2-Halofuryl/Thienyl-3-Carboxamides

Abstract

Novel 2-halofuryl/thienyl-3-carboxamides of the formula (I)

Description

PREPARATION EXAMPLES

Example 1

Under protective gas (argon), 0.56 ml (3.38 mmol) of N,N-diisopropylethylamine and 1.18 g (2.5 mmol) of bromotrispyrrolidinophosphonium hexafluorophosphate (PyBrop) are added to a solution of 516 mg (2.0 mmol) of 2-iodothiophene-3-carboxylic acid and 300 mg (1.7 mmol) of 2-(1,3-dimethylbutyl)phenylamine in 10 ml of acetonitrile. The reaction mixture is stirred at room temperature for 24 hours and, for work-up, added to water, extracted with ethyl acetate, dried over sodium sulphate and concentrated under reduced pressure. Column chromatography (cyclohexane/ethyl acetate gradient) gives 150 mg (21% of theory) of N-[2-(1,3-dimethylbutyl)phenyl]-2-iodothiophene-3-carboxamide [log P (pH 2.3)=4.14].

Example 2

Under protective gas (argon), 0.56 ml (3.38 mmol) of N,N-diisopropylethylamine and 1.18 g (2.5 mmol) of bromotrispyrrolidinophosphonium hexafluorophosphate (PyBrop) are added to a solution of 483 mg (2.02 mmol) of 2-iodofuran-3-carboxylic acid and 300 mg (1.7 mmol) of 2-(1,3-dimethylbutyl)phenylamine in 10 ml of acetonitrile. The reaction mixture is stirred at room temperature for 24 hours and, for work-up, added to water, extracted with ethyl acetate, dried over sodium sulphate and concentrated under reduced pressure. Column chromatography (cyclohexane/ethyl acetate gradient) gives 130 mg (18% of theory) of N-[2-(1,3-dimethylbutyl)phenyl]-2-iodo-3-furamide [log P (pH 2.3)=3.88].

The compounds of the formula (I) listed in Table 1 below were also obtained analogously to Examples 1 and 2 and in accordance with the details given in the general description of the preparation processes (a) to (h) according to the invention:

TABLE 1
	(I)
No.	A	Hal	R	Ma)	Zb)	logP
3	O	I	H			3.72
4	O	I	H			3.58
5	S	I	H			4.57
6	S	I	H			4.42
7	O	I	H			4.16
8	S	I	H			3.93
9	S	I	H			3.82
10	O	I	H			3.89
11	O	I	H			3.62
12	S	I	H			3.94
13	S	I	H			4.11
14	S	I	H			4.78
15	O	I	H			4.49
16	O	I	H			4.45
17	S	I	H			4.69
18	S	I	H			4.43
19	S	I	H			4.18
20	S	I	H			4.17
21	S	I	H			4.28
22	S	I	H			3.89
23	S	I	H			4.01
24	S	I	H			4.13
25	S	I	H			3.89
26	S	I	H			3.89
27	S	Br	H			4.24
28	S	Br	H			4.51
29	S	Br	H			3.99
30	S	Br	H			4.25
31	S	Br	H			3.91
32	S	I	H			4.21
33	S	I	H			3.67
34	S	I	H			2.20
35	S	I	H			3.69
36	S	I	H			4.67
37	S	I	H			4.16
38	S	I	H			3.79
39	S	I	H		4.09
40	S	I	H			3.79
41	S	I	H			4.17
42	S	I	H			4.44
43	S	I	H			4.22
44	S	Br	H			4.30
45	S	Br	H			4.30
a)The bond marked “*” is attached to the amide, the bond marked “#” is attached to the radical Z.
b)The bond marked “+” is attached to the radical M.

The logP values given were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reverse-phase column (C 18). Temperature: 43° C.

Mobile phases for the determination in the acidic range (pH 2.3): 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.

Calibration was carried out using unbranched alkan-2-ones (having 3 to 16 carbon atoms) with known logP values (determination of logP values by retention times using linear interpolation between two successive alkanones).

The lambda-max values were determined in the maxima of the chromatographic signals using the UV spectra from 200 nm to 400 nm.

USE EXAMPLES

Example A

Sphaerotheca Test (Cucumber)/Protective

Solvents:	24.5	parts by weight of acetone
	24.5	parts by weight of dimethylacetamide
Emulsifier:	1	part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, one part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. The plants are then placed in a greenhouse at about 23° C. and a relative atmospheric humidity of about 70%.

Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

TABLE A
Sphaerotheca test (cucumber)/protective
	Application rate of
Active compound	active compound in	Efficacy
according to the invention	g/ha	in %
	100	98
	100	98
	100	100
	100	100
	100	100
	100	100
	100	100
	100	100
	100	100
	100	100
	100	100
	100	100
	100	100
	100	100
	100	100
	100	98
	100	95
	100	100
	100	98
	100	100
	100	93
	100	100
	100	100
	100	97
	100	98
	100	92
	100	100
	100	97
	100	100
	100	100
	100	100
	100	100
	100	100

Example B

Venturia Test (Apple)/Protective

Solvents:	24.5	parts by weight of acetone
	24.5	parts by weight of dimethylacetamide
Emulsifier:	1	part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, one part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen Venturia inaequalis and then remain in an incubation cabin at about 20° C. and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse at about 21° C. and a relative atmospheric humidity of about 90%.

Evaluation is carried out 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

TABLE B
Venturia test (apple)/protective
	Application rate of
Active compound	active compound in	Efficacy
according to the invention	g/ha	in %
	100	100
	100	94
	100	100
	100	100
	100	97
	100	98
	100	100
	100	100
	100	100
	100	98
	100	89
	100	100
	100	100
	100	100
	100	100
	100	99
	100	100
	100	100
	100	91
	100	100
	100	100
	100	99
	100	100
	100	99
	100	100
	100	100
	100	100
	100	100
	100	100
	100	100
	100	100
	100	98
	100	100
	100	100
	100	100
	100	100
	100	100

Example C

Botrytis Test (Bean)/Protective

Solvents:	24.5	parts by weight of acetone
	24.5	parts by weight of dimethylacetamide
Emulsifier:	1	part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amounts of solvent and emulsifier, and the concentrate was diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, 2 small pieces of agar colonized by Botrytis cinerea are placed onto each leaf. The inoculated plants are placed in a dark chamber at about 20° C. and 100% relative atmospheric humidity.

The size of the infected areas on the leaves is evaluated 2 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

TABLE C
Botrytis test (bean)/protective
	Application rate of
Active compound	active compound in	Efficacy
according to the invention	g/ha	in %
	500	100
	500	99
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	99
	500	100

Example D

Puccinia Test (Wheat)/Protective

Solvent:    50 parts by weight of N,N-dimethylacetamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are sprayed with a conidia suspension Puccinia recondita. The plants remain in an incubation cabin at 20° C. and 100% relative atmospheric humidity for 48 hours.

The plants are then placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of 80% to promote the development of rust pustules.

Evaluation is carried out 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

TABLE D
Puccinia test (wheat)/protective
	Application rate of
Active compound	active compound in	Efficacy
according to the invention	g/ha	in %
	500	100
	500	100
	500	97
	500	97
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	93
	500	94
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100
	500	100

Example E

Alternaria Test (Tomato)/Protective

Solvent:    49 parts by weight of N,N-dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young tomato plants are sprayed with the preparation of active compound at the stated application rate. One day after the treatment, the plants are inoculated with a spore suspension of Alternaria solani and then remain at 100% relative humidity and at 20° C. for 24 hours. The plants then remain at 96% relative atmospheric humidity and a temperature of 20° C.

Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

TABLE E
Alternaria test (tomato)/protective
	Application rate of
Active compound	active compound in	Efficacy
according to the invention	g/ha	in %
	750	94
	750	100
	750	94

Claims

1. 2-Halofuryl/thienyl-3-carboxamides of the formula (I)

2. 2-Halofurylthienyl-3-carboxamides of the formula (I) according to claim 1 in which A represents O (oxygen) or S (sulphur),Hal represents fluorine, chlorine, bromine or iodine,R represents hydrogen, C1-C6-alkyl, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C3-alkoxy-C1-C3-alkyl, C3-C6-cycloalkyl; C1-C4-haloalkyl, C1-C4-haloalkylthio, C1-C4-haloalkylsulphinyl, C1-C4-haloalkylsulphonyl, halo-C1-C3-alkoxy-C1-C3-alkyl, C3-C8-halocycloalkyl having in each case 1 to 9 fluorine, chlorine-and/or bromine atoms; formyl, formyl-C1-C3-alkyl, (C1-C3-alkyl)carbonyl-C1-C3-alkyl, (C1-C3-alkoxy)carbonyl-C1-C3-alkyl; halo-(C1-C3-alkyl)carbonyl-C1-C3-alkyl, halo-(C1-C3-alkoxy)carbonyl-C1-C3-alkyl having in each case 1 to 13 fluorine, chlorine-and/or bromine atoms; (C1-C6-alkyl)carbonyl, (C1-C4-alkoxy)carbonyl, (C1-C3-alkoxy-C1-C3-alkyl)carbonyl, (C3-C6-cycloalkyl)carbonyl; (C1-C4-haloalkyl)carbonyl, (C1-C4-haloalkoxy)carbonyl, (halo-C1-C3-alkoxy-C1-C3-alkyl)carbonyl, (C3-C6-halocycloalkyl)carbonyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms, or —C(═O)C(═O)R1, —CONR2R3 or —CH2NR4R5,R1 represents hydrogen, C1-C6-alkyl, C1-C4-alkoxy, C1-C3-alkoxy-C1-C3-alkyl, C3-C6-cycloalkyl; C1-C4-haloalkyl, C1-C4-haloalkoxy, halo-C1-C3-alkoxy-C1-C3-alkyl, C3-C6-halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,R2 and R3 independently of one another each represent hydrogen, C1-C6-alkyl, C1-C3-alkoxy-C1-C3-alkyl, C3-C6-cycloalkyl; C1-C4-haloalkyl, halo-C1-C3-alkoxy-C1C3-alkyl, C3-C6-halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,R2 and R3 furthermore together with the nitrogen atom to which they are attached form a saturated -heterocycle having 5 or 6 ring atoms which is optionally mono- to tetrasubstituted by identical or different substituents from the group consisting of halogen and C1-C4-alkyl, where the heterocycle may contain 1 or 2 further non-adjacent heteroatoms from the group consisting of oxygen, sulphur and NR6,R4 and R5 independently of one another represent hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl; C1-C4-haloalkyl, C3-C6-halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms,R4 and R5 furthermore together with the nitrogen atom to which they are attached form a saturated heterocycle having 5 or 6 ring atoms which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen and C1-C4-alkyl, where the heterocycle may contain 1 or 2 further non-adjacent heteroatoms from the group consisting of oxygen, sulphur and NR6,R6 represents hydrogen or C1-C4-alkyl,M represents one of the cycles below,

3. Process for preparing the 2-halofurylthienyl-3-carboxamides of the formula (I) according to claim 1, characterized in that a) carboxylic acid derivatives of the formula (II)

4. Compositions for controlling unwanted microorganisms, characterized in that they comprise at least one 2-halofuryl/thienyl-3-carboxamide of the formula (I) according to claim 1, in addition to extenders and/or surfactants.

5. Use of 2-halofuryl/thienyl-3-carboxamides of the formula (I) according to claim 1 for controlling unwanted microorganisms.

6. Method for controlling unwanted microorganisms, characterized in that 2-halofuryl/thienyl-3-carboxamides of the formula (I) according to claim 1 are applied to the microorganisms and/or their habitat.

7. Process for preparing compositions for controlling unwanted microorganisms, characterized in that 2-halofuryl/thienyl-3-carboxamides of the formula (I) according to claim 1 are mixed with extenders and/or surfactants.

8. Halocarboxamides of the formula (IV)

9. Boronic acid derivatives of the formula (VI)

10. Hydroxyalkylcarboxamides of the formula (VIII)

11. Ketones of the formula (XI)