PL164853B1

Composition containing novel propargillic exhibiting microbiocidal and herbicidal effect

Abstract

The invention relates to propargyl compounds, their use and processes for their preparation. Compounds of the formula in which Y and Z independently of one another are O, S or NR; X is H, Br or I; A and R independently of one another are either unbranched or branched C 1-18 -alkyl; C3-8 cycloalkyl; C3-6 alkenyl; C 3-6 alkynyl except propargyl; C7-12 aralkyl; C6-12 aryl optionally substituted by one or more halogen atoms, C1-4 alkyl or haloalkyl, C1-4 alkoxy, nitro, cyano, carboxyl (C1-4) alkoxycarbonyl, C1-4 alkylthio, S (O) nR2, wherein n is 1 or 2 and R2 is C1-4 alkyl; a 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl or 4-pyridyl moiety, each optionally substituted by halogen or nitro; or H are on the condition that R is H only when XI or Br, are described as useful microbicidal agents and herbicides. Formula (I) {propargyl compounds; Use; method; manufacture; microbicidal agent; Herbicide}

Term

No projected expiry on record.

6 claims: 2 independent, 4 dependent

1
Patent claims Zastrzeżenia patentowe 1. A microbicidal and herbicidal composition containing the active substance and known auxiliaries, characterized in that as the active substance it contains a new propargyl compound represented by formula 1, wherein Y and Z are each independently O, S or NR;X is H, Br or J;A and R are each independently a straight or branched chain (C1 to C1s) alkyl group;a (C3 to Cs) cycloalkyl group;(C3 to C6) alkenyl;(C3 to C6) alkynyl with the exception of propargyl;(C7 to C ^ aralkyl group;(C6 to C12) aryl group optionally substituted by one or more halogen atoms, (C1 to C4) alkyl or haloalkyl group, (C1 to C4) alkoxy group, nitro, cyano, carboxyl (C1 to C4) alkoxycarbonyl, (C1 to C4) alkylthio, S (O) nR2in which n is 1 or 2 and R2 is a (C1 to C4) alkyl group;a 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl or 4-pyridyl group, each of which is optionally substituted by halogen or nitro;or is H, with the proviso that R is H only when X is J or Br. 1. Środek mikrobiocydowy i chwastobójczy zawierający substancję czynną oraz znane środki pomocnicze, znamienny tym, że jako substancję czynną zawiera nowy związek propargilowy, przedstawiony wzorem 1, w którym Y i Z każdy niezależnie oznacza O, S lub N-R;X oznacza H, Br lub J;A i R każdy niezależnie oznacza prostołańcuchową lub rozgałęzioną grupę (C1 do C1s)alkilową;grupę (C3 do Cs)cykloalkilową;grupę (C3 do C6)alkenylową;grupę (C3 do C6)alkinylową z wyjątkiem propargilowej;grupę (C7 do C^aralkilową;grupę (C6 do C12)arylową ewentualnie podstawioną jednym lub większą liczbą atomów chlorowca, grupą (C1 do C4)alkilową lub chlorowcoalkilową, grupą (C1 do C4)alkoksylową, grupą nitrową, cyjanową, karboksylo(C1 do C4)alkoksykarbonylową, grupą (C1 do C4)alkilotio, grupą S(O)nR2, w której n ma wartość 1 lub 2 i R2 oznacza grupę (C1 do C4)alkilową;grupę 2-tienylową, 3-tienylową, 2-furylową, 3-furylową, 2pirydylową, 3-pirydylową lub 4-pirydylową, z których każda jest ewentualnie podstawiona atomem chlorowca lub grupą nitrową;lub oznacza H, z tym ograniczeniem, że R oznacza H tylko wtedy, gdy X oznacza J lub Br.
3
3-pirydylową, 3-bromofenylową, 3-etoksyfenylową, n-propylową, 2-chlorofenylową, 2-propynylową, 3-jodo-2-propynylową, cykloheksylową, 2-furylową, 3,5-dimetoksyfenylową, 2,5-dimetoksyfenylową, 3,4,5-trimetoksyfenylową, 2,5-dichlorofenylową, n-heptylową lub metylo-n-butylową:a pozostałe podstawniki mają znaczenia podane w zastrz. 1. 3-pyridyl, 3-bromophenyl, 3-ethoxyphenyl, n-propyl, 2-chlorophenyl, 2-propynyl, 3-iodo-2-propynyl, cyclohexyl, 2-furyl, 3,5-dimethoxyphenyl, 2,5-dimethoxyphenyl, 3,4,5-trimethoxyphenyl, 2,5-dichlorophenyl, n-heptyl or methyl-n-butyl: 1. 3. The agent according to claim A compound according to claim 1 or 2, characterized in that it contains a compound of formula 1, wherein X is J or Br, preferably J, and the other substituents are as defined in claim 1. 1. 3. Środek według zastrz. 1 albo 2, znamienny tym, że zawiera związek o wzorze 1, w którym X oznacza J lub Br, korzystnie J, a pozostałe podstawniki mają znaczenia podane w zastrz. 1.

Independent claims2

752 paragraphs in 14 sections, as filed

The present invention relates to a microbicide and herbicide containing new propargyl compounds. The "propargyl compound" is a compound containing the propargyl group -CH2-C = CH; in the halogen propargyl compound the terminal hydrogen atom is replaced by a halogen atom.

Some groups of iodopropargyl compounds have already been proposed as microbicidal compounds, but none of these groups have achieved commercial success. As used herein, the term "microbicide agent includes, but is not limited to, bactericides, fungicides, and algicides, and microbicidal activity refers to both the removal of microorganisms such as bacteria, fungi and algae, as well as inhibiting their growth.

From the publication of the US patent application US-A-4616004 the fungicidal activity of the compounds of formula 6 is known, and in the US-A-4639460 the compounds of formula 7 are presented as

164 853 compounds with fungicidal activity. In US-A-4520023 there are 3- (3-iodopropargyl) -benzo-1,2,3-triazolin-4-ones and their use as microbicidal agents. JP-A-60/218379 (Nippon Noyaka KK) discloses compounds of formula 8. The addition of a further unsubstituted propargyl group in position 4 gives a herbicidal compound. Both compounds were obtained by reacting 2-propynyl halide with a 1,2,4-triazolin-5-one derivative. There is no information that another related relationship may be active.

There is no information in the prior art that the compounds used in the composition according to the invention can be used to combat microorganisms.

The object of the invention is to provide new agents for controlling microorganisms.

The agent according to the invention contains as active substance a new compound of general formula 1, wherein Y and Z, each independently, is O, S or or NR; X is H, J or Br; A and R are each independently a straight or branched chain (C 1 to C 18) alkyl group; (C3 to C)) cycloalkyl; (C3 to C6) alkenyl; (C3 to C6) alkynyl with the exception of propargyl; (C7 to C12) aralkyl; (C6 to Ci2) aryl group optionally substituted by one or more halogen atoms, (Ci to C4) alkyl or haloalkyl group, (Ci to C4) alkoxy, nitro, cyano, carboxyl (Ci to C4) alkoxycarbonyl, (Ci to C4) alkylthio, an S (O) groupnR, where n is i or 2, and R is a (C1 to C4) alkyl group; a 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl or 4-pyridyl group, each of which is optionally substituted by halogen or nitro; or is hydrogen, with the proviso that R is H only when X is J or Br.

The agent also contains known excipients such as an agriculturally acceptable carrier, cosmetic agent, cooling lubricant oil, soap or synthetic detergent, propargyl compound stabilizer, film-forming material or the like.

Preferred are compositions according to the invention which as active substance contain a compound of formula I in which A or R each independently represents a hydrogen atom, a methyl, ethyl, isopropyl, 4-chlorophenyl, 3-chlorophenyl, 2-methylphenyl, 4-methylphenyl group , 3-methylphenyl, 2-thienyl, 2-nitrophenyl, 3-nitrophenyl, 4-trifluoromethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 4-bromophenyl, 2-fluorophenyl, 2-chloro-4-nitrophenyl, 2,4-chlorophenyl . 3,4-dichlorophenyl, 2,4,5-trichlorophenylmethyl, n-butyl, t-butyl, allylphenyl, 4-nitrophenyl, 3-fluorophenyl, i-naphthyl, 2-naphthyl, 3-pyridyl, 3-bromophenyl, 3- ethoxyphenyl, n-propyl, 2-chlorophenyl, 2-propynyl, 3-iodo-2-propynyl, cyclohexyl, 2-furyl, 3,5-dimethoxyphenyl, 2,5-dimethoxyphenyl, 3,4,5-trimethoxyphenyl, 2, 5-dichlorophenyl, n-heptyl or methyl-n-butyl; and the other substituents have the meanings set out above.

The composition according to the invention containing the new propargyl compounds can be used as a microbicidal or herbicidal agent.

Especially compositions containing compounds of formula I in which X = Br or J (halopropargyl compounds) have microbicidal or herbicidal applications; whereas compounds in which X = H can advantageously be used as herbicides. .

In herbicidal compounds, Z is preferably NR, wherein R is a lower alkyl group, such as methyl or ethyl, and A is an optionally substituted phenyl group. Usually, 5-one compounds (Y = C) are also preferred.

Iodopropargyl compounds, i.e. those in which X is J, are preferred for the microbicidal effect. 5-one compounds, i.e., those in which Y = 0) are also preferred.

The compositions according to the invention have a wide range of usefulness and serve to protect against microorganisms or to control microorganisms from various groups including fungi, bacteria, algae, viruses and yeast and to control weeds. Microbicidal agents are preferably used to protect wood, paints, glue, binder, paper, textiles, leather, plastics, cardboard, lubricants, cosmetics, food, seals, feed and industrial cooling water against microorganisms.

The compositions according to the invention intended for microbicidal or herbicidal application may contain from 0.000i to 99.9999% of the compound of formula I, preferably from 0.0005 to 95%.

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Listed below are the individual industries and applications of the microbicidal agents of the invention:

<td>Industry</td><td>Application</td>

<td>binders, sealants, agriculture - food chain</td><td>binders, pipe joint seals, sealants, auxiliary preservatives, active substances for agriculture, chemical preservatives for agriculture, protective preparations for agriculture, food protection for animals, chemicals for dairies, protection of fertilizers, food protection, chemicals for food processing, grain protection, post-harvest protection measures, sugar processing, tobacco</td>

<td>construction materials</td><td>asphalt / concrete, cement modifiers, construction products, roof sealing compounds, synthetic plasters, wall sealing compounds, cement for joints</td>

<td>cosmetics and toilet products</td><td>cosmetics, raw materials for cosmetics, toilet products, toilet products</td>

<td>disinfectants, bactericidal emulsions, dispersions</td><td>bactericides, disinfectants aqueous dispersions, dispersed pigments, latexes, photographic emulsions, pigment suspensions, polymeric latexes</td>

<td>preparations used in the household</td><td>agents for fabrics, agent for broadcasting sweat, waxes, hand dishwashing detergents, raw materials, liquid detergents, hand soaps</td>

<td>industrial processing, various</td><td>paints, baths, rinsing for electroplating, pre-treatment before electroplating, baths after electroplating, protection of industrial liquids, pasteurization baths, securing auxiliary processes</td>

<td>industrial water purification</td><td>scrubber, external, cooling towers, cooling water, water protection, processing of moldings and building elements of wooden cooling towers, heaters, pasteurization in breweries, water cooling systems in a closed circuit</td>

<td>Cleanings</td><td>household products ©, art- washed dust, washing water, laundry and disinfection</td>

<td>leather, leather products</td><td>ί leather, raw leather products and dressed up</td>

<td>greases, hydraulic fluids</td><td>ί car lubricants, conveyor lubricants, greases, hydraulic fluids, lubricants</td>

<td>medical equipment</td><td>enzymes, kits medical</td>

<td>metalworking and associated applications odor control (active substance)</td><td>coolants, metal cleaners, treatment puffs, metal conditioning, flooding, animal litter, cat waste, chemical toilet preparations, deodorants, humidifiers, industrial deodorants, sanitary preparations, toilet bowls</td>

<td>paints and coatings paper and wood pulp, their products</td><td>emuljje, aarby absorbent materials from ρ3ρϊεπι and wood pulp, packaging materials made of paper and wood pulp, paper, paper products, paper processing, soap packaging, wood pulp, wood pulp products</td>

<td>paper mill</td><td>agent, slimy, up to ρ3ρίεπ, slurry of pulp and paper</td>

164 853

<td>oil refining, fuels</td><td>aviation fuels (fuels for turbojet engines, aviation gas), crude oils, combustion chambers, diesel oil for diesel and turbine engines, carbon suspensions, diesel fuel additives, diesel oils, fuels, gasoline, heating oils, hydrocarbons, kerosene, liquid gas , petrochemical raw materials, petroleum products - storage, transport and production, circulating petroleum products, residual diesel oils, turbine oils</td>

<td>photography chemicals and processes</td><td>photographic processes, washing water, phisers, photographic technological process, chemicals for processing photographic plates (developers, fixatives, etc.)</td>

<td>printing</td><td>spray (printing) solutions, printing ink components (pigments, resins, solvents, etc.), printing inks</td>

<td>disinfectants (active)</td><td>disinfectants, dairy disinfectants, dental disinfectants, fermentation disinfectants, food disinfectants, food disinfectants, medical disinfectants, fat smelting disinfectants, veterinary disinfectants</td>

<td>soaps, detergents, cleaning agents</td><td>cleaners, detergents, household cleaners, industrial cleaners, liquid soaps, grease and oil removers, powdered soaps, raw cleaning materials, soaps, surfactants</td>

<td>textiles</td><td>nonwovens, sack fabrics, tarpaulin, tarpaulin products, carpet backing, rugs, fabrics, coated fabrics, curtains, draperies, technical fabrics, fibers, geotextiles, products made of fabrics, knitted fabrics, nets, nonwovens, ropes, rugs, textile accessories, products textiles, textiles, upholstery, fabrics, yarn</td>

<td>textile technological processes</td><td>dyeing fixatives, dyes, fiber lubricants, grip modifiers, sizes, fluids in textile processing</td>

<td>therapeutic agents (active or protective)</td><td>animal health (veterinary, aquaculture, teeth, human health, pharmaceutical) therapeutic</td>

<td>water purification</td><td>charcoal deposits, deionization resins, filters, diaphragms, reverse osmosis membranes, ultrafilters, water purification, water purification pipes, pipes</td>

<td>wood use various</td><td>wood stains, wood, wood products alcohols, water or layering gels, ceramics, washing out contact lens packaging, electronic circuit assemblies, electronics chemicals, enzymatic food production, enzymes, enzyme industry, gel pads, anti-lichen agents, anti-mold agents, wood, plastics, laundry , mining, natural rubber latexes, Injection water in the oil field, including enhanced recovery of injection fluids, drilling, breaking and make-up fluids, pipes, plastics, polymer systems, polymers and resins (synthetic and natural), reagent protection, rubber, rubber products, skin removers, solid coatings protective / decorative, stain, swimming pools, marshlands, water deposits</td>

164 853

The amount of compound used depends on the type of application. Useful amounts for specific applications are similar to those used for other microbicidal compounds.

The agents of the invention may be used in combination with other microbicides.

Compounds of formula I can be prepared in various ways. One suitable method is to react a compound of formula 9 with a compound of formula LCH2C = CH, wherein L is a leaving group in the presence of a base such as potassium carbonate. Suitable leaving groups include halogen atoms such as Br or Cl, a sulfonyl group such as p-MePhSOzO- or p-NO2PhSO2-. In this way, the compound of formula 5 is obtained. These compounds can then be further reacted with an iodinating or brominating agent to obtain iodopropargyl or bromopropargyl equivalents.

Suitable iodinating or brominating agents include, for example, iodine, bromine, iodine compound such as morpholine-iodine complex, morpholine-bromine complex, Nbromosuccinimide (MBS) and N-iodosuccinimide (NIS), with the latter being the most preferred.

When iodine, bromine or an iodine compound is used, a base should preferably be used, preferably sodium or potassium hydroxide, and a solvent such as methanol, ethanol and aqueous ethanol should also be used. When NIS or NBS is used, a catalyst such as, for example, silver nitrate or the like should be used in the presence of a solvent such as acetone, methyl ethyl ketone, tetrahydrofuran and the like.

The reaction time is about 20 minutes to about 24 hours and the reaction temperature is about 0 ° C to about 25 ° C.

The following examples illustrate the invention. All parts and percentages are by weight unless otherwise stated.

Listed below are some representative compounds used as active ingredients in the composition of the invention:

1. 2- (4-chlorophenyl) -4- (3-jodopropargilo) -1,3,4-oxadiazolin-5-one

2. 2 ((2-metyloffnylo)) 4--3-jodopropaΓgiIo) -l, 3,4-oxadiazolin (5-on

3. 2- (4-methyl [of'enylo)) 4--3-jodopropargilo) -1,3,4-oxadiazolin-5-one

4. 2- (3-metyloffnylo)) 4- (3-jodopropargilo) -1,3,4-oxadiazolin (5-on

5. 2- (2-chlorophenyl) -4- (3-JodopΓOpaΓgilo) -1,3,4-oxadiazolin-5-one

6. 2 ((3-chlorophenyl)) 4--3 - odopropargilo) -1,3,4-oxadiazolin (5-on

7. 2- (2-thienyl) -4- (3-jodopΓopargilo) -l, 3,4 ~ oxadiazolin (5-on

8. 2 (n (propyl-4- (3- (odopropargilo) -1,3,4-oxadiazolin (5-on

9. 2- (4-nitrophenyl) -4- (3-jodopropargilo) -1,3,4-oxadiazolin-5-one

10. 2- (3-nltrofenylo) -4- (3 - odopropargilo) -1,3,4-oxadiazolin-5 (On

11. 2- (2-nitΓofenylo) -4--3- (odopropargllo) -1,3,4-oxadiazolin (5 (He

12. 2- (4-trifluoromethylphenyl) -4- (3- (odopropargilo) -1,3,4-oksadiazolm-5-one

13. 2- (2-methoxyphenyl)) 4--3-jjDdopropargilo) -1,3,4-oxadiazolin-5-one

14. 2 ((4-methoxyphenyl)) 4- (3-jodopropargilo) 1, -, 4-oxadiazolin-5-one

15. 2- (3-methoxyphenyl)) 4-3-iodopropargyl) -1 J -oxadiazolin ^ -one

16. 2- (4-bromophenyl) -4--3-jc) dopropargilo) -1,3,4-oxadiazolin-5-one

17. 2- (2-Ωuorofenylo) -4- (3-jodopropargilo) -1,3,4-oxadiazolin-5-one

18. 2- (2-furyl) -4--3-jodopropargllo) -1,3,4-oxadiazolin-5 (On

19. 1 ((- iodopropargyl) (3 ((4-methylphenyl- (4-ethyl-1 ^^ - triazolin ^ -one)

twenty. l ((- (jodopropargilo) (3- (4-chlorophenyl) (4- (ethyl-1,2,4-triazolin-5-one

21.1 ((3-iodopropargyl) -3-phenyl-4-ethyl (1,2,4-triazolin-5-one

22. l ((- (Codopropargilo) (3- ((4- (nitrophenyl) (4-ethyl-1,2,4-triazolin-5 (On

23. l - (- (jodopropargiIo) -3- (4-methoxyphenyl) -4-ethyl-1,2,4-triazolin-5 (On

24. l ((3- (jodopropargilo) -3- (2-thienyl) -4-ethyl-1,2,4-triazolm-5-one

25. 1 ((- (odopropargilo) -3- ((3- (methyl) -4-ethyl-1,2,4-triazolin-5 (On

26. | ((3- (Codopropargilo) -3- (2- (methyl phenyl (4-ethyl-1,2,4-triazolin-5-one

27. l - (- (jodopropargilo) -3- (3- (Πuorofenylo- (4- (ethyl-1,2,4-triazolin (5-on

28. l- (3- (jodopropargilo) -3- (1 (naphth - 4-ethyl-1,2,4-triazolin-5-one

164 853

29. 1- (3-jodopropargilo) -3- (2-naphthyl) -4-ethyl-1,2,4-triazolin-5-one

thirty. l- (3-jodopropargilo) -3- (4-bromophenyl) -4-etyIoi, 2,4-triazolin-5-one

31.1 - (3-iodopropargyl) -3- (2-fluorophenyl) -4-ethyl-1,2,4-triazolin-5-one

32. 1- (3-jodopropargilo) -3- (4-fluorophenyl) -4-ethyl-1,2,4-tnazolin-5-one

33. 1- (3-jodopropargilo) -3- (3-pyridyl) -4-ethyl-1,2,4-tnazolin-5-one

34. 1- (3-iodopropargyl) -3- (2-methoxyphenyl) -4-ethyl-1,2,4-triazolin-5-one

35. 1- (3-iodopropargyl) -3- (3-nitrophenyl) -4-ethyl-1,2,4-triazolin-5-one

36. 1- (3-jodopropargilo) -3- (3-chloIofenyio) -4-ethyl-i, 2,4-triazolin-5-one

3Ί. 1- (^ - iodopropargyl ^-^ - bromophenyl ^ -ethyl-1,2,4-triazolin-5-one

38. 1- (3-Jodopropargilo) -3- (3-methoxyphenyl) -4-ethyl-1,2,4-triazolin-5-one

39. 1- (3-Jodopr ^ o ^ f ^^ rgillo) - ^^ ^ 3 (3-ethoxyphenyl) -4-ethyl-1,2,4-triazolin-5-one

40. 1- (3-iodopropargyl) -3- (4-methylphenyl) -4-n-butyl-1,2,4-triazolin-5-one

41. 1- (3-jodopropargilo) -3- (4-methylphenyl) -4 --- propyl-1,2,4-triazolin-5-one

42. 1- (3-jodopropargilo) -3-n-propylsulfanyl-4-ethyl-1,2,4-triazolin-5-one

43. 1- (3-Jodopropargllo) -3- (4-chIorofenylo) -4-phenyl-1,2,4-triazolin-5-one

44. 1- (3-jodoprof ^^ i ^ g; yl) -3- (2-chlorophenyl) -4-ethyl (o-1,2,4-triazolin-5-one

45. 1- (3-jodopropargilo) -3- (4-chlorophenyl) -4- (4-chlorophenyl) -1,2,4-triazolin-5-one

46. 1- (3-jodopropargilo) -3- (4-chlorophenyl) -4- (4-methylphenyl) -1,2,4-triazolin-5-one

4Ί. 1- (3-Jodopropargilo) -3-methyl-4-phenyl-1,2,4-tπazoiin-5-one

48. 1- (3-jodopropargilo) -3-methyl-4- (4-chlorophenyl) -1,2,4-triazolin-5-one

49. 1- (3-jodopropargilo) -4- (4-chlorophenyl) -1,2,4-triazolin-5-one

50. 1- (3-jodopropargilo) -4-phenyl-l, 2,4-triazolin-5-one

51. 1- (3-jodopropaΓgίlo) -3- (4-bromophenyl) -4-methyl-1,2,4-triazolin-5-one

52. 1-O-iodopropargyl ^ - ^ - chlorophenyl ^ -methyl- 1,2,4-triazolin-5-one

53. 1- (3-jodopropargilo) -3- (4-fluorophenyl) -4-methyl-1,2,4-triazolin-5-one

54. 1- (3-iodopropargyl) -3- (3-chlorophenyl) -4-methyl-1,2,4-triazolin-5-one

55. 1- (3-jodopropargilo) -3- (3-bromophenyl) -4-methyl-1,2,4-triazolin-5-one

56. 1- (3-iodopropagglo) -3- (3-fluorophenyl) -4-methyl-1,2,4-tnazolin-5-one

5Ί. 1- (3-jodopropargilo) -3- (2-nuorofenylo) -4-methyl-1,2,4-triazolin-5-one

58. 1- (3-jodopropargilo) -3-t-tertbutyl-4-phenyl-1,2,4-triazolin-5-one

59. 2-phenyl-4-jodopropargilo-1,2,4-thiadiazole-5-one

Table 1 shows the structure and physical properties of these and other representative compounds of formula 2 (oxadiazolones), formula 3 (triazolones) and formula 4 (thiodiazolones). For compounds No. 1 to 121 X is J, for compound No. 122 to 148 X is H.

Table 1

<td>No.</td><td>Pattern</td><td>AND</td><td>R</td><td>Melting temperature</td><td>NMR shifts (ppm)</td>

<td>Ί</td><td> 2</td><td>2-thiophene</td><td> -</td><td>1 ^^^ 151 ° C</td><td></td>

<td> 8</td><td> 2</td><td>n-propyl</td><td> -</td><td>42-46 ° C</td><td>4.60 (2H, s, CH2), 2.55 (2H, t, CH2), 1.Ί4 (2H, m, CH2), 1 02 (3H, t, CH3)</td>

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<td> 18</td><td> 2</td><td>2-furyl</td><td> -</td><td>140-142 ° C</td><td></td>

<td> 23</td><td> 3</td><td>4-OMe-Ph</td><td>et</td><td>Oil</td><td>7 20 (4H, aromatic H), 4.75 (2H, s, CH2), 3.84 (3H, s, CH3), 3 75 (2H, q, CH2), 1.28 (3H, t, CH3)</td>

<td> 24</td><td> 3</td><td>2-thiophene</td><td>et</td><td>134-136 ° C</td><td></td>

<td> 25</td><td> 3</td><td>3-Me-Ph</td><td>et</td><td>Oil</td><td>7.34 (4H, m, aromat. H), 4.78 (2H, s, CH2) 3 80 (2H, q, CH2), 2.40 (3H, s, CH3), 1.25 (3H, t, CH3)</td>

<td> 26</td><td> 3</td><td>2-Me-Ph</td><td>et</td><td>Oil</td><td>7.35 (4H, m, aromat. H), 4.80 (2H, s, CH2), 3.56 (2H, q, CH2, 2.29 (3H, s, CH3), 1.12 (3H, t, CH3)</td>

<td> 28</td><td> 3</td><td>1-naphthyl</td><td>et</td><td>148-152 ° C</td><td></td>

<td> 29</td><td> 3</td><td>2-naphthyl</td><td>et</td><td>63-70 ° C</td><td></td>

<td> 33</td><td> 3</td><td>3-pyridyl</td><td>et</td><td>129-131 ° C</td><td></td>

<td> 36</td><td> 3</td><td>3-Cl-Ph</td><td>et</td><td></td><td>7.60 (4H, m, aromat. H), 4.81 (2H, s, CH2), 3.85 (2H, q, CH2), 1.32 (3H, t, CH3)</td>

<td> 37</td><td> 3</td><td>3-Br-Ph</td><td>et</td><td></td><td>7.80 to 7.40 (4H, m, aromat. H), 4.80 (2H, s, CH2), 3.84 (2H, q, CH2), 1.30 (3H, t, CH3)</td>

<td> 38</td><td> 3</td><td>3-OMe-Ph</td><td>et</td><td></td><td>7.50 to 7.00 (4H, m, fragrance H), 4.80 (2H, s, CH2), 3.85 (4H, r, CH3CH &2), 1.30 (3H, t, CH3)</td>

<td> 39</td><td> 3</td><td>3-OEt-Ph</td><td>et</td><td></td><td>7.50 to 7.00 (4H, m, flavor H), 4.80 (2H, s, CH2), 4.10 (2H, q, CH2), 3.84 (2H, q, CH2), 1.46 (3H, t, CH3), 1.26 (3H, t, CH3)</td>

<td> 58</td><td> 3</td><td>t-Butyl</td><td>ph</td><td>I7O-174 ° C</td><td></td>

<td> 60</td><td> 2</td><td>1-naphthyl</td><td> -</td><td>167-I69 ° C</td><td></td>

(2Η, m, CH2), 1.42 (2H, m, CH2), 0.95 (3H, t, CH3)

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<td> 77</td><td> 2</td><td>n-Heptyl</td><td> -</td><td>Oil</td>

4.62 (2H, s, CH2), 2.58 (2H, t, CH2), i.70 (2H, m, CH2), i.32 (i2H, m, 4CH2), 0.90 (3H, t, CH3)

4.72 (2H, s, CH2), 3.42 (3H, s, CH3), i.40 (9H, s, 3CH3)

4.70 (2H, s, CH2), 3.88 (2H, q, CH2), and .38 (i2H, m, 4CH3)

4.68 (2H, s, CH2), 3.72 (2H, q, CH2), 2.26 (3H, s, CH3), i.30 (3H, t, CH3)

4.82 (2H, s, CH2), 3.70 (2H, q, CH2), 2.40 (2H, t, CH2), i.66 (2H, m, CH2), i.38 (5H, m), 0.98 (3H , t, CH3)

<td> 92</td><td> 3</td><td>Me</td><td>n-Hexyl</td><td>Oil</td>

<td> 93</td><td> 3</td><td>Me</td><td>benzyl</td><td>I70-I72 ° C</td>

<td> 94</td><td> 3</td><td>Me</td><td>Cyclohexyl</td><td>103-I06 ° C</td>

<td>II2</td><td> 3</td><td>H</td><td>Cyclohexyl</td><td>ii8-i22 ° C</td>

<td>II3</td><td> 3</td><td>H</td><td>benzyl</td><td>ii9-I24 ° C</td>

7.22 (4H, q, arom. H), 4.76 (2H, s, CH2), 3.85 (3H, s, CH3), 2.40 (2H, t, CH2), i.58 (2H, m, CH2), 0.90 (3H, t, CH3)

7.55-7.02 (4H, m, arom. H), 4.78 (2H, s, CH2), 3.86 (3H, s, CH3), 2.32 (2H, q, CH2), and .60 (2H, m, CH2) , 0.90 (3H, t, CH3)

4.70 (2H, s, CH2), 3.60 (2H, t, CH2), 2.26 (3H, s, CH3), i.64 (2H, m, CH2), i.34 (6H, m, 3CH2), 0.9 and (3H, t, CH3)

7.42 (iH, s) 4.64 (2H, s, CH2), 3.70 (2H, q, CH2), i.34 (3H, t, CH3)

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<td> 114</td><td> 3</td><td>H</td><td>n-Hexyl</td><td>Oil</td><td>7.45 (1H, s, olefinic H), 4 74 (2H, s, CH2), 3.64 (2H, t, CH2), 1.72 (2H, m, CH2), 1.35 (6H, m, 3CH2), 0.90 (3H , t, CH3)</td>

<td> 120</td><td> 3</td><td>H</td><td>n-Octyl</td><td>Oil</td><td>7.44 (1H, s, olefinic H), 4.72 (2H, s, CH2), 3 62 (2H, t, CH2), 1.72 (2H, m, CH2), 1.30 (10H, m, 5CH2), 0.90 (3H, t, CH3)</td>

<td> 121</td><td> 3</td><td>H</td><td>n-Dodecyl</td><td>50-52 ° C</td><td></td>

(For all compounds below X = H)

<td> 125</td><td> 3</td><td>4-Meopham</td><td>et</td><td>Oil</td>

<td> 127</td><td> 3</td><td>2-thienyl</td><td>et</td><td>57-60 ° C</td>

Example 1. Method for producing 2- (4-chlorophenyl) -4- (3-iodopropargyl) -1,3,4-oxadiazolin-5-one (compound 1).

To a suspension of 8.53 g (0.05 mol) in 100 ml of methylene chloride contained in a reaction flask equipped with a magnetic stir bar, nitrogen inlet, dropping funnel and outlet connected to a dilute solution of a base for catching HCl gas, 5.94 g (dropwise) 0.03 mol) trichloromethyl chloroformate. After the addition was complete, the reaction mixture was heated to reflux for 2 hours. The reaction mixture was cooled to room temperature and poured into a mixture of 500 ml water and 200 ml hexane and stirred for 10 to 20 minutes. The resulting precipitate was collected by suction filtration and washed with hexane to give a solid product. The product was air-dried at room temperature overnight to give 5.5 g (60% yield) of 2- (4-chlorophenyl) -1,3,4-oxadiazolin-5-one as a solid, m.p. 225-227 ° C . NMR and IR spectra showed the desired structure. The product was used in the next step without further purification.

To a suspension of 2g (0.01 mol) 2- (4-chlorophenyl) -1,3,4-oxadiazolin-5-one in 50ml acetone was added 2 g (0.015 mol) potassium carbonate, followed by 1.6 g (80% in toluene, 0.0106 mol) propargyl bromide, induction stirring under nitrogen for 3 hours. The reaction mixture was cooled to room temperature. The suspension was filtered by suction filtration and the solid was washed with acetone. The filtrate was concentrated to approximately 10 mL and poured into 200 mL. The resulting precipitate was collected by suction filtration and washed with water and hexane to obtain 0.85 g (yield

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36%) after air drying, 2 ((4-chlorophenyl)) 4-p-phenyl-1,3,4-oxadiazolin-5 (Onu as a solid with a melting point of 125-127 ° C. NMR and IR spectra showed the desired The compound was used in the next step without further purification.

To a suspension of 0.6 g (0.00256 mole- 2- (4-chlorophenyl) -4-p-propargyl-1, - 4-oxadiazolin (5-one in 20 ml of acetone, 0.6g was added with induction stirring at room temperature) 0.00266 mol-) N-iodosuccinimide followed by 0.040g (0.00024 mol) silver nitrate The reaction mixture was stirred at room temperature for an hour The suspension was filtered by gravity and the solid was rinsed with acetone. The filtrate was poured into 300 ml of water. The resulting precipitate was collected by suction filtration and air dried to give 0.8g (92% yield) 2- (4-chlorophenyl) -4- (3- (odopropa-gyl) -1, -, 4 (Oxadiazolin (5 (Onu in the form solid substance, m.p. 151-152 ° C. Proton NMR spectrum was consistent with the desired structure.

Example II Process for producing 1- (3 (iodopropargyl) --- (4 (Chlorophenyl) (4-ethyl-1,3,4-triazolin-5-one (compound 20).

To a suspension of 98.5 g (0.05 mol) of 4-chlorobenzhydrazide in 100 ml tetrahydrofuran at room temperature, slowly adding 4.2 g (0.05 mol) of ethylisocyanate while stirring inductively. The reaction was slightly exothermic and the reaction mixture turned into a thick paste. Stirring was continued for a further 30 minutes after which the solid was collected by suction filtration and washed with a small amount of tetrahydrofuran and dried to give 11.6 g (96.6% yield) of 1- (4-chlorobenzoyl) -4 (ethylsemicarbazide as a white solid) mp 242-243 ° C. 10 g (0.0414 mol) of the above semicarbazide were dissolved in 100 ml of 1 N sodium hydroxide solution with stirring for 16 hours. The solution was cooled to about 10 ° C in an ice bath and neutralized with concentrated hydrochloric acid to pH 2. The resulting white solid was collected by suction filtration and washed with water to obtain 8.65 g (93.5% yield) 2- (4-chlorophenyl) -4- ethyl-1,2,4-triazolin-5-one as a white solid, mp 190-197 ° C. Proton NMR spectra were consistent with the desired structure.

To a solution of 2.23 g (0.01 mol) 3- (4 ^ c ^ 1 ^ lorophenyl) - ^ ';^ - ^ and ^ tt ^ to-1,2,4-triazolin-5-Qnu in 40 ml dry acetone, 1.67 g (0.012 mol) potassium carbonate was added at room temperature, followed by 1.8 g (80% in toluene, 0.012 mol) propargyl bromide. The reaction mixture was then heated to reflux with stirring for 6 hours. The mixture was cooled to room temperature and the solvent was evaporated to give a residue. The product was purified by crystallization from hexane / ether to give 1.8 g (69.2% yield) of 1-propargylQ-3- (4-chloro-phenyl) -4-ethyl-1,2,4-triazQlin (5-one as a white solid) substance at 115-119 C. Proton NMR spectra were consistent with the desired structure.

To a solution of 1.0g (3.82 mmol) 1-prQpargilQ (- ((4-chlorophenyl-4-ethyl-1,2,4-triazolm-5-one in 20 ml of dry acetone was added 0.95 g (4 , 2 mmol) N-iodosuccinimide, followed by 50 mg (0.29 mmol) of silver nitrate, with induction stirring at room temperature. The reaction mixture was stirred for an hour. The resulting suspension was filtered and the filtrate poured into 250 ml of water. A yellowish solid precipitated slowly, which was collected by suction filtration and washed with water to give 1.12 g (76% yield) 1- (3- (odoprQpargilQ) --- (4-chlorophenyl) -4-ethyl-1,2, 4-triazolin ^ -one as a pale yellow solid with a melting point of 115-120 C. Proton NMR was consistent with the desired compound.

Example III. Production method for 2-phenyl-4- (odopropargyl-1,4- thiadiazlin-5-one (compound 59).

A. Method for producing thiobenzhydrazide.

A cold solution of 12.25 g (57.6 mmol) of S ((tiQbenzoylQ - tiQglikQlowegQ) in 60 ml (60 mmol NaOH) 1 N NaOH was slowly added to a solution of 6g (123.8 mmol) hydrazine monohydrate in 5 ml water at a temperature of about 5 ° C. with induction stirring After completion of the addition, the resulting yellow suspension was stirred at room temperature for an hour The mixture was cooled to 5 ° C and acidified with concentrated HCl to pH 6. The yellow solid was collected by suction filtration and washed with water to give 3.70 g of product after drying in air, mp 66-68 ° C.

B. Process for preparing 2-phenyl-1,3,4-thiadiazQlm (5-one.

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To a solution of 3.7 g (23.34 mmol) of thiobenzhydrazide in a 50 ml methylene chloride contained in a reaction flask equipped with a magnetic stirrer, nitrogen inlet and outlet connected to a trap containing diluted NaOH solution, 4 g (20.2 mmol) of chloroformate were added. trichloromethyl. The reaction mixture was stirred at room temperature for an hour. The mixture was diluted with 100 mL methylene chloride and washed 3 times with 50 mL brine. The organic layer was dried over MgSO4. After filtering the drying agent, the filtrate was concentrated. The resulting residue was triturated with hexane and the solid product was collected by suction filtration to give 3.7g of powder, m.p. 140-143 ° C.

C. Process for preparing 2-phenyl-4-propargyl-1,3,4-thiadiazolin-5-one.

To a solution of 3g (16.85mmol) 2-phenyl-1,3,4-thiadiazolin-5-one in 30ml dry acetone under nitrogen, 3g (22mmol) potassium carbonate was added with induction stirring followed by 3g (80%) in toluene, 20 mmol) propargyl bromide at room temperature. The mixture was heated to reflux for an hour. The reaction mixture was cooled to room temperature and the solid was filtered off by suction filtration. The filtrate was diluted with 200 ml ether and washed twice with 50 ml brine. The organic layer was dried over sodium sulfate. After drying, the drying agent was filtered off and the filtrate was concentrated to about 5 ml. Hexane was added to precipitate the product. The product was collected by suction filtration and washed with a small amount of hexane to give 2g of 2-phenyl-4-propargyl-1,3,4-thiadiazolin-5-one as a powder, mp 73-75 ° C.

D. Method for the preparation of 2-phenyl-4-iodopropargyl-1,3,4-thiadiazolin-5-one.

To a solution of 1.6 g (7.4 mmol) 2-phenyl-4-propargyl-1,3,4-thiadiazolin-5-one in 25 ml dry acetone, a catalytic amount of 0.1 g (0.58) was added with induction stirring. mmol) silver nitrate, followed by 1.85 g (8.15 mmol) of N-iodosuccinimide. The mixture was stirred at room temperature for 20 hours. The solid was filtered off by suction filtration using a celite filter. The filtrate was diluted with 200 mL water and extracted twice with 100 mL ethyl acetate. The organic layer was washed with twice 50 ml water, brine and dried over sodium sulfate. The drying agent was filtered off and the filtrate was concentrated. The resulting residue was triturated with hexane and the product was collected by suction filtration to obtain 1.75 g of semi-crystallized compound, m.p. 117-119 ° C. The NMR protein spectrum showed the desired compound.

Example IV Microbiocidal evaluation of compounds.

The following evaluations were carried out on compounds of formula 1 in which X = J.

The value of the minimum inhibitory concentration (MIC) is obtained by conducting a broth test and two-fold dilution as follows: A stock solution or dispersion of the test compound is prepared in a 5: 2: 2 mixture of acetone, methanol and water to obtain a liquid medium typically at a concentration of 1% . This solution is dosed into the medium in such an amount that an initial concentration of 500 ppm, 250 ppm and 125 ppm of compound is obtained in the initial test.

Each vessel in the dilution series, except the first, contains an equal volume of medium without compound. The first vessel contains twice the volume of medium with the initial concentration of test compound. Half of the medium from the first vessel is transferred to the second vessel. After mixing, half the resulting volume is removed from the second vessel and transferred to the third vessel. The whole cycle is repeated until consecutive concentrations of 500, 250, 125.63, 31.16, 8 and 4ppm or 250, 125.63.32, 16.8, 1.0, 0.5, 0.25 and 0.12 (or 100 , 50,25,12,5,6,2, 3,1,1,6 and 0.8) respectively.

Each vessel is then inoculated with a cell suspension of the respective test organism. Bacteria grow in medium, fungi on agar slants, and algae grow in the cooling tower environment at a time and temperature suitable for the species being tested. At the end of the growth period, the medium is centrifuged to disperse the cells. In the case of mushrooms, the spores are collected by pipetting the water diagonally, removing the spores using a sterile loop. The cell / spore suspension is standardized by controlling the incubation time, temperature and solvent volume. The suspension is then used to inoculate vessels containing the compound with the broth medium. The vessels are then incubated at the appropriate temperature. After incubation, the growth / lack of growth is examined. The minimum inhibitory concentration (MIC) is defined as the lowest concentration of compound that causes complete inhibition of the growth of the test organism.

164 853 i3

Organisms tested to demonstrate microbicidal activity include:

Bacteria: Pseudomonas fluorescens (Ps. Fl.), Gram-negative, Pseudomonas aerugenosa (Ps. Ae.), Gram-negative, Escherichia coli (E. c.), Gram-negative, Staphylococcus aureus (S. a.), Gram-positive bacteria. Mushrooms: Aspergillus niger (A. n), Aureobasidium pullulans (A. p).

Algae: Chlorella pyroidenosa (see Table 5).

Table 2 Biocidal assessment

Minimal inhibitory concentration (MIC) test results MIC (ppm)

<td>Compound No.</td><td>Psfl</td><td>Psae</td><td>Ecol</td><td>Saur</td><td>AMG</td><td>APUL</td>

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Example V. In vitro fungicidal properties of compounds on plants.

The following organisms are used in the text: PYU Pythium ultimum (Oomycete); PHY Phytophthora capsici (Oomycete); PIR Piricularia oryzae (Ascomycete); HEL Cochliobolus sativus (Ascomycete); BOC Botrytis cinerea (Ascomycete); FUS Fusarium roseum (Ascomycete); SEP Septoria nodorum (Ascomycete); RHI Rhizoctonia solani (Basidiomycete); XAN Xanthomonas campestris (bacteria).

methods:

1. Maintenance of the culture: Transfer in stages 1 and 2 is carried out under a laminar flow shield. All 8 fungi and bacteria used in the test are transferred and maintained on potato dextrose agar plates weekly (2 plates per organism). Organisms of the following age are used: a / weekly: PYU, PHY, RHI; b / bi-weekly: XAN, PIR, BOC, HEL, FUS, SEP. Pythium ultimum and Phytophthora capsici are transferred to shaken culture on asparagine-sucrose broth (ASB). Rhizoctonia solani, Fusarium roseum and Xanthomonas campestris are kept in yeast-dextrose (YDB) broth on a shaker. Each culture flask is inoculated with 6 pieces of mycelium (except Pythium, which is only inoculated with 3 pieces), taken from PDA plates. All liquid cultures are used after 2 days of growth.

2. Preparation of material for vaccination. Conidia and mycelium from PIR, BOC, HEL and SEP are lightly scraped into YDB so that mainly conidia is used as the grafting material. The conidia suspension is filtered through a double layer of gauze to remove mycelial clumps. One plate produces enough conidia or mycelium to inoculate with 100 ml YDB. The XAN broth culture is poured (1 ml culture / WOml broth) into YDB. PYU, PHY, PHI and FUS cultures are crushed (2-3.5 seconds disrupted in a mixer) and all but Pythium and Phytophthora are filtered through a double layer of sterile gauze to remove large clods of mycelium. 10 ml of culture solutions of R. brine and E. roseum are added to 90 ml of ASB and 10 ml of P. capsici are added to 90 ml of ASB. 2 ml culture solution P. ultimum is added to 98 ml ASB. Be careful not to vaccinate too much (e.g. solutions should be completely clear, however, when exposed to light, a slight turbidity should be visible), because the patterns will not behave properly.

Mixtures of seed material are placed in microtiter plates using a 12-drop pipette. 175 μΐ (single dose) or 100 μΐ (dose-response test) of the vaccine broth are placed in each microtiter well. Inoculated plates are placed in the fridge overnight. Two replicates are performed for each trial.

3. Adding a relationship. This operation is carried out under the hood. 245 μ w of water is first added to the wells of the six microtiter plates. 10 mg of compounds, which is the active substance of the agent, are placed in 1 ml of 1: 1 acetone.methanol, to obtain the liquid agent of the invention, 5 μΐ of the solution is pipetted into the wells of a plate mixture containing sterile water according to a grid. There are 45 compounds per plate and 3 control procedures. Two replicates are performed for each treatment. 25 ΐΐ of the solution is transferred to the inoculated plates using a 96-well replicator. The replicator is sterilized with burning alcohol, rinsed with sterile water and dried with sterile paper between each transfer.

Table 3

In vitro fungicidal tests results

<td rowspan="2">Relationship</td><td rowspan="2">(Ppm) dose</td><td></td><td></td><td></td><td></td><td>% control</td><td></td><td></td><td></td><td></td>

<td>Pyu</td><td>XAN</td><td>PIR</td><td>PHY</td><td>BOC</td><td>HELIUM</td><td>RHI</td><td>PUS</td><td>SBP</td>

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Example VI. Evaluation of the fungicidal action of compounds.

The compounds of the invention were tested for their in vivo fungicidal activity against mildew cucumber (CDM), rice blight (RB), rice rhizoctoniosis (RSB), later tomato rust (TLB), powdery mildew wheat (WPM), and wheat stem rust (WSR ) and wheat leaf rust (WLR) and the results are presented in Table 4. In cereal tests (except for rice used to test rice blight), plants were pruned about 24 hours before using the fungicide compound to obtain a uniform plant height and to facilitate uniform application of the compound and inoculation with the fungus. The compounds were dissolved in a 2: 1: 1 mixture of water and acetone and, to obtain the agent of the invention from a liquid form, sprayed the plants with it, allowed to dry (4 to 6 hours), and then the plants were inoculated with a fungus. Each test used plants that were sprayed with a mixture of water, acetone and methanol and inoculated with a fungus. The rest of the technique for each test is given below and the results are presented as the percentage control of the disease (percentage of plants treated with the agents of the invention showing signs or symptoms of the disease compared to untreated control plants).

Powdery mildew (CDM): Pseudoperonospora cubensis was kept on the leaves of live Merketer cucumber plants at a constant room temperature of 20 ° C to 25 ° C in humid air with moderate light intensity for 7 to 8 days. An aqueous spore suspension was prepared from infected leaves, and the spore concentration was adjusted to about 100,000 per ml of water.

Marketer cucumber seedlings were infected by spraying the underside of the leaves with a DeYilbiss spray until small droplets were observed on the leaves. Infected plants were incubated in the chamber

164 853 mists for 24 hours at a temperature of about 22 ° C and then incubated sequentially for 6 to 7 days at a controlled temperature of 18 ° C to 24 ° C and in the fog. Seven days after infection, the percentage control of the disease was determined.

Rice blight (RB): Nato rice plants were infected with Piricularia oryzae (about 20,000 conidia per ml) by spraying leaves and stems with a spray gun until a uniform layer of contaminating material was observed on the leaves. The infected plants were incubated in a humid environment (24 ° C to 30 ° C) for about 24 hours, then placed in a greenhouse (21 ° C to 24 ° C). Seven to eight days after infection, the percentage control of the disease was determined.

Rhizoctonic rice (RSB): Pellicularia filamentosa (f. Sasiki) was grown on an autoclaved mixture of agitated rice seeds and potato dextrose broth (100 g rice seeds per 30 ml potato dextrose broth) in a 500 ml Erlenmayer flask. After 10 days, the culture was mixed in a mixer to obtain a homogeneous infection. Approximately one teaspoon of infectious material was sprayed onto the soil surface among the Lebonnet rice seedlings in each 7.5 cm pot. The infected plants were incubated for 5 days in a humidity chamber (30 ° C to 32 ° C). Percent control of the disease was determined immediately after removal of the cuttings from the chamber.

Late tomato rust (TLB): Phytophthora infestans were grown on four week old Pixie tomato plants in a controlled atmosphere room (18 ° C to 21 ° C and 100% relative humidity). After storage, the spores were washed off the leaves with water and dispersed with a DeVilbiss sprayer on three week old Pixie tomato plants that were sprayed with previously tested fungicides. The infected plants were placed in a humidity chamber at 21 ° C and constant haze for 24 hours for infection. The plants were then transferred to a room with controlled environment as above and marked after three days of incubation. The disease control level is presented as the percentage control four days after infection and five days after compound spraying.

Wheat mealworm (WPM): Erysiphe graminis (f. Sp. Tritici) was grown on Pennol wheat seedlings in a room controlled from 18 ° C to 25 ° C. Powdery mildew spores were shaken from cultured plants to Pennol wheat seedlings. previously sprayed with a fungicide compound. Infected seedlings were kept in a room with a controlled temperature of 18 ° C to 25 ° C and irrigated the subsoil. Percent control of the disease was assessed 8 to 10 days after infection.

Wheat stem rust (WSR): Puccinia graminis (f. Sp. Tritici Race 15B-2) was grown on Wanzer wheat seedlings for a period of 14 days in a greenhouse. An aqueous suspension of spores from infected plants was obtained and the spore concentration was adjusted to about 200,000 spores per ml of demineralized water. Wanzer wheat plants, which had previously been treated with fungicides, were infected by applying a spore suspension of rust on wheat stalks until they flowed off with a DeVilbiss spray at 5 pounds / in2. After infection, the plants were placed in a humid room at approximately 24 ° C, where they were exposed to the following light conditions: 12 hours of continuous darkness and then a minimum of 3 to 4 hours of light at approximately 500 candelas / stop. The temperature in the chamber did not exceed 30 ° C. At the end of the lighting period, the plants were placed in a greenhouse, where the plants could grow for a period of two weeks, during which the percentage control of the disease was determined.

Wheat leaf rust (WLR): Puccinia recóndita (f. Sp. Tritici Races PKB and PLD) were grown on seven-day-old wheat (Fielder) for 14 days in a greenhouse. The spores were collected from the leaves using a centrifugal vacuum cleaner or by settling on an aluminum foil. The spores were purified by sieving through a 250 micron sieve and stored or used fresh. Sealed bags in an ultra-low temperature freezer were used for storage. When stored, the spores must be subjected to heat shock for 2 minutes at 4 ° C before use. A spore suspension is prepared from dry uredia by adding 20 mg (9.5 min) per ml of Sotrol oil. The suspension is dosed into gelatin capsules (0.7 ml) which are attached to an oil sprayer. One capsule is applied to the surface of a 142 cm2 pot with seven-day Fielder wheat. After waiting for 15 minutes for the oil to evaporate from the leaves of wheat, the plants were placed in a dark fog chamber (temperature 855 i9 round i8-20 ° C and i00% relative humidity) for 24 hours. The plants were then placed in a greenhouse for an incubation period and disease levels recorded after i0 days. Protective and healing tests were carried out the day after and two days in succession before spraying the plants with the test chemicals.

Table 4

The results of the greenhouse test in combating plant diseases

<td rowspan="2">Relationship</td><td rowspan="2">Dose ppm</td><td colspan="6">% eradication</td>

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Table 5

Green algae test results

<td colspan="2">Mio (ppm) Chlorella</td>

Example VII. Herbicidal activity of the agents according to the invention.

The following procedure was used to demonstrate herbicidal activity. Seeds of selected plants, which were identified below, were strained in pots. Spray liquids were prepared by dissolving the active ingredient in a suitable solvent, usually acetone. The means were applied pre-emergence, directly after sowing, spraying them with the surface of the earth in an amount of 4800g / ha of active substance. Then the pots were moistened by pouring water. In the post-emergence test, the test medium was sprayed on plants that had risen and grown for 10 to 21 days. Each series of tested plants was selected for homogeneity, size and development. The plants in the post-emergence test were moisturized only by hydration from below.

Plant growth status was observed approximately 10-21 days after application of the test agent and evaluated on a scale of 0-100, in which 0 means no activity and 100 means complete control.

The following are the species of weeds tested and the symbols used to determine them: BYG - Japanese millet (Echinocloa crus-galli); CKL - common turnip (Xanthium strumarium); FOX - trichinosis (Setaria viridis); JON - Jonson's grass (Sorghum halepense); MG - purple wolf (Ipomoea lacunosa); NUT - cyprus (Cyperus esculentus); PIG - white quinoa (Amaranthus retroflexus); SMT - knotweed (Polygonum lapathifolium); VEL - common rosewood (Abutilon theophrasti); WO - deaf oats (Avena fatua).

Table 6 shows the results of testing the compositions according to the invention for herbicidal activity.

Table 6

Herbicidal activity

<td>Compound No.</td><td>BYG</td><td>CKL</td><td>FOX</td><td>ION</td><td>MG</td><td>NUT</td><td>PGI</td><td>SMIT</td><td>VEL</td><td>VO</td>

-X

Ν-Ν

PATTERN 1

Ν-Ν

A-4'o> = O

PATTERN 2

N- N ~

A— ^ 5 = 0 and

R

MODEL 3

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NN A - <. 'S9 = O

Ξ -X

Walkthrough level 4 = -H

NN

A— (') = Y

MODEL 5

ABOUT

R1SFROM

CN

MODEL 6

MODEL 7

- N ^-

N ^ = O and

H

MODEL 8

N- NH A — i>from)=\

MODEL 9

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Priority claims
Document	Office	Kind	Date
37037389	United States of America	A	1989-06-22
89370373	–	–	–
US19890370373	–	–	–

Members30

Family members, oldest first
Document	Office	Kind
HU903955D0	Hungary	D0	1990-11-28
CA2019162A1	Canada	A1	1990-12-22
IE902253L	Ireland	L	1990-12-22
EP0404498A2	European Patent Office (EPO)	A2	1990-12-27
AU5764590A	Australia	A	1991-01-03
IE902253A1	Ireland	A1	1991-01-16
KR910000676A	Republic of Korea	A	1991-01-30
ZA904776B	South Africa	B	1991-03-27
JPH0374373A	Japan	A	1991-03-28
IL94800D0	Israel	D0	1991-04-15
HUT55008A	Hungary	A	1991-04-29
EP0404498A3	European Patent Office (EPO)	A3	1991-07-24
BR9002959A	Brazil	A	1991-08-20
DD295365A5	German Democratic Republic (until 1990)	A5	1991-10-31
US5064845A	United States of America	A	1991-11-12
PL285732A1	Poland	A1	1992-06-15
AU636358B2	Australia	B2	1993-04-29
NZ234130A	New Zealand	A	1993-12-23
US5292762A	United States of America	A	1994-03-08
EP0404498B1	European Patent Office (EPO)	B1	1994-10-19
PL164853B1This record	Poland	B1	1994-10-31
DK0404498T3	Denmark	T3	1994-11-14
AT113041T	Austria	T	1994-11-15
DE69013408D1	Germany	D1	1994-11-24
ES2063273T3	Spain	T3	1995-01-01
US5391561A	United States of America	A	1995-02-21
DE69013408T2	Germany	T2	1995-03-30
MY106408A	Malaysia	A	1995-05-30
IE65031B1	Ireland	B1	1995-10-04
IL94800A	Israel	A	1996-05-14

Composition containing novel propargillic exhibiting microbiocidal and herbicidal effect

Abstract

Term

-X

PATTERN 1

PATTERN 2

R

MODEL 3

NN

MODEL 5

ABOUT

CN

MODEL 6

MODEL 7

H

MODEL 8

MODEL 9

Priority claims3

Members30

Numbers

Titles

Classification