AP220A - Novel fungicidal imidazole complexes. - Google Patents
Novel fungicidal imidazole complexes. Download PDFInfo
- Publication number
- AP220A AP220A APAP/P/1991/000263A AP9100263A AP220A AP 220 A AP220 A AP 220A AP 9100263 A AP9100263 A AP 9100263A AP 220 A AP220 A AP 220A
- Authority
- AP
- ARIPO
- Prior art keywords
- prochloraz
- complex
- accordance
- metal complex
- plant
- Prior art date
Links
- 230000000855 fungicidal effect Effects 0.000 title claims description 15
- 150000002460 imidazoles Chemical class 0.000 title 1
- 239000005820 Prochloraz Substances 0.000 claims description 50
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 40
- 241000196324 Embryophyta Species 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 201000010099 disease Diseases 0.000 claims description 14
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 241000233866 Fungi Species 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000004563 wettable powder Substances 0.000 claims description 10
- 241000221785 Erysiphales Species 0.000 claims description 9
- 150000004696 coordination complex Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 241001284615 Frangula californica Species 0.000 claims description 6
- 235000004433 Simmondsia californica Nutrition 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 description 24
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 238000009472 formulation Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical class [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 8
- 239000011592 zinc chloride Chemical class 0.000 description 8
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical class [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- 235000007319 Avena orientalis Nutrition 0.000 description 3
- 244000075850 Avena orientalis Species 0.000 description 3
- 240000008067 Cucumis sativus Species 0.000 description 3
- 240000005979 Hordeum vulgare Species 0.000 description 3
- 235000007340 Hordeum vulgare Nutrition 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000004464 cereal grain Substances 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 235000009849 Cucumis sativus Nutrition 0.000 description 2
- 239000005789 Folpet Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 150000004700 cobalt complex Chemical class 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- HKIOYBQGHSTUDB-UHFFFAOYSA-N folpet Chemical compound C1=CC=C2C(=O)N(SC(Cl)(Cl)Cl)C(=O)C2=C1 HKIOYBQGHSTUDB-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004487 negative regulation of sporulation resulting in formation of a cellular spore Effects 0.000 description 2
- 231100000208 phytotoxic Toxicity 0.000 description 2
- 230000000885 phytotoxic effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 235000000832 Ayote Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000004244 Cucurbita moschata Species 0.000 description 1
- 235000009854 Cucurbita moschata Nutrition 0.000 description 1
- 235000009804 Cucurbita pepo subsp pepo Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- 241000579741 Sphaerotheca <fungi> Species 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 244000037666 field crops Species 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 235000015136 pumpkin Nutrition 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000028070 sporulation Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011135 tin Chemical group 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention concerns improved crystalline
Description
BACKGROUND OF THE INVENTION
The present invention concerns an improved metal complexes of the fungicide l-(N-propyl-N-2-(2,4,6-trichlorophenoxy)-ethyl-carbamoyl]-imidazole, known by the common name prochloraz, its improved formulations and their use in combating fungi, especially powdery mildew (Sphaerotheca fuliginia) and coffee berry disease ( Colletotrickum cof feanum).
Prochloraz is a protectant and eradicant fungicide, effective against a wide range of diseases affecting field crops, fruit, turf and vegetables. Its use was first reported in United Kingdom patent numbers 1,469,772 and 1,576,277, whose contents are incorporated by their mention. Prochloraz is sold under two different types of formulation. One form is an emulsifiable concentrate, which contains the free compound as active ingredient.
The second formulation is a wettable powder where the active ingredient is in the form of a metal complex. The metal complexes of prochloraz were first reported in
United Kingdom patent number 1,567,521 (Israel patent no.
54,304), whose contents are incorporated by its reference.
The metal complexes of prochloraz were intended to solve two problems found in using the free, non-complexed pro25 chloraz. The first was, that non-complexed prochloraz was found difficult to handle and formulate on a solid powder carrier. It was found necessary to first absorb it on a cuiiici prior to preparing a powder, causing loss of material, lowering the fungicidal activity and preventing the preparation in a highly concentrated form. The second problem was that tree, non-complexed prochloraz was found to be phytotoxic to some crops. However, the metal complexes of prochloraz were found to avoid these problems. Thus the metal complexes of prochloraz, generally were found to be solid, distinctly melting compounds, readily formulated with a solid carrier or concentrate, without the phytotoxic problems found on susceptible crops.
Patent coverage on the metal complexes of prochloraz was obtained in many countries (i.e. GB 1,567,521 and US
4,250,179). The metals exemplified or disclosed were divalent metals such as copper, manganese, iron, nickel and cobalt. Nowhere were metal salts of SnCl2 or ZnCl2 with prochloraz disclosed or claimed. Indeed, there are indications from the prior art that these specific salts cannot be prepared. With regard to the cobalt complex, while it was disclosed, it was not claimed, nor was this complex exemplified. Thus, the present invention is a selection patent of those patents covering metal complexes of prochloraz.
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OBJECTIVES OF THE INVENTION
It is. the objective of the present Invention to provide crysta-lLine metal complexes of prochloraz with SnCl2,
ZnCl2l or CoCl2. It is an objective of the present invention to also provide a formulation of these complexes, which can be readily formulated as a wettable powder. A. fur ther objective is the provision of formulations of the complexes having unusual and unexpected fungicidal activity, especially against powdery mildew and coffee berry disease. These and other objectives of the invention will become apparent to those skilled in the art from the following description.
SUMMARY,OF THE INVENTION
In accordance with the present invention, there is provided crystalline metal complexes of prochloraz having the formula :
- C - N -(CH2)2- 0 <!:h i2ch2ch3
2C1 wherein M is zinc, tin or cobalt this invention are definite melting points enables them to be easily
The metal complexes produced by crystalline solids having sharp compositions. This formulated as wettable powders.
and defined handled and invention also provides an improved method of fungi, especially powdery mildew, applying to material or plant a composition containing amount of tfne of these metal complexes.
The present controlling the infested an effective
DETAILED DESCRIPTION OF THE INVENTION
The complex containing zinc is a white crystalline solid having a melting point of 100°C-102°C. Analysis of its compared to a value of zinc content showed 7.29% zinc 7.35%, which correlates with a molecule of ZnCl2 per molecule complex containing one of prochloraz. The complex containing tin is a white crystalline solid Jiaving a, bad original
AP ο Ο Ο 2 2 Ο melting point of 95°C. Analysis of its tin content showed /9.9% tin , which correlates with a complex of one molecule of SnCl2 per two molecules of prochloraz. The complex containing cobalt is a white crystalline solid having a melting point of 136°C_ 138°C. Analysis of its cobalt content showed 6.68% cobalt, which correlates with a complex of one molecule of CoCl2 per two molecules of prochloraz.
The nuclear magnetic resonance spectrum of these complexes in solution showed a definite shift in the singlet hydrogens belonging to the imidazole group. This shows complexation, and that the complexation takes place on the imidazole group. Details of the spectrum are shown in Table 1 .
These complexes are prepared by adding a water solution of SnCl2, ZnCl2 or CoCl2 to a clear alcoholic solution of prochloraz in a molar ratio of 1:2 metal salt to prochloraz. While most common alcohols give good results, alcohols such as ethanol or isopropanol were found to be preferred.
The reaction temperature is conveniently chosen within the range of from 10°C to 60°C, preferably room temperature ,
According to a further feature of the invention, there Is provided a fungicidal composition which comprises a compound of the invention together with a carrier. The active compound can be employed as a wide variety of formulations, for example as an aqueous dispersion, a dispersible powder, a seed dressing, granules or dust.
As a dispersion the composition comprises an active compound together with a dispersing agent dispersed in a liquid medium, preferably water. It can be in the form of a concentrated primary composition which requires dilution with a suitable quantity diluent before application. Such are a convenient way of supplying preferred example is a dispersible powder comprises an active compound, and a solid carrier. The latter can kaolin, talc, or diatomaceous earth and, dispersible powder can contain a wetting of water or other primary compositions the consumer and a powder. A dispersible a dispersing agent be, for example, in addition, the agent.
Other formulations include seed dressings, granules or dusts, in all of which the active compound is associated with a solid carrier and which are intended for direct application. They can be made by methods well known in the art. Preferably all compositions comprising a solid
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TABLE 1
PROTON MAGNETIC SPECTRA OF PROCHLORAZ AND ITS METAL COMPLEXES
| Prochloraz· | Zn Complex of | Prochloraz | ||
| Triplet | 0.93 | (3H) | 0.95 | (3H) |
| Quartet | 1.75 | ( 2H) | 1.76 | (2H) |
| Triplet | 3.55 | (2H) | 3 . 54 | (2H) |
| Triplet | 3.87 | (2H) | 3.85 | (2H) |
| Triplet | 4.22 | (2H) | 4.20 | (1H) |
| Singlet | 7.11 | (1H) | 7.29 | <1H) |
| Singlet | 7.31 | (1H) | 7 . 32 | (2H) |
| Singlet | 7.32 | (2H) | 7.47 | (1H) |
| Singlet | 7.96 | ( 1H ) | 8.41 | (1H) |
| a = In ppm. |
BAD ORIGINAL $ . AP ο 0 0 2 2 0 carrier are made by mixing the active compound in particulate form with a particulate carrier.
The concentration of the active compound in the composition of the invention can vary widely. In the case of a primary composition it is preferably from 151 to 951 by weight, more especially from 501 to 801 by weight. A composition intended for direct application to a crop preferably comprises from 0.0011 10 101, more especially from 0.0051 to 51 by weight of the active compound, although the aerial spraying of a crop is contemplated compositions having a higher concentration, for example up to 301 by weight may be chosen in preference.
Also included in the invention is a method for controlling a phytopathogemc fungus which comprises applying to seeds, plants or their habitat a compound of the invention. For convenience and effectiveness it is preferred to apply the active compound in the form of a composition as described above.
In the method of the invention the compound is applied to seeds, plants or their habitat. Thus the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of the fungus as a protective measure. In both such cases the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged. For cereal crops such as wheat, barley and oats, it is often desirable to spray the plant at or before growth stage 5 (Feeke’s Scale) although additional treatments by spraying when the plant is more mature can augment resistance to the growth or spread of fungi.
Sometimes it is practicable to treat the roots of a plant before or during planting, for example by dipping the roots in a suitable liguid or solid composition. When the active compound is applied directly to the plant, a suitable rate of application is from 0.01 to 10 kilograms per hectare.
Alternatively, the compound can be applied directly to the soil at the same time as drilling, so that the presence of active compound in the soil controls the growth of fungi which attack the seed. When the soil is treated directly, the active compound can be applied in any manner which allows it to be intimately mixed with the soil by applying the active ingredient ac the same time as drilling, inserting it in the same drill as the seed.
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A suitable application rate is within the range of from 0.1 to 10 kilograms per hectare.
In a further method of the invention, the active compound an be applied to the seed as a dressing in order to combat seed-borne diseases. This method is of particular use in the treatment of cereal grain against attack by, for example, leaf spot of oats and leaf stripe of barley.
When the cereal grain is stored in a store-room or container, the store-room or container can be treated with the active compound instead of or in addition to the treatment of the cereal grain itself. A suitable rate of application for a seed dressing is from 0.05 to 5 grams per kilogram, such as for example from 0.1 to 1 grams per kilogram.
A more particular method of the invention is one for controlling fungal diseases on a cereal crop, such as for example wheat, barley, oats, or rye, which comprises applying to the crop a compound of the invention. For any particular compound it is necessary to choose the most effective method from amongst those described above at a suitable rate of application ensuring fungus control.
The crystalline metal complexes of prochloraz of the present invention showed particularly good results against powdery mildew and coffee berry disease, especially when compared to the results of known commercial metal complexes of prochloraz.
While the invention will now be described in connection with certain preferred embodiments in the following examples it will be understood that it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention as defined by the appended claims. Thus, the following examples which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purposes of illustrative discussion of preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of procedures as well as of the principles and conceptual aspects of the invention.
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AP Ο Ο Ο 2 2 Ο
EXAMPLE 1: PREPARATION OF THE TIN COMPLEX OF PROCHLORAZ prochloraz in temperature of thirty minutes a water. The resulting two hours and the water and solvent originwhite crystalline powder having a
To a stirred, homogeneous solution of 80 g 500 ml ethanol or isopropanol kept at room a period in 100 ml a further was added dropwise over solution of 225 g SnCl2 mixture was stirred for resulting crystals filtered, rinsed with ethanol or isopropanol (depending on the ally used) to afford a melting point of 95°C.
EXAMPLE 2: PREPARATION OF THE ZINC COMPLEX OF PROCHLORAZ
To a stirred homogeneous solution of 80 g prochloraz in 500 ml ethanol or isopropanol kept at room temperature, period of thirty minutes a in 20 ml water. The resulting further 2.5 hours and the resulting crystals filtered, washed with water and alcohol to afford a white crystalline powder having a melting point of 100°C-102°C. Elemental analysis:
Zinc: 7.351 calculated, 7.291 found;
Chloride: 7.97% calculated, 8.02% found.
was added dropwise over a solution of 13.6 g ZnCl2 mixture was stirred for a
EXAMPLE 3: PREPARATION OF THE COBALT COMPLEX OF PROCHLORAZ
Following the method of Example white crystalline CoCl2 complex prepared. Its melting point was but using CoCl2, of prochloraz was 136°C-138°C.
the
EXAMPLE 4: PREPARATION OF A WETTABLE POWDER FORMULATION OF THE ZINC CHLORIDE COMPLEX.
A wettable powder formulation was prepared by mixing together the following ingredients: Bis-(l-{N-propyl-N-2-(2,4,6-tr ichlorophenoxy)-ethylcarbamoyl}-imidazole )-zinc chloride complex 54% Sodium 1ignosulfonate (as dispersant) 3% Wettol NT-1 (wetting agent) 2% Wessalon (precipitated silica carrier) 5%
Kaolin to complete to 100% by weight
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EXAMPLE 5: PREPARATION OF A WETTABLE POWDER
FORMULATION OF THE TIN (II) CHLORIDE COMPLEX
A wettable powder formulation was prepared by mixing together the following ingredients: Bls-[l-(N-propyl-N-2-(2,4,6-trichlorophenoxy) - ethy110 carbamoylJ-imidazole]-tin(II) chloride complex 54% Sodium 1ignosulfonate (as dispersant) 3% Wettol NT-1 (wetting agent) 2% Vessalon (precipitated silica carrier) 5%
Kaolin to complete to 100% by weight
EXAMPLE 6: PREPARATION OF A WETTABLE POWDER
FORMULATION OF COBALT(II) CHLORIDE COMPLEX
A wettable powder formulation was prepared by mixing together the following ingredients·. Bis-[l-(N-propyl-N-2-(2,4,6-tr ichlorophenoxy)-ethylcarbamoyl) - imidazole ]-cobal t (II) chloride complex 51%
Sodium 1ignosulfonate (as dispersant) 3%
Wettol NT-1 (wetting agent) 2%
Wessalon (precipitated silica carrier) 5%
Kaolin to complete to 100% by weight
EXAMPLE 7: FUNGICIDAL ACTIVITY OF THE COMPLEXES AGAINST POWDERY MILDEW,
Cucumbers sensitive to powdery mildew were sprouted in trays and then transferred to pots of 16 cm diameter, two plants per pot. They were Kept in a hot-house at 18°C25°C at a relative humidity of 60%-70%. The cucumber plants were contaminated with powdery mildew collected from pumpkin leaves by passing the contaminated leaf over the leaves of the plants to be tested and the plants then sprayed with water. First treatment was with the first appearance of the disease, by spraying until dripping.
All treatments were at a concentration of 0.03%, except for the commercial Myclobutanal (a systemic fungicide of Rohm and Haas Co.), where a concentration of 0.006% was used. The status of the disease was determined by three different people. The experiment was conducted in blocks, at random, with repetitions. Four blocks of four repetitions of ten treatments (total 160 pots) at three evaluation periods. The results appear in Table 2.
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AP000220
TABLE 2
DISEASE INDEX· OF CUCUMBERS INOCULATED WITH POWDERY MILDEW AND TREATED WITH FORMULATIONS OF VARIOUS METAL COMPLEXES OF PROCHLORA2 .
| 5 | Active Compound | Disease Index Days After Treatment | |||||
| 7 | Ad AB | 14 | B B | ||||
| Myclobutanol SnCl2 complex | of | Prochloraz | 1.34 1.97 | 0.81 0.78 | |||
| 10 | ZnCl2 complex | of | Proch1oraz | 1.63 | AB | 0.94 | BC |
| CoCl2 complex | of | Prochloraz | 2.06 | B | 1 . 38 | D | |
| Octave0 | 2.69 | CD | 1.50 | D | |||
| Control® | 4.44 | E | 4.66 | F |
a - Key: Q-clean; 1-101-201 sick; 2-201-301 sick;
3-301-401 sick; 4-401-50% sick; 5-over 501 sick.
b = Trademark for Boots’ Mn(II)Cl2 complex of prochloraz.
c = All ingredients of formulations except the active one .
d - Numbers followed by dissimilar letters within columns, are significantly different (P - 0.05).
BAD ORIGINAL
EXAMPLE 8: FUNGICIDAL ACTIVITY OF THE
ZINC COMPLEX AGAINST COFFEE BERRY DISEASE
The zinc complex of prochloraz was tested for its activity against coffee berry disease as follows: Approximately 3.5 mm sections of colonized branches are washed in a solution of Teepol or similar wetting agent to remove any initial spore load. Sections are laid on moistened cellosine wadding in plastic boxes, 12 sections per box. Three boxes are sprayed with each concentration of the candidate material, closed and incubated for three days. After incubation the spores are removed by vigorous shaking of each of the 12 twigs in 10 ml water and are counted, using a haemocytometer slide. the sections of the branch are measured and their volume taken by displacement. The parameters measured were concentration of the formulation and expressed as per cent active ingredient (A.I.) and percent Inhibition of sporulation. The inhibition of sporulation was expressed in relation to the sporulation of unsprayed control and folpet as the standard fungicide. Each determination was done in triplicate and repeated at least three times.
The dose response curves were analyzed by linear regression and the different formulations were compared at the 80% inhibition point. The results as they appear in Table 3 show the very good activity of the zinc complex of prochloraz, especially as compared to the results of known commercial metal complexes. Thus, the zinc complex shows activity against coffee berry disease more than two times greater than that shown for the commercial Octave.
bad original $
TABLE 3
AP Ο Ο 02 2 Ο
7, J'
Κ >·,
INHIBITION OF COFFEE BERRY DISEASE BY THE ZINC COMPLEX OF PROCHLORAZ AND COMPARISON WITH THE ACTIVITY OF KNOWN METAL COMPLEXES OF PROCHLORAZ
Active Compound Per Cent Active Ingredient for 80% Inhibition
| ZnCl2 complex | of | prochloraz | 0.09 |
| NiC12 complex | of | prochloraz | 0.12 |
| Octave® | 0.20 | ||
| Folpet | 0.62 |
a = Trademark of Boots Mn(II)Cl2 complex of prochloraz.
Claims (10)
1. A crystalline metal complex of prochloraz having the formula: 0 C1
Znl
7-J
N - C - N - (CH2)2-07 O/Cl ch,ch2ch3
’.Cl having a melting point of 100°C-i02°C containing approximately 7.35% zinc .
A crystalline metal complex of prochloraz having the formula :
Cl
Sn
N
- C - N- (CH,) 2-θ/θ/ C1) Ch2CH2CH3 CI>2C1 having a melting point of 95°C, containing approximately 7.99* t
Fungicidal compositions containing a solid or liquid diluent or carrier and a fungicidally effective amount of a crystalline metal complex of prochloraz having the formula
Cl
Zn
N - C - N - (CH^^o/Q >C1 CH2 ffl2CH3
2C1
4 . Fungicidal compositions containing a solid or liquid diluent or carrier and a fungicidally effective amount of a crystalline metal complex of prochloraz having the formula: Cl
Sn
CH2ai,CH3 C1
- C - N - (CH7)7- 0
2C1
BAD ORIGINAL $
AP 0 0 0 2 2 0
5. Fungicidal compositions diluent or carrier and a amount of a crystalline having the formula: -
2C1 containing a solid or liquid fungicidally effective metal complex of prochloraz
N CHOCH
6. Fungicidal compositions in accordance with any of Claims 3 to 5 in the form of a wettable powder.
A method of applying to compos i t ion crys ta11ine Claim controlling fungi which the infected material or containing an effective complex of prochloraz in 1 or 2.
comprises plant a amount of a accordance with
8. A method of controlling powdery mildew which comprises applying to the infected material or plant a composition containing an effective amount of a crystalline metal complex of prochloraz in accordance with Claim i or 2.
9. A method of controlling coffee berry disease, which comprises applying to the infected material; or plant a composition containing an effective amount of a crystalline zinc complex of prochloraz in accordance with Claim 1.
10. A fungicidal composition in accordance with Claim 4 in the form of a wettable powder.
11. A method of controlling fungi which comprises applying to the infected material or plant a composition containing an effective amount of a crystalline complex of prochloraz in accordance with Claim 2.
12. A method of controlling powder mildew which comprises applying to the infected material or plant a composition containing an effective amount of a crystalline metal complex of prochloraz in accordance with Claim 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IL9363690A IL93636A (en) | 1990-03-05 | 1990-03-05 | Crystalline zinc or tin complexes of prochloraz and compositions containing them |
| IL97181A IL97181A0 (en) | 1991-02-07 | 1991-02-07 | Novel fungicidal imidazole complexes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AP9100263A0 AP9100263A0 (en) | 1991-07-31 |
| AP220A true AP220A (en) | 1992-10-21 |
Family
ID=26322061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| APAP/P/1991/000263A AP220A (en) | 1990-03-05 | 1991-02-25 | Novel fungicidal imidazole complexes. |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5206232A (en) |
| EP (1) | EP0445656B1 (en) |
| AP (1) | AP220A (en) |
| AR (1) | AR246737A1 (en) |
| AT (1) | ATE115950T1 (en) |
| BR (1) | BR9100916A (en) |
| DE (1) | DE69106015T2 (en) |
| DK (1) | DK0445656T3 (en) |
| ES (1) | ES2066245T3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022053116A1 (en) * | 2020-09-11 | 2022-03-17 | Alfa Smart Agro | Metal prochloraz complexes and the production of them in water based suspension concentrates |
| CN115684321A (en) * | 2022-10-13 | 2023-02-03 | 桂林理工大学 | A molecularly imprinted sensor based on phenylalanine-prochloraz and its preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2604847A1 (en) * | 1975-02-21 | 1976-09-02 | Polva Nederland Bv | METHOD AND DEVICE FOR MANUFACTURING A PLASTIC PART WITH A RESISTOR ELEMENT |
| GB1567521A (en) * | 1977-03-26 | 1980-05-14 | Boots Co Ltd | Funigicidal complexes of metal salts with imidazoles |
| DE3210009A1 (en) * | 1981-03-20 | 1982-10-14 | Hokko Chemical Industry Co. Ltd., Tokyo | IMIDAZOLE DERIVATIVES AND THIS FUNGICIDAL COMPOSITION |
| EP0290204A1 (en) * | 1987-05-08 | 1988-11-09 | Schering Agrochemicals Limited | Fungicidal mixtures with prochloraz |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3789122A (en) * | 1969-03-05 | 1974-01-29 | Du Pont | Fungicidal compositions of transition metal complexes of substituted 2-benzimidazolecarbamic acid, alkyl esters |
| HU171736B (en) * | 1974-12-11 | 1978-03-28 | Eszakmagyar Vegyimuevek | FUNGICID SODERZHAHHIJ 8-OXYCHINOLIN V KACHESTVE ACTIVITY ACTIVITY I SPOSOB POLUCHENIA |
-
1991
- 1991-02-25 AP APAP/P/1991/000263A patent/AP220A/en active
- 1991-02-28 EP EP91103024A patent/EP0445656B1/en not_active Expired - Lifetime
- 1991-02-28 ES ES91103024T patent/ES2066245T3/en not_active Expired - Lifetime
- 1991-02-28 DK DK91103024.5T patent/DK0445656T3/en active
- 1991-02-28 AT AT91103024T patent/ATE115950T1/en not_active IP Right Cessation
- 1991-02-28 DE DE69106015T patent/DE69106015T2/en not_active Expired - Fee Related
- 1991-03-01 US US07/662,650 patent/US5206232A/en not_active Expired - Lifetime
- 1991-03-01 AR AR91319143A patent/AR246737A1/en active
- 1991-03-04 BR BR919100916A patent/BR9100916A/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2604847A1 (en) * | 1975-02-21 | 1976-09-02 | Polva Nederland Bv | METHOD AND DEVICE FOR MANUFACTURING A PLASTIC PART WITH A RESISTOR ELEMENT |
| GB1567521A (en) * | 1977-03-26 | 1980-05-14 | Boots Co Ltd | Funigicidal complexes of metal salts with imidazoles |
| DE3210009A1 (en) * | 1981-03-20 | 1982-10-14 | Hokko Chemical Industry Co. Ltd., Tokyo | IMIDAZOLE DERIVATIVES AND THIS FUNGICIDAL COMPOSITION |
| EP0290204A1 (en) * | 1987-05-08 | 1988-11-09 | Schering Agrochemicals Limited | Fungicidal mixtures with prochloraz |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2066245T3 (en) | 1995-03-01 |
| DE69106015T2 (en) | 1995-08-10 |
| AR246737A1 (en) | 1994-09-30 |
| DK0445656T3 (en) | 1995-02-20 |
| EP0445656A1 (en) | 1991-09-11 |
| BR9100916A (en) | 1991-11-05 |
| EP0445656B1 (en) | 1994-12-21 |
| US5206232A (en) | 1993-04-27 |
| DE69106015D1 (en) | 1995-02-02 |
| ATE115950T1 (en) | 1995-01-15 |
| AP9100263A0 (en) | 1991-07-31 |
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