The compounds of formula (I) are prepared by methods known or analogous to known procedures.

Compounds of formula I wherein R, ^R10 and ^u are as defined above are prepared by cyclisation of a compound of formula II

wherein R ¹⁰ and R ¹¹ are as defined above in Formula I and X is

O II

R = C-NH- or

- R - CH = N - wherein R is as defined in formula I, except for aminophenyl or acetamidophenyl, using a dehydrating agent when X is

R — C — NH—,

II o

or using an oxidizing agent, when X is R-CH = N-, and optionally reducing a compound of formula I wherein R ⁸ is a nitro group to give a compound wherein R ⁸ is amino, and further optionally acylating the compound wherein ^R8 is amino, and to prepare a compound wherein R ⁸ is acetamido.

Suitable dehydrating agents are phosphoric acid, formic acid, phosphorus pentachloride, phosphorus pentoxide in the presence of strong acid and benzoic acid and alkanoic acid chlorides and anhydrides. Preferred dehydrating agents are strong acids, especially methanesulfonic acid and concentrated sulfuric acid.

The dehydration cyclization is carried out at temperatures from about 20 to about 80 ° C, preferably at room temperature. Preferably, the reaction is conveniently carried out without solvent, although if desired, the reaction may be carried out in solvents including halogenated benzenes, and halogenated alkanes such as chlorobenzene, dichlorobenzenes, chloroform and methylene dichloride.

The preferred oxidizing agent is ferric chloride. Other effective oxidizing agents, such as calcium ferric cyanide, may also be used. The oxidative cyclization is preferably carried out in lower alkanols, for example ethanol or propanol, at the boiling point of the reaction mixture. Generally, temperatures from about 50 ° C to about 100 ° C are used.

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 analysis and mass spectroscopy.

The first group of preparations and examples describe typical cyclizations using dehydrating agents.

Preparation 1

1- (4-Chlorobenzoyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbazide

1S

A solution of 0.76 g ammonium thiocyanate was heated to 70 ° C in a 20 mL chlorobenzene in a 100 mL flask. After a few minutes, 2.0 g of 2,6-dimethoxybenzoyl chloride in 30 ml of chlorobenzene are added dropwise and the mixture is stirred for 15 minutes after completion of the dropwise addition. 1.7 g of 4-chlorobenzoylhydrazine suspended in 20 ml of chlorobenzene are then added and the mixture is stirred at 70 ° C for 30 minutes. The solvent was removed in vacuo and 50 ml of water was added to the residue. After stirring the aqueous mixture for three hours, the solids were collected, dried and 2.7 g of 1- (4-chlorobenzoyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbazide, m.p. 206 DEG-208 DEG C. were obtained.

Found% C 51.84 52.12% H 4.09 4.35% N 10.67 10.67

Example 1

N- [5- (4-Chlorophenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide g of the above intermediate was slowly added to 5 g of concentrated sulfuric acid with stirring and cooling. The mixture was stirred at room temperature for 4 hours and then poured into 300 ml of ice. The solids were collected, dried and crystallized from ethyl acetate to give 0.45 g of N- [5- (4-chlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, mp 238-240 ° C. .

Found% C 54.33 54.01% H 3.75 3.84% N 11.18 11.22

Preparation of 2 -, (4-Hydroxybenzoyl) -4- (2,6-dimethoxybenzoyl) thlosemicar bazid

Dissolve 2.0 g of 2,6-dimethoxybenzoyl chloride in 20 ml of tetrahydrofuran and add to 0.76 g of ammonium thiocyanate in 10 ml of tetrahydrofuran at reflux. After the addition was complete, the mixture was stirred at boiling point for 15 minutes and then 1.5 g of 4-hydroxybenzoylhydrazine in 20 ml of tetrahydrofuran was added. The reaction mixture was further heated for 30 minutes, cooled and evaporated in vacuo to give an oily residue, consisting mainly of 1- (4-hydroxybenzoyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbazide. Example 2

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

The residue obtained above is stirred and 20 g of methanesulfonic acid are added dropwise. After stirring at room temperature for four hours, the solution is poured into 300 ml of ice water and the pH of the solution is adjusted to 7.5 with ammonium hydroxide. The precipitate was collected and recrystallized from acetone. 2.5 g of N- [5- (4-hydroxyphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide are obtained, m.p. above 260 ° C. Found% C 57.13 56.98% H 4.23 3.96% N 11.76 11.52

Example 1a

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

Following the procedure of Examples 1 and 2, 2.2 g of 2,6-dimethoxybenzoyl chloride was reacted with 1.4 g of 4-pyridylcarbonylhydrazine to prepare the corresponding 1- (4-pyridylcarbonyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbazide.

Thiosemicarbazide, the liquid is stirred and 20 g of methanesulfonic acid are added dropwise with cooling. After stirring at room temperature for 5 hours, the reaction mixture is worked up as described above to give 2.9 g of N- [5- (4-pyridyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, mp 241-243 ° C. Found% C 55.90 56.13% H 4.21 4.12% N 16.47 16.36

Example 4

N- [5- (5-Chloro-2-benzo [h] thienyl) -1,3,4-thladiazol-2-yl] -2,6-dimethoxybenzamide 1 - [(5-chloro-2-benzo [ b] thienyl) carbonyl] -4- (2,6-dimethoxybenzoyl) thiosemicarbazide prepared above is added to 20 g of methanesulfonic acid and about

1.1 g of N- [5- (5-chloro-2-benzo [b] thienyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, m.p. above 260 ° C.

Calculated · Found C 52.84 ^J 52.62% H 3.27 3.48% N 9.73 9.78

Example 1 a d 5

N- [5- (2-Benzothiazolyl) -1,3,4-thiadiazazol-2-yl] -2,6-dimethoxylbenzamide

4.2 g of 1 - [(2-benzothiazolyl) carbonyl] -4- (2,6-diinethoxybenzoyl) thiosemicarbazide was added to 16 g of methanesulfonic acid with stirring. Product 2.6 g of N- [5- (2-benzothiazolyl) 198218

-1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, mp > 260 ° C.

Calculated

Found: C, 54.26;% H, 3.54;% N, 14.00

Example 6

54.38

3.72

13.81

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

To 10 g of methanesulfonic acid is added 1.4 g of 1- (2-chlorobenzoyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbazide, maintaining the temperature at or below 35 ° C. 1.2 g of N- [5- (2-chlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, mp 235-237 ° C, are obtained as the product of the reaction.

The following example shows a typical cyclization using an oxidizing agent.

Example 1 9

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

3.78 g of 4-chlorobenzaldehyde, 4- (2,6-dimethoxybenzoyl) thiosemicarbazone are added to 400 ml of ethanol and 10.8 g of ferric chloride hexahydrate, the mixture is stirred at boiling point for one hour, then cooled and concentrated in vacuo. The solids were filtered and dissolved in ethanol, the solvent was evaporated in vacuo and the residue was recrystallized from ethyl acetate to give 2.1 g of N- [5- (4-chlorophenyl)]. -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, mp 246-248 ° C.

Calculated%

% w / o

C 54.33 H 3.75 N 11.18

Found

54.57

3.95

11.19

Calculated

Found C 54.33% H 3.75% N 11.18

54.19

3.47

11.27

Example 1 a d 7

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

2.0 g of 2,6-dimethoxybenzoyl chloride was reacted with 1.9 g of (2-quinolyl) carbonylhydrazine to give the corresponding 1- (2-quinolylcarbonyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbazide, which was cyclized with methanesulfone. acid to give 1.75 g of N- [5- (2-quinolyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, mp > 260 ° C.

Calculated

Found% C 61.21% H 4.11% N 14.28

Example 8

61.09

4.30

13.95

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

According to the above example, 2.09 g of 2,6-dimethoxybenzoyl chloride was reacted with (3-quinolyl) carbonylhydrazine to give 1- (3-quinolylcarbonyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbazide, which was cyclization with methanesulfonic acid to give 1.7 g of N- [5- (3-quinolyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, mp 242-243 ° C.

Calculated

Found: C, 61.22;% H, 4.11; N, 14.28

60.97

4.17

14.01

The following examples of compounds are synthesized according to the above examples. Examples of compounds are first named and then the table shows the melting points and elemental analyzes of the product. Example 10

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

Example 11

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

Example 12

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

Example 13

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

Example 14

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

Example 15

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

Example16

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

Example 17

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

Example 1 a d 18

N- (5-Phenyl-1,3,4-thiadlazol-2-yl) -2,8-dlchlorobenzamide.

Example 19

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

Example 20

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

Example 21

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

Example 22

N [5- (4-Chlorophenyl) -1,3,4-thiadlazol-2-yl] -2,6-dimethybenzamide. ’. · -

Example 23

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

Example 24

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

Example 25

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

Example 26

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

Example 27

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

Example 28

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

Example 29

N- (5-Phenyl-1,3,4-thladlazol-2-yl) -2,6-dimethylbenzamide.

Example 30

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

Example 31

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

Example 32

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

Example 33

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

Example 34

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

Example 35

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

Example 36

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

Example 37

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

Example 38

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

Example 39

N- [5- (4-Chlorophenyl) -1,3,4-thiadiazol-2-yl) -2-methoxybenzamide.

Example 40

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

Example 41

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

Example 42

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

Example 43

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

Example 44

N-15- [4- (4-Fluorophenyl) -phenyl] -1,3,4-thiadiazol-2-yl 3-2,6-dimethoxybenzamide.

Example 45

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

Example 46

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

Example 47

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

Example 48

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

Example 49

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

Example 50

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

Example 51

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

Example 52

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

Example 53

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

Example 1 4

N- (5- (3-Furyl) -1,3,4-thiadiazazol-2-yl) -2,6-dimethoxybenzamide.

Example 55

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

Example 1 a d 5 6

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

Example 1 a d 5 7

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

Example 58

N- {5- (5-Chloro-2-thienyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide.

Example 1 a d 5 9

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

/

Π

τ. ° C % c '% Η θ / ο Ν 209—210 64.24 4.58 10.88 > 260 49.56 3.17 10.30 249-251 49.89 3.25 10.49 216—218 57.00 4.07 11.75 > 260 46.60 1.90 10.75 > 260 58.82 3.85 15.09 236—237 48.01 2.81 9.07 248—249 57.12 3.74 11.77 232—237 51.22 2.59 11.99 > 260 45.96 1.90  9.96  258—260 52.61 2.91 11J58 > 260 50.97 2.57 11.86 247—249 59.42 4.22 11.94 > 260 42.27 2.13 9.58 254—256 47.84 4.55 11.24 > 260 54.35 3.66 11.16 231—233 62.16 4.52 12.70 240—242 57.19 4.04 11.30 250—252 52.23 3.80 11.11 248-250 65.72 - 4,77 13.28 248-251 ' 57.11 3.95 11.53 256—259 52.06 3.92 11.74 233-235 54.39 4.12 12.52 228—230 60.63 4.77 11.66 236—239 66.02 4.92 10.39 183—185 52.59 3.43 10.49 213—214 54.60 4.02 11.38 217—220 52.56 3.37 10.37 253—255 60.09 4.77 11.99 214—216 55.40 3.63 11.91 > 260 57.10 3.82 11.19 259—261 55.45 3.53 8.84 259-261 61.02 3.84 9.36 240—243 48.36 3.55 10.29 255-257 63.08 4.19 10.00 230—232 64.43 4.66 11.01 255—257 50.04 3.24 10.25 243—245 57.38 4.36 12.01 239—241 58.29 4.88 11.46 > 260 53.07 3.51 14.36 > 260 59.24 4.27 12.17 235—237 69.91 4.95 11.43 230—232 51.16 2.68 9.36 260 52.13 3.82 12.06 255—257 54.23 4.22 12.44 207—209 43.72 3.10 10.18 180—182 43.85 3.12 8.85 259-261 45.89 3.21 13.02 259—260 47.46 3.36 11.14 228-229 50.39 3.85 16.62

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

Example 60

N- (4-Aminophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide

3.6 g of the nitrophenyl compound prepared in Example 49 was hydrogenated in tetrahydrofuran in the presence of 5% palladium on carbon catalyst. After hydrogenation, the solvent was evaporated to dryness in vacuo and the residue was recrystallized from ethyl acetate. The catalyst was washed with ethanol and dimethylformamide and the solvent was evaporated to dryness. The residue was then recrystallized from ethyl acetate to give 1.8 g of N- (4-aminophenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide, m.p. 232-234 ° C.

Found% C 57.30 56.95% H 4.49 4.67 o / o N 15.73 15.41

Example 61

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

0.5 g of the product of Example 60 was dissolved in 20 ml of pyridine and 0.2 ml of acetic anhydride in 5 ml of tetrahydrofuran was added while the reaction mixture was cooled to maintain the temperature below 35 ° C. After the addition was complete, the mixture was stirred at room temperature for 16 hours and evaporated to dryness in vacuo. The residue was recrystallized from ethyl acetate to give 0.25 g of N- [5- (4-acetamidophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, mp 211-213 ° C.

H, 4.31; 4.61;% N, 14.10. 13.80

The compounds of formula I were tested on live insects to determine the extent of their insecticidal activity. The following tests show typical experiments and results obtained.

In many cases, repeated tests were performed using a single 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 dose. The compounds were identified by the example numbers.

Test 1

Test for Epilachna varivestis and Spodoptera eiridania

Each test compound was treated by dissolving 10 mg of the compound 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 liter. (Toximul R and S are trademarks of a mixture of sulfonate non-ionic surfactants produced by Stepan Chemical Co., Notthfield, Illinois). Each sample was 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. The dispersions are sprayed evenly over 10-day bean plants and allowed to dry.

The leaves are removed from the plants and the ends of the leaves are covered with cotton wool soaked in water. The two leaves are placed in each of a 100 mm plastic Petri dish and each of them is loaded with 5 second or third instar larvae of Epilachna varivestis or 5 second or third instar larvae of Spodoptera eridania. Three dishes were used for each test compound. The plates were kept for 4 days at 25 ° C and 51% relative humidity, after which a first evaluation of insecticidal activity was performed. Some of the dishes were left for a further three days, at which time another evaluation was performed.

Insecticidal efficacy was evaluated according to the following scale, comparing solvent controls and untreated controls.

= no dead larvae.

= 1 to 7 dead larvae = 8 to 14 dead larvae = 15 dead larvae

The following table shows the results of tests on typical compounds.

Table 1

Compound Quantity ppm

Epllačhna varlvestis 4 days 7 days

Spodoptera ertdania 4 days 7 days

1 ·. 1000 2 3 3 100 ALIGN! 2 2 3 50 2 2 . 2 25 2 2 1 10 1 2 0 2 1000 1 2 0 100 ALIGN! 1 2 0 3 1000 2 3 2 100 ALIGN! 0 0 0 4 1000 0 2 0 5 1000 1 3 1 100 ALIGN! 0 2 1 8 1000 1 3 2 100 ALIGN! 1 2 1 7 1000 2 0 8 1000 2 3 0 10 1000 1 2 2 100 ALIGN! 0 1 0 11 1000 1 2 2 100 ALIGN! 1 1 1 12 1000 0 0 3 100 ALIGN! 0 0 2 50 1 28 0 13 1000 1 2 3 100 ALIGN! 0 2 2 14 1000 0 1 3 100 ALIGN! 0 0 1 15 Dec 1000 0 0 2 100 ALIGN! 0 0 0 18 1000 1 1 3 100 ALIGN! 0 1 3 50 1 1 3 25 2 2 2 10 1 1 2 5 0 1 1 17 1000 2 3 3 100 ALIGN! 1 2 1 50 1 2 0 25 1 2 0 18 1000 0 0 3 100 ALIGN! 0 0 19 Dec 1000 0 0 3 100 ALIGN! 0 0 1 20 May 1000 1 2 3 100 ALIGN! 1 1 2 21 1000 0 0 2 100 ALIGN! 0 0 0 22nd íooo 2 2 3 100 ALIGN! 1 2 2 50 2 3 1 25 , 1 2 1 23 1000 0 0 2 100 ALIGN! 0 0 0 24 1000 0 0 3 100 ALIGN! 0 0 1 25 1000 1 1 0 100 ALIGN! 0 0 0

σισίΝΝτΗοασιοΗπΗΗΗ NcjHNammNrvmNixiHNOíammmNiMNoqoNocar-icoNNOtncaNHWcmt-iMo

Compound Quantity

Epilachna varivestis

Spodoptera eridania

number PPm 4 days 7 days 4 days 7 days 26 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 1 1 27 Mar: 1000 2 3 3 3 100 ALIGN! 1 2 2 2 50 0 1 1 2 25 0 1 0 1 28 1000 2 2 X, 3 3 100 ALIGN! 1 2 2 2 50 1 2 1 2 25 1 1 0 0 29 1000 1 2 2 3 100 ALIGN! 1 2 0 0 30 1000 2 3 3 3 100 ALIGN! 1 2 3 3 50 1 2 2 2 25 0 2 1 2 31 1000 1 0 3 2 100 ALIGN! 0 0 0 0 32 1000 2 2 2 2 100 ALIGN! 1 2 0 1 33 1000 1 3 2 2 100 ALIGN! 0 2 0 0 34 1000 0 0 3 3 100 ALIGN! 0 0 2 2 35 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 5 1 2 2.5 1 1 36 1000 2 3 2 3 100 ALIGN! 2 2 2 2 50 1 2 25 1 1 37 1000 2 3 3 3 100 ALIGN! 2 2 3 3 50 3 3 3 3 25 3 3 10 2 3 38 1000 2 3 3 3 100 ALIGN! 0 1 0 0 39 1000 0 1 3 3 100 ALIGN! 0 0 0 0 40 1000 2 2 2 2 100 ALIGN! 0 0 0 0 41 1000 0 0 2 3 100 ALIGN! 0 0 0 0 42 1000 0 0 3 3 100 ALIGN! 0 0 1 2 43 1000 0 2 1 3 100 ALIGN! 1 2 - 3 3 50 1 3 1 2 25 1 2 2 2 44 1000 0 0 3 3 100 ALIGN! 1 1 2 2 50 0 1 2 2 25 0 1 0 1

Amount ppm

Epilachna varivéstis 4 days 7 days

Spodoptera eridania 4 days 7 days

1000 0

100 1

1000 1

100 0

1000 1

100 0

1000 2

100 0

1000 2

100 0

1000 2

100 0

1000 1

100 o

1000 1

100 o

1000 1

100 o

1000 1

100 o

1000 3>. 100 1

1000 3

100 2

3

1

1000 o

100 o

1000 1

100 o

1000 1

100 o

1000 2

100 o

1000 1

100 o

o o

o o

o o

o o

o o

o o

O o

o o

o o

O

O

O

O 1 O 1 o 3 3 O O

O 2 3 3 2 1 1 2 O 2 1 3 O O O 1 O

HOnHOOOOOOOOQOrOCOOOMOCOCOCONHKCMHCCrH O O O O

Test 2

Adult developmental test Epílachna varivestis from pupae

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

Compounds are treated as described in Test 1 above. The bean plants are treated as described in Test 1 and the leaves of the treated plants are used for third instar larvae

Epílachna varivestis. Three larvae are used for each dish. If necessary, new leaves are added to the dishes and the larvae are kept until pupa, for about 3-5 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 of hatch control compared to the untreated control and solvents as control. Different numbers of larval dishes were used for the different assays, in each case all dishes were pooled to determine the percentage of control.

Table 2

Compound Concentration% Control No. ppm

1 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 22nd 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 26 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 27 Mar: 100 ALIGN! 100 ALIGN! 50 48 25 3 10 x 11 30 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 35 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 36 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 100 ALIGN! 10 100 ALIGN! 37 100 ALIGN! 93 50 50 25 65 10 50

Test 3

Eating cycle test Epílachna 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 counting after complete pupation and adult development in the untreated control.

199218

Table 3 Compound number Amount ppm % of larval control % control of adult development 14 1000 60 12 100 ALIGN! 70 0 50 60 0 25 50 0

Test 4

Life cycle test Epllachna varivestis

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

day after treatment. The first evaluation reported a larvieid effect as larvae had not yet started to pupate. On the twenty-first day adults were hatched from pupae. In any case, the results below indicate the percentage of conc

trolls compared to the control experiment.

Compound Quantity

No. ppm

Table 4

Percentage of control

Day 3 Day 8 Day 21

1000 100

1000

1000

1000

1000

T e s t 5

Test for Phormia regina

This test demonstrates the efficacy of typical compounds on Phormia regina.

Each test compound was treated by dissolving 4 mg in 0.4 mL acetone and mixing with 40 g homogenized bovine liver to give a concentration of 100 ppm. Lower concentrations of compounds are prepared using an acetone solution containing appropriate amounts of the compound.

The processed liver is divided into two 250 ml plastic flasks and each batch is infected with two-day Phor- larvae.

11 100 ALIGN! 100 ALIGN! 22nd 100 ALIGN! 100 ALIGN! 0 60 100 ALIGN! 0 0 71 0 20 May 100 ALIGN! 0 0 42 0 6 100 ALIGN! 0 100 ALIGN! 100 ALIGN!

mia regina. The liver is placed on a layer of wood shavings and overlaid with another batch of shavings. All flasks, including solvent flasks and untreated controls, are maintained in a temperature and humidity controlled room until pupation: All pupae are then removed, placed in clean plastic petri dishes and held until the adult control pups have emerged. .

The number of flasks per flask is counted when they are placed in petri dishes. The number of adults hatched per dish is also calculated and the percentage of adult control is shown in Table 5 below.

and

38

Table 5

Compound No. Amount of ppm% control of adults 1. 100 ALIGN! 100 ALIGN! 10 15 Dec 1 0 22nd 100 ALIGN! 0 - 10 0 1 0 26 100 ALIGN! 45 10 0 1 0 27 Mar: 100 ALIGN! 25 10 0 1 0 30 100 ALIGN! 100 ALIGN! 10 45 1 0 35 100 ALIGN! 20 May 10 0 1 0 36 100 ALIGN! 10 10 0 1 0 37 100 ALIGN! 25 * 10 0 1 0 Test 6 25 g baby oat porridge, 10.6 ml of honey a 8.0 ml glycerin, 5.3 ml water and 0.5 ml ca- Larvicide test Galleriá mélionella vitamins. Acetone is allowed to evaporate

and the treated food is divided into three Petri

This test was performed to determine the yields and five larvae were added to each the effect of certain compounds on Galleria mello- second and third instar. The dishes are maintained nella, bee hive parasite. seven days under controlled conditions; and Compound in an amount sufficient to determine the percentage of larval control compared to dissolve the desired concentration in 5 ml of controls, acetone and mixed with 49 g of a diet consisting of Table 1k and 6 Compound No. Amount of ppm% control 1 500 0 100 ALIGN! 0 50 0 25 0 12.5 0 22nd 500 100 ALIGN! 100 ALIGN! 100 ALIGN! 50 100 ALIGN! 25 13 12.5 0 26 500 100 ALIGN! 100 ALIGN! 100 ALIGN! 50 0 25 0 12.5 0 27 Mar: 500 100 ALIGN! 100 ALIGN! 100 ALIGN! 50 86 25 13 12.5 0

Compound No.

Amount of ppm% control

500 100 ALIGN! 100 ALIGN! 100 ALIGN! 50 13 25 0 12.5 0 500 100 ALIGN! 100 ALIGN! 100 ALIGN! 50 0 25 . ..O 20 May 0 12.5 13 .10 0 5 0 2.5 0 500 .0 100 ALIGN! 0 50 0 25 0 12.5 0 500 100 ALIGN! 100 ALIGN! -13 50 0 25 0 20 May .7 12.5 0 10 0 5 0 2.5 0

Test 7

Sterilization test for Epilachna varivestis

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. The adults are left on these plants until the females start laying eggs, with tufts of eggs from 20 to 30 eggs removed. and incubate. None of the adult eggs fed to the plants treated with the compound of Example 35 hatch. The compound completely sterilizes beetles fed on the treated leaves.

Test 8

Test for Lepidoptera in the field of Brussels sprouts

Compounds of formula I are tested against lepidopteran pests in the field of Brussels sprouts. 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 compounds is described in the table below as a percentage reduction in insect numbers compared to the number of insects attacking untreated control plants.

Brussels sprouts are preferably attacked by two species of Pieris rapae and Trichoplusla ni. The 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 Lepldopterá 1 0.14 49 24 39 0.28 77 38 61 0.56 67 45 58 1.1 91 52 75 16 0.14 91 72 83 0.28 100 ALIGN! 31 72 0.56  100 ALIGN! 66 86 ' 1.1 100 ALIGN! 79 92 22nd 0.14 40 0 11 0.28 49 52 50 0.56 72 17 50 1.1 91 45 · 72 35 0.14 44 17 33 0.28 77 59 69 0.56 95 24 67 1.1 91 59 78 37 0.14 95 72 86 0.28 86 , 52 72 0.56 95 72 86 1,1 ¹ 100 ALIGN! 31 72

Test 9 The methods described in Test 8, except that the compounds are applied only twice instead

Pieris rapae test on Brussels sprouts three times. The only insect observed in this test was Pieris rapae.

This test is carried out according to the method of

Compound No. Amount kg / ha Percentage of control 1 0.28 66 0.56 81 1.1 97 . 2.2 97 16 0,28 97 0.56 97 1.1 100 ALIGN! 2.2 100 ALIGN! 22 0,28 65 0.56 81 1.1 94 . 2.2 97 35 0,28 75 0.56 88 1.1 97 2.2 97 37 0.28 97  0.56 100 ALIGN! 1.1 100 ALIGN! 2.2 100 ALIGN! The following test was performed according to the above nocarbonyl) -2,6-difluorobenzamide. Results of the tests described and tested in various tests my insecticide Dimilin, N- (4-chlorophenylamino) - below. concentrations are given Amount of ppm of Epilachna varivestis Spodoptera eridania 4 days, 7 days 4 days 7 days

1000 3

1000 2

100 0

100 1

0 1 0 0 v

The above data indicate a potent insecticidal effect of the compounds of Formula I. It will therefore be apparent to the entomologist that the compounds are widely useful for controlling insects of various orders which adversely affect humanity and its economic business.

For example, the compounds are useful for controlling Coleoptera such as Anthonomus grandis, Orambus caliginosellus, Oulema melanopus, Leptinotarsa decemlineata, Hypera postica, Anthrenus scrophularia, Tribolium confusum, Lyctldae species, Agriotes species, Sitophilus oryzae, Nodonota puncticollusis and Conodototarachcticusis; Diptera such as Musea domestica, Stomoxys calcitrans, Haematobia irritans, Phormia regina, Hylemya brasslcae and Psilla rosae; Lepidoptera such as Laspeyresia pomonella, Euxoa species, Plodia Interpunctella, Tartricidae species, Heliothis zea, Ostrinia nubilalis, Hellula rogatalls, Trichoplusia ni, Thyridopteryx ephemeraeformis, Malacosoma amerlcanum and Spodoptera frugiperda; and Orthoptera such as Blatella germanica and Periplaneta americana.

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

An insect can ingest a compound by applying the compound to any substance that the insect eats. For example, plant infesting insects are readily suppressed by applying the compound to the parts of the plant that eat the insects, especially the leaves. Insects that attack and eat textiles, paper, wood products, etc. is readily suppressed by applying the compound to these products. The compounds can be used equally effectively for the protection of stored grain and seeds.

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

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 will die. In other cases, some insects are killed and others survive 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 populations' means a reduction in the number of living insect organisms which, in some but not all cases, causes the disappearance of the treated insect population.

The magnitude of the reduction in insect population caused by the compound depends, of course, on the amount of compound applied. 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. Insecticidal effective amounts range from 1 to 1000 ppm.

The amount of insecticide applied is normally expressed as ¹ concentration of insecticide in the dispersion in which it is applied. The amount applied is measured in this way since it is preferable to apply a sufficient amount of dispersion to cover the leaves or other substances to be treated with a thin layer of dispersion. Thus, the amount of dispersion to be applied depends on the surface area of the substance to be tested 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 which are new, however, because they contain the novel compounds of the present invention. Most commonly 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, generally comprising from 5 to 90 percent of the compound, are conveniently in the form of emulsified 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 to about 90 percent by weight. The inert powder is typically selected from attapulgite clays, montmorillonite clays and diatomaceous clays or purified silicates. Active surfactants comprised in an amount of 0.5 to 10% based on the wettable powder are, for example, sulfonated lignins, condensed naphthalene sulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates and nonionic surfactants such as ethylene oxide adducts to alkylphenol.

Typical emulsifiable compound concentrates include conventional concentrations of compounds, such as 50-500 g per liter of liquid, equivalent to 50-150% dissolved in an inert carrier that is a mixture of a water-immiscible organic solvent and an emulsifier. Useful organic solvents include aromatic compounds, especially xylenes and kerosene fractions, especially high boiling naphthalene and olefinic kerosene fractions, such as heavy aromatic naphtha. Likewise, other organic solvents such as turpentic solvents including resin derivatives and complex alcohols such as 2-ethoxyethanol can be used. Suitable emulsifiers for emulsifiable concentrates are selected from the same types and concentrations as were used for wettable powders.

Likewise, it is practical to apply the compounds in the form of solutions in an appropriate organic solvent, usually in fine petroleum oil, as oil sprays, which are widely used in agricultural chemistry.

Further, the compounds can 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 typically clay, such as pyrophyllite, bentonite or volcanic deposit or montmorillonite. Dusts typically contain compound concentrations in the range of about 0.1% to about 10%.

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

Claims (12)

vynalezu 1) one of R ¹³ and R ¹ · ⁴ may be hydrogen if and only if the other is methoxy, 1] R ²² 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 with bromine, chlorine or fluorine or 1) one of R ¹⁰ and R ¹¹ can be hydrogen if and only if the other is methoxy, 1) R ⁶ and R ⁷ are hydrogen, one of R ⁸ and R ⁹ is hydrogen and the other i is hydrogen, chlorine, methoxy or bromine, iodine, fluorine, trifluoromethyl, methyl, hydroxyl, phenyl or phenyl monosubstituted with bromine, chlorine or fluorine; or A process for the preparation of thiadiazolylbenzamides of the general formula I DN- R where R o, R ¹ and R ² are independently hydrogen, chlorine or bromine, wherein at least one of R o, R ¹ and R ² 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 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 b) R ²² and R ²⁴ are hydrogen and one or both of R ²³ and R ²⁵ are trifluoro are hydrogen or methyl; R ( ²²⁾ and R ( ²³⁾ are hydrogen and R ( ²⁴⁾ and R ( ²⁵⁾ independently of one another are chlorine, fluorine or bromine; or 2) at least one of R ¹⁹ and R ¹¹ must be methyl or methoxy, unless a) R ⁸ is not an atom. hydrogen 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, 2. The process of item 1, for preparing a compound of formula V 2) R ⁶ and R ⁷ are hydrogen and R ⁸ and R ⁹ are independently chlorine, fluorine or bromine; or 3. Process according to claim 1 for preparing a compound of formula I, ·, wherein R ¹⁰ and R ¹¹ are as defined in paragraph 1 wherein R is wherein R o, R ^1, R ^2, R®, R ⁷ and R ⁸ and R ⁹ are as defined in item 1, characterized in that the compound of the formula wherein R is as defined above is cyclized, wherein R ® is not amino or acetamido and R ¹⁰ and R ¹¹ are as defined in point 1 using a dehydrating agent and optionally reducing the compound of formula I wherein R ® is nitro to obtain a compound wherein R ® is amino and further optionally acylated a compound wherein R ® is amino to form a compound wherein R ® is acetamido. 3) neither R ²⁴ nor R ²⁵ are phenyl or substituted phenyl, unless both R ¹³ and R ¹⁴ are methoxy; 3] R ²² and R ²⁴ are hydrogen and R ²³ and R ²⁵ are independently chlorine, fluorine, thunder or trifluoromethyl; or 3) neither R ⁸ nor R ⁹ are phenyl, acetamido, methoxy, nitro group, amino, cyano or substituted phenyl unless both ^R10 and R ^u are methoxyiy, 3) R ⁶ and R ⁸ are hydrogen and R ⁷ and R ⁹ are independently chlorine, fluorine, bromine or trifluoromethyl or 4. A process according to claim 1 for the preparation of N- (5- (4-chlorophenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethylbenzamide, characterized in that 1- (4-chlorobenzoyl) is cyclized. -4- (2,6-dimethyl-benzoyl) -thiosemicarbazide with a dehydrating agent. 4) two of R ²³ , R ²⁴ and R ²⁵ are hydrogen, unless both R ¹³ and R ¹⁴ are methyl or methoxy; 5) both R ¹³ and R ¹⁴ are methoxy when R is pyridyl, naphthyl, furyl or lithienyl, characterized by cyclizing a compound of formula VIII wherein R ¹² , R ¹³ and R ¹⁴ are as defined in formula V by reaction with a dehydrating agent. 4) R ²³ and R ²⁵ are hydrogen and R ²² and R ²⁴ are independently chlorine, fluorine or bromine; or R), R ^23, R ²⁴ and R ²⁵ are hydrogen and R ²² is chlorine, fluorine or bromine, ·, R 13 _and R j _{SOU to SO} bg independently hydrogen, chlorine, fluorine, bromine, methyl or methoxy, wherein 4) two of R ⁷ , R ⁸ and R ⁹ are hydrogen, unless R ¹⁰ and R ¹¹ are methyl or methoxy; 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. The process of item 1 for the preparation of N- (5- (4-fluorophenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethylbenzamide, characterized in that 1- (4-fluorobenzoyl) is cyclized. -4- (2,6-dimethylbenzoyl) thiosemicarbazide dehydrating agent. 5) both R ¹⁰ and R ^u are methoxy or methyl when R represents pyridyl, naphthyl, furyl or thienyl, 5) R ⁷ , R ⁸ and R ⁹ are hydrogen and R ⁶ is chlorine, fluorine or bromine, or 6. The process of item 1 for the preparation of N- (5- (4-trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethylbenzamide, characterized in that 1- (4) -trifluoromethylbenzoyl) -4- (2,6-dimethylbenzoyl) thiosemicarbazide dehydrating agent. 6) both R ¹⁰ and R ¹¹ are methoxy when R is benzothlazolyl, benzoxazolyl, benzothienyl, benzofuryl, isoxazolyl, quinolyl or thiazolyl characterized by cyclizing a compound of formula IV 188218 41 wherein R ¹⁵ , R ¹⁶ are 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 ²⁰ is hydrogen, chlorine, bromine or methyl and either 6) R ^6, R ⁷ and R ⁹ are hydrogen and R ⁸ is an acetamido, nitro, amino or cyano, R¹⁰ _{and R¹¹} NJ _{SOU to S} each independently hydrogen, chlorine, fluorine, bromine, methyl or methoxy, with, where R ¹⁰ and R ¹¹ are as defined for formula I and X is O II R — C — NH— or · Wherein R is as defined in formula I, except for aminophenyl or acetamidophenyl, with a dehydrating agent at 20 to 80 ° C if X is R = C = NH-. ·. '(,) ·· Λ · O or with an oxidizing chip at 50 to 100 ° C, R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms and R ²² forges a compound of formula I wherein R ⁸ is nitro to form a compound wherein R ⁸ is amino and is further optionally acylating a compound wherein R ⁸ is an amino group to form a compound wherein R ⁸ is acetamido. 7. A process according to claim 1 for the preparation of N- [5- (4-chlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, characterized in that 1- (4-chlorobenzoyl) is cyclized. -4- (2,6-dimethoxybenzoyl) thiosemicarbazide dehydrating agent. 8. A process according to claim 1 for the preparation of N- (5- (4-fluorophenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide, characterized in that 1- (4) is cyclized. -fluorobenzoyl) -4- (2,6-dimethoxybenzoyl) thiosemicarbazole dehydrating agent. 9. The process of item 1 for the preparation of N-15- (4-trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, characterized by cyclizing 1- (3- trifluoromethylbenzoyl) -4- (2,6-dimethoxybenzoyl) thioemicarbazide dehydrating agent. 10. A process according to claim 1 for the preparation of N- [5- (3-chlorophenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, characterized in that 1- (3) is cyclized. -chlorobenzoyl) -4- (2,6-dimethoxybenzoyl) -thlosemicarbazide dehydrating agent. 11. The process of item 1 for the preparation of N- [5- (4-trifluoromethylphenyl) -1,3,4-thiadiazol-2-yl] -2,6-dimethoxybenzamide, characterized by cyclizing 1- (4- trifluoromethylbenzoyl) -4- (2,6-dimethoxybenzoyl) thiosemylcarbazide dehydrating agent. 12. A process according to item 1 for the preparation of N- (5- (3,5-bis (trifluoromethyl) phenyl) -1,3,4-thiadiazol-2-yl) -2,6-dimethoxybenzamide, characterized in that: is cyclized with 1- [3,5-bis (trifluoromethyl) benzoyl] -4- (2,6-dimethoxybenzoyl) thiosemicarbazide with a dehydrating agent. Stverojriit, n. 7, Mott