MD1636Z - Use of (Z)-4,4-dimethyl-1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-one as a fungicidal agent against Alternaria alternata and Fusarium aquaeductuum - Google Patents
Use of (Z)-4,4-dimethyl-1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-one as a fungicidal agent against Alternaria alternata and Fusarium aquaeductuum Download PDFInfo
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- MD1636Z MD1636Z MDS20220025A MDS20220025A MD1636Z MD 1636 Z MD1636 Z MD 1636Z MD S20220025 A MDS20220025 A MD S20220025A MD S20220025 A MDS20220025 A MD S20220025A MD 1636 Z MD1636 Z MD 1636Z
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- triazol
- dimethyl
- pent
- dichlorophenyl
- fusarium
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- 241000223602 Alternaria alternata Species 0.000 title claims abstract description 15
- 241000001619 Fusicolla aquaeductuum Species 0.000 title claims abstract description 13
- LFLAXRVXFCJYOI-MLPAPPSSSA-N (z)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-one Chemical compound C1=NC=NN1/C(C(=O)C(C)(C)C)=C\C1=CC=C(Cl)C=C1Cl LFLAXRVXFCJYOI-MLPAPPSSSA-N 0.000 title claims abstract description 8
- 239000000417 fungicide Substances 0.000 title description 3
- 230000000855 fungicidal effect Effects 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 18
- 230000002464 fungitoxic effect Effects 0.000 abstract description 6
- 230000003032 phytopathogenic effect Effects 0.000 abstract description 6
- FBOUIAKEJMZPQG-BLXFFLACSA-N diniconazole-M Chemical compound C1=NC=NN1/C([C@H](O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-BLXFFLACSA-N 0.000 abstract description 5
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 abstract description 4
- 241000223218 Fusarium Species 0.000 abstract description 4
- 231100000676 disease causative agent Toxicity 0.000 abstract description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 241000233866 Fungi Species 0.000 description 9
- 241000209140 Triticum Species 0.000 description 7
- 235000021307 Triticum Nutrition 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 201000010099 disease Diseases 0.000 description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 4
- 230000002538 fungal effect Effects 0.000 description 4
- 239000001965 potato dextrose agar Substances 0.000 description 4
- FBOUIAKEJMZPQG-AWNIVKPZSA-N (1E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-AWNIVKPZSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 244000052769 pathogen Species 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YSFBEAASFUWWHU-UHFFFAOYSA-N 2,4-dichlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C(Cl)=C1 YSFBEAASFUWWHU-UHFFFAOYSA-N 0.000 description 2
- 241000371644 Curvularia ravenelii Species 0.000 description 2
- 241000221785 Erysiphales Species 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- 241000223600 Alternaria Species 0.000 description 1
- 241000352690 Alternaria kikuchiana Species 0.000 description 1
- 241001465178 Bipolaris Species 0.000 description 1
- 241000530549 Cercospora beticola Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241001645342 Diaporthe citri Species 0.000 description 1
- 241000611205 Fusarium oxysporum f. sp. lycopersici Species 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 241000122123 Penicillium italicum Species 0.000 description 1
- 241000233679 Peronosporaceae Species 0.000 description 1
- 241001270527 Phyllosticta citrullina Species 0.000 description 1
- 241000228453 Pyrenophora Species 0.000 description 1
- 241000228454 Pyrenophora graminea Species 0.000 description 1
- 241000233639 Pythium Species 0.000 description 1
- 241001361634 Rhizoctonia Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 241001512566 Valsa mali Species 0.000 description 1
- 241000228452 Venturia inaequalis Species 0.000 description 1
- 241001123669 Verticillium albo-atrum Species 0.000 description 1
- 241001360088 Zymoseptoria tritici Species 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012677 causal agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000035614 depigmentation Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000007918 pathogenicity Effects 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 230000008659 phytopathology Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 triazolyl ketone Chemical class 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Invenţia se referă la chimie şi agricultură, în special la aplicarea unui compus heterociclic, derivat al 1,2,4-triazolului, în calitate de remediu fungicid contra Alternaria alternata şi Fusarium aquaeductuum.Esenţa invenţiei constă în aceea că în calitate de remediu fungicid contra ciupercilor fitopatogene Alternaria alternata şi Fusarium aquaeductuum, care sunt agenţi cauzali ai putregaiului de radacină, se propune (Z)-4,4-dimetil-1-(2,4-diclorfenil)-2-(1H-1,2,4-triazol-1-il)pent-1-en-3-onacu formula:.Rezultatul tehnic constă în sporirea activităţii fungitoxice a compusului sus-menţionat în raport cu diniconazolul cu 10…25% pentru fungul Alternaria alternata şi 18…33% pentru Fusarium aquaeductuum.The invention relates to chemistry and agriculture, in particular to the application of a heterocyclic compound, derivative of 1,2,4-triazole, as a fungicidal remedy against Alternaria alternata and Fusarium aquaeductuum. The essence of the invention is that as a fungicidal remedy against phytopathogenic fungi Alternaria alternata and Fusarium aquaeductuum, which are causative agents of root rot, (Z)-4,4-dimethyl-1-(2,4-dichlorophenyl)-2-(1H-1,2,4- triazol-1-yl)pent-1-en-3-one with the formula: The technical result consists in increasing the fungitoxic activity of the above-mentioned compound in relation to diniconazole by 10...25% for the Alternaria alternata fungus and 18...33% for Fusarium aquaeductum.
Description
Invenţia se referă la chimie şi agricultură, şi în special la aplicarea unui compus heterociclic, derivat al 1,2,4-triazolului, în calitate de remediu fungicid contra Alternaria alternata şi Fusarium aquaeductuum. The invention relates to chemistry and agriculture, and in particular to the application of a heterocyclic compound, a derivative of 1,2,4-triazole, as a fungicidal remedy against Alternaria alternata and Fusarium aquaeductuum.
Putregaiul de rădăcină (picioruşul negru) la culturile agricole este una din cele mai răspândite şi severe maladii, şi are manifestări specifice fazelor ontogenetice ale plantei. De exemplu la grâu, putregaiul de rădăcină se exteriorizează prin putrezirea seminţei şi gemulei, rădăciniţelor primare şi secundare, coleoptilului, nodului de înfrăţire, bazei tulpinii, ofilirea în faza de plantulă, obturarea vaselor conducătoare cu miceliu şi pătulirea grânelor, depigmentarea tulpinii şi spicului, spice goale cu palete aspre, seminţe şiştăvite sau cu embrion negru la plantele mature (Tunali B. et al. Root and crown rot fungi associated with spring, facultative, and winter wheat in Turkey. Plant Disease, 2008, vol. 92 (9), p. 1299-1306; Xu X. et al. Relationship between the fungal complex causing Fusarium head blight of wheat and environmental conditions. Phytopathology, 2008, vol. 98, p. 69-78). Root rot (black leg) in agricultural crops is one of the most widespread and severe diseases, and has manifestations specific to the ontogenetic phases of the plant. For example, in wheat, root rot is manifested by rotting of the seed and bud, primary and secondary roots, coleoptile, twinning node, stem base, wilting in the seedling phase, clogging of the conducting vessels with mycelium and coating of the grains, depigmentation of the stem and spike, empty spikelets with rough blades, shrunken seeds or with black embryo in mature plants (Tunali B. et al. Root and crown rot fungi associated with spring, facultative, and winter wheat in Turkey. Plant Disease, 2008, vol. 92 (9), p. 1299-1306; Xu X. et al. Relationship between the fungal complex causing Fusarium head blight of wheat and environmental conditions. Phytopathology, 2008, vol. 98, p. 69-78).
La culturile cerealiere, putregaiul de rădăcină este produs de un ansamblu vast de ciuperci ubicuitar răspândite în sol, cu patogenitate facultativă sau obligatorie, care fac parte din mai multe genuri: Fusarium, Helminthosporium (Bipolaris/Drechslera), Pythium, Rhizoctonia, Alternaria, dintre care specia A. alternata face parte dintre patogenii cu frecvenţă înaltă, atingând în anii favorabili creşterii şi dezvoltării frecvenţa de 35,9% din complexul fungic implicat în dezvoltarea maladiei la grâul comun de toamnă (Controlul genetic al caracterelor de rezistenţă şi productivitate la grâul comun. Coord. Lupaşcu G. Chişinău: Tipografia AŞM, 2015, 176 p.). In cereal crops, root rot is produced by a vast ensemble of fungi ubiquitously distributed in the soil, with facultative or obligate pathogenicity, which are part of several genera: Fusarium, Helminthosporium (Bipolaris/Drechslera), Pythium, Rhizoctonia, Alternaria, of which the species A. alternata is one of the pathogens with high frequency, reaching in years favorable for growth and development the frequency of 35.9% of the fungal complex involved in the development of the disease in common winter wheat (Genetic control of resistance and productivity traits in common wheat. Coord. Lupaşcu G. Chişinău: Tipografia AŞM, 2015, 176 p.).
Unul din impedimentele de bază pentru combaterea maladiei constă în lipsa preparatelor eficiente, dependenţa activităţii lor de condiţiile de mediu, înalta adaptabilitate a agenţilor cauzali ai maladiei la remediile nou create, toxicitatea pronunţată a acestora pentru plantă şi mediul ambiant. În legătură cu cele menţionate, identificarea noilor compuşi cu activitate antifungică prezintă un mare interes practic în sistemul de protecţie a plantelor. One of the main obstacles to combating the disease is the lack of effective preparations, the dependence of their activity on environmental conditions, the high adaptability of the causative agents of the disease to newly created remedies, their pronounced toxicity for the plant and the environment. In connection with the above, the identification of new compounds with antifungal activity is of great practical interest in the plant protection system.
Este cunoscut compusul (Z)-4,4-dimetil-1-(2,4-diclorfenil)-2-(1H-1,2,4-triazol-1-il)pent-1-en-3-ona care a fost propus în calitate de regulator al creşterii plantelor şi de agent fungicid pentru unele specii de fungi fitopatogeni, aşa ca: Helminthosporium gramineum, Penicillium italicum, Venturia inaequalis, Valsa mali, Mycosphaerella melonis, Diaporthe citri, Verticillium albo-atrum, Septoria tritici, Cercospora beticola, Fusarium oxysporum f.sp. lycopersici, Alternaria kikuchiana [1]. The compound (Z)-4,4-dimethyl-1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-one is known and has been proposed as a plant growth regulator and fungicidal agent for some species of phytopathogenic fungi, such as: Helminthosporium gramineum, Penicillium italicum, Venturia inaequalis, Valsa mali, Mycosphaerella melonis, Diaporthe citri, Verticillium albo-atrum, Septoria tritici, Cercospora beticola, Fusarium oxysporum f.sp. lycopersici, Alternaria kikuchiana [1].
Dezavantajul acestui compus este că el nu-şi manifestă proprietăţile fungicide şi pentru aşa severi fungi fitopatogeni ca: Alternaria alternata şi Fusarium aquaeductuum. The disadvantage of this compound is that it does not exhibit its fungicidal properties even for such severe phytopathogenic fungi as: Alternaria alternata and Fusarium aquaeductuum.
Mai este cunoscut compusul (E)-1-(2,4-diclorfenil)-4,4-dimetil-2-(1H-1,2,4-triazol-1-il)pent-1-en-3-ol, cel mai apropiat după activitatea fungicidă, utilizat comercial pe scară largă ca preparat Diniconazol. Acest preparat manifestă un spectru larg de acţiune antimicrobiană pentru infecţiile stabilite în seminţe. La tratarea seminţelor cu diniconazol, acesta este ulterior transportat în partea aeriană a plantei şi la etapele timpurii de dezvoltare o apără de infectarea aerogenă cu făinare şi diverşi alţi fitopatogeni [2]. The compound (E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol is also known, the closest in fungicidal activity, widely used commercially as the preparation Diniconazole. This preparation exhibits a broad spectrum of antimicrobial action for infections established in seeds. When seeds are treated with diniconazole, it is subsequently transported to the aerial part of the plant and at the early stages of development protects it from airborne infection with powdery mildew and various other phytopathogens [2].
Avantajele lui constau în aceea că este un fungicid activ, aprobat pentru utilizare împotriva bolilor grâului de primăvară şi de iarnă (tăciunele prăfos, mălura, mucezirea seminţelor, putregaiul de rădăcină provocat de ciupercile Fusarium şi Helminthosporium), orzului de primăvară şi de iarnă (putregaiul de rădăcină, mucezirea seminţelor). Its advantages are that it is an active fungicide, approved for use against diseases of spring and winter wheat (powdery mildew, downy mildew, seed mold, root rot caused by Fusarium and Helminthosporium fungi), spring and winter barley (root rot, seed mold).
Dezavantajele constau în aceea că el nu-şi manifestă activitatea antifungică la un nivel suficient de înalt. The disadvantages are that it does not exhibit antifungal activity at a sufficiently high level.
Problema pe care o soluţionează invenţia constă în extinderea gamei de preparate din clasa 1,2,4-triazolilor cu activitate fungitoxică care ar putea fi utilizate cu succes în agricultură pentru combaterea putregaiului de rădăcină provocat de fungii Alternaria alternata şi Fusarium aquaeductuum. The problem solved by the invention consists in expanding the range of preparations from the class of 1,2,4-triazoles with fungitoxic activity that could be successfully used in agriculture to combat root rot caused by the fungi Alternaria alternata and Fusarium aquaeductuum.
Esenţa invenţiei constă în aceea că în calitate de remediu contra ciupercilor fitopatogene din speciile Alternaria alternata şi Fusarium aquaeductuum - unii din agenţii cauzali ai putregaiului de rădăcină se propune (Z)-4,4-dimetil-1-(2,4-diclorfenil)-2-(1H-1,2,4-triazol-1-il)pent-1-en-3-ona. Concentraţiile active variază în diapazonul 0,0025…..0,1% în dependenţă de specia de fung testată. The essence of the invention is that (Z)-4,4-dimethyl-1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-one is proposed as a remedy against phytopathogenic fungi of the species Alternaria alternata and Fusarium aquaeductuum - some of the causative agents of root rot. The active concentrations vary in the range of 0.0025…..0.1% depending on the tested fungal species.
Avantajele invenţiei constau în aceea că compusul (Z)-4,4-dimetil-1-(2,4-diclorfenil)-2-(1H-1,2,4-triazol-1-il)pent-1-en-3-ona contribuie la sporirea activităţii fungitoxice pentru unii din agenţii cauzali ai putregaiului de rădăcină - A. alternata şi F. aquaeductuum în raport cu soluţia cea mai apropiată. The advantages of the invention consist in the fact that the compound (Z)-4,4-dimethyl-1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-one contributes to increasing the fungitoxic activity for some of the causative agents of root rot - A. alternata and F. aquaeductuum in relation to the closest solution.
Rezultatul tehnic constă în sporirea activitatii fungitoxice a compusului din invenţie în raport cu soluţia cea mai apropiată cu 10...25% pentru fungul A. alternata şi 18…33% pentru F. aquaeductuum. The technical result consists in increasing the fungitoxic activity of the compound of the invention compared to the closest solution by 10...25% for the fungus A. alternata and 18...33% for F. aquaeductuum.
Exemplu de realizare a invenţiei Example of embodiment of the invention
Deşi compusul este cunoscut din stadiul tehnicii, el a fost obţinut printr-un procedeu modificat, care prevede interacţiunea cetonei, obţinută conform MD4505 C1, cu 2,4-diclorbenzaldehida în benzen în prezenţa piperidinei şi acidului acetic (cantităţi catalitice). Although the compound is known from the prior art, it was obtained by a modified process, which provides for the interaction of the ketone, obtained according to MD4505 C1, with 2,4-dichlorobenzaldehyde in benzene in the presence of piperidine and acetic acid (catalytic amounts).
Procedeul efectuat în condiţiile menţionate este stereospecific şi conduce la formarea substanţei de interes α,β-nesaturate 2. Procedeul decurge conform ecuaţiei: The process carried out under the mentioned conditions is stereospecific and leads to the formation of the α,β-unsaturated substance of interest 2. The process proceeds according to the equation:
La soluţia alcătuită din 1,67 g (0,01 mol) triazolil-cetona - 3,3-dimetil-1-(1H-1,2,4-triazol-1-il)butan-2-ona 1 şi 1,66 g (0,011 mol) 2,4-diclorbenzaldehida în 300 ml benzen se adaugă piperidină (0,05 mol/%) / acid acetic (0,17 mol/%). Amestecul se fierbe timp de 5 ore (controlat periodic cu ajutorul CSS) cu distilarea azeotropă a apei formate, folosind aparatul Dean-Stark, apoi soluţia de benzen se răceşte până la temperatura camerei, rămăşiţele de catalizator se extrag cu apă, apoi soluţia benzenică a produsului final se usucă cu Na2SO4. Solventul se distilează, iar reziduul se recristalizează din etanol. To a solution of 1.67 g (0.01 mol) of triazolyl ketone - 3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one 1 and 1.66 g (0.011 mol) of 2,4-dichlorobenzaldehyde in 300 ml of benzene is added piperidine (0.05 mol/%) / acetic acid (0.17 mol/%). The mixture is boiled for 5 hours (periodically controlled by means of TLC) with azeotropic distillation of the water formed, using the Dean-Stark apparatus, then the benzene solution is cooled to room temperature, the catalyst residues are extracted with water, then the benzene solution of the final product is dried with Na2SO4. The solvent is distilled off, and the residue is recrystallized from ethanol.
Randamentul reacţiei este de 53% (1,72 g), P.t.= 117-120°С. The reaction yield is 53% (1.72 g), mp= 117-120°С.
Structura compusului 2 este confirmată pe baza analizei elementelor şi datelor spectrale: The structure of compound 2 is confirmed based on elemental analysis and spectral data:
C15H15Cl2N3O C15H15Cl2N3O
Masa exactă: 323,06 Exact mass: 323.06
Calculat,(%): C 59,99; H 5,37; N 18,66, C 55,57; H 4,66; N 12,96. Calculated, (%): C 59.99; H 5.37; N 18.66, C 55.57; H 4.66; N 12.96.
Stabilit,(%): C 59,83; H 5,22; N 18,62. Determined (%): C 59.83; H 5.22; N 18.62.
IR (ν/cm-1): 3118, 2970, 2297, 1636, 1630, 1505, 1473, 1384, 1138, 1104, 1005, 934, 848, 834, 771, 673. IR (ν/cm-1): 3118, 2970, 2297, 1636, 1630, 1505, 1473, 1384, 1138, 1104, 1005, 934, 848, 834, 771, 673.
Spectrul RMN 1H (400 MHz, CDCl3, δ, ppm, J/Hz): 8,07 (s, 1H), 7,93 (s, 1H), 7,62 (s, 1H), 7,45 (1H, d, J = 1,9), 7,04 (1H, dd, J = 8.4, 1,9), 6,47 (1H, d, J = 8,4), 1,28 (s, 9H). 1H NMR spectrum (400 MHz, CDCl3, δ, ppm, J/Hz): 8.07 (s, 1H), 7.93 (s, 1H), 7.62 (s, 1H), 7.45 (1H, d, J = 1.9), 7.04 (1H, dd, J = 8.4, 1.9), 6.47 (1H, d, J = 8.4), 1.28 (s, 9H).
Spectrul RMN 13C (100 MHz, CDCl3, δ, ppm): 201,90, 152,8, 144,9, 136,8, 135,7, 134,3, 130,8, 129,97, 129,87, 128,9, 127,7, 44,23, 27,6. 13C NMR spectrum (100 MHz, CDCl3, δ, ppm): 201.90, 152.8, 144.9, 136.8, 135.7, 134.3, 130.8, 129.97, 129.87, 128.9, 127.7, 44.23, 27.6.
Obţinerea unui singur izomer - Z este confirmată prin metoda RMN. The obtaining of a single Z-isomer is confirmed by NMR.
Izolarea fungilor A. alternata şi F. aquaeductuum - agenţii cauzali al putregaiului de rădăcină la grâu s-a efectuat în condiţii aseptice pe mediu PDA (Potato Dextrose Agar) (Методы экспериментальной микологии. Киев: Наукова думка, 1982, p. 550). Acest mediu este unul din cele mai optime medii pentru izolarea, cultivarea şi cercetarea caracterelor morfologo-culturale ale patogenilor menţionaţi. Au fost utilizate fragmente mici de ţesut cu semne de putrefacţie de la baza tulpinii de grâu. Fragmentele au fost aseptizate în soluţie de hipoclorură de var de 2% timp de 1-2 min, după care s-au clătit de 2-3 ori în apă distilată, presate între 2 foiţe de hârtie de filtru şi plasate pe mediu în preajma flăcării de gaz. The isolation of the fungi A. alternata and F. aquaeductuum - the causal agents of root rot in wheat was carried out under aseptic conditions on PDA (Potato Dextrose Agar) medium (Методы експериментальной микологии. Kiev: Наукова думка, 1982, p. 550). This medium is one of the most optimal media for the isolation, cultivation and research of the morphological and cultural characters of the mentioned pathogens. Small fragments of tissue with signs of rotting from the base of the wheat stem were used. The fragments were asepticized in a 2% lime hypochlorite solution for 1-2 min, after which they were rinsed 2-3 times in distilled water, pressed between 2 sheets of filter paper and placed on the medium near a gas flame.
Identificarea patogenilor s-a efectuat în baza caracteristicelor macro- şi microscopice conform determinatoarelor (Билай В.И. Фузарии. Киев: Наукова думка, 1977, p. 422; Barnett H.L., Hunter B.B. Illustrated Genera of Imperfect Fungi, Fourth Edition. APS Press, 1998, 218 pp.) Identification of pathogens was carried out based on macro- and microscopic characteristics according to the determinants (Bilay V.I. Fuzarii. Kiev: Naukova Dumka, 1977, p. 422; Barnett H.L., Hunter B.B. Illustrated Genera of Imperfect Fungi, Fourth Edition. APS Press, 1998, 218 pp.)
Compuşii din invenţie şi solutia cea mai apropiată au fost suplimentaţi la mediul nutritiv PDA în concentraţiile 0,01 (1); 0,005 (2); 0,0025 (3); 0,00125% (4) care s-a aseptizat prin autoclavare la presiunea de 0,5 atm timp de 30 min. Mediul aseptizat, fierbinte s-a turnat în cutii Petri, câte 10 ml în fiecare. După solidificarea mediului, fungii au fost însămânţaţi - câte un disc de PDA cu miceliul fungului, cu diametrul de 4 mm în centrul cutiei Petri. Cutiile cu fungii însămânţaţi, au fost menţinute în termostat la temperatura de 24°C. Înregistrarea diametrului coloniilor (câte 2 diametre perpendiculare, media cărora a servit ca indice biometric) s-a efectuat din ziua 3-4 de la însămânţare, în dependenţă de viteza de creştere a fungilor. Experienţele s-au efectuat în 5 repetiţii. Datele au fost prelucrate statistic în pachetul de soft STATISTICA 7. The compounds of the invention and the closest solution were supplemented to the PDA nutrient medium in concentrations of 0.01 (1); 0.005 (2); 0.0025 (3); 0.00125% (4) which was sterilized by autoclaving at a pressure of 0.5 atm for 30 min. The sterilized, hot medium was poured into Petri dishes, 10 ml each. After the medium solidified, the fungi were seeded - a PDA disk with the fungal mycelium, with a diameter of 4 mm in the center of the Petri dish. The boxes with the seeded fungi were maintained in a thermostat at a temperature of 24°C. The colony diameter was recorded (2 perpendicular diameters, the average of which served as a biometric index) from day 3-4 after seeding, depending on the growth rate of the fungi. The experiments were performed in 5 repetitions. The data were statistically processed in the STATISTICA 7 software package.
Tabelul 1 Table 1
Acţiunea inhibitorie a compusului din invenţie şi din cadrul soluţiei celei mai apropiate asupra fungului fitopatogen A. alternata în ziua 7 de cultivare Inhibitory action of the compound of the invention and of the closest solution on the phytopathogenic fungus A. alternata on day 7 of cultivation
Compuşi Diametrul coloniei, mm 0,01% 0,005% 0,0025% Martor absolut 58,6±0,9 58,6±0,9 58,6±0,9 Invenţia (Z)-4,4-dimetil-1-(2,4-diclorfenil)-2-(1H-1,2,4-triazol-1-il)pent-1-en-3-ona (1% - concentraţia iniţială a compusului în solvent DMSO) 28,0±2,0* 33,8±1,7* 38,3±1,0* Soluţia cea mai apropiată (E)-1-(2,4-diclorfenil)-4,4-dimetil-2-(1H-1,2,4-triazol-1-il)pent-1-en-3-ol (Diniconazol) (1% - concentraţia iniţială a compusului în solvent sol. C2H5OH) 42,6±0,6* 39,7±0,6* 47,1±1,0*Compounds Colony diameter, mm 0.01% 0.005% 0.0025% Absolute control 58.6±0.9 58.6±0.9 58.6±0.9 Invention (Z)-4,4-dimethyl-1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-one (1% - initial concentration of the compound in solvent DMSO) 28.0±2.0* 33.8±1.7* 38.3±1.0* Closest solution (E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol (Diniconazole) (1% - initial concentration of the compound in solvent sol. C2H5OH) 42.6±0.6* 39.7±0.6* 47.1±1.0*
*- deosebire veridică de martor, p <0,05. *- true difference from control, p <0.05.
Conform rezultatelor prezentate, se atestă sporirea activităţii fungitoxice a compusului din invenţie în raport cu cel din cadrul soluţiei celei mai apropiate asupra A. alternata cu 10...25% în intervalul de concentraţii 0,0025...0,01%. According to the presented results, the fungitoxic activity of the compound of the invention is increased compared to that of the closest solution on A. alternata by 10...25% in the concentration range 0.0025...0.01%.
Tabelul 2 Table 2
Acţiunea inhibitorie a compusului din invenţie şi din cadrul soluţiei celei mai apropiate asupra fungului fitopatogen F. aquaeductuum în ziua 14 de cultivare Inhibitory action of the compound of the invention and of the closest solution on the phytopathogenic fungus F. aquaeductuum on day 14 of cultivation
Compuşi Diametrul coloniei, mm 0,01% 0,005% 0,0025% Martor 56,4 ± 1,8 56,4 ± 1,8 56,4 ± 1,8 Invenţia (Z)-4,4-dimetil-1-(2,4-diclorfenil)-2-(1H-1,2,4-triazol-1-il)pent-1-en-3-ona (1% - concentraţia iniţială a compusului în solvent DMSO) 33,3 ± 1,9* 36,5± 0,6* 39,1± 0,9* Soluţia cea mai apropiată (E)-1-(2,4-diclorfenil)-4,4-dimetil-2-(1H-1,2,4-triazol-1-il)pent-1-en-3-ol (Diniconazol) (1% - concentraţia iniţială a compusului în solvent sol. C2H5OH) 43,7 ± 0,9* 55,0± 0,7* 52,6±2,0*Compounds Colony diameter, mm 0.01% 0.005% 0.0025% Control 56.4 ± 1.8 56.4 ± 1.8 56.4 ± 1.8 Invention (Z)-4,4-dimethyl-1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-one (1% - initial concentration of the compound in DMSO solvent) 33.3 ± 1.9* 36.5± 0.6* 39.1± 0.9* Closest solution (E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol (Diniconazole) (1% - initial concentration of the compound in solvent sol. C2H5OH) 43.7 ± 0.9* 55.0± 0.7* 52.6±2.0*
*- deosebire veridică de martor, p <0,05. *- true difference from control, p <0.05.
Conform rezultatelor prezentate, se atestă sporirea activităţii fungitoxice a compusului din invenţie în raport cu cel din cadrul soluţiei celei mai apropiate asupra F. aquaeductuum cu 18,44 …32,8% în intervalul de concentraţii 0,01…0,0025%. According to the presented results, the fungitoxic activity of the compound of the invention is increased compared to that of the closest solution on F. aquaeductuum by 18.44...32.8% in the concentration range 0.01...0.0025%.
1. US 4554007 A 1985.11.19 1. US 4554007 A 1985.11.19
2. Андреева Е.И., Зинченко В.А. Системные фунгициды - ингибиторы биосинтеза эргостерина. Журнал «АгроXXI», №4, 2002, с.14-15. 2. Andreeva Е.И., Zinchenko В.А. System fungicides - ergosterine biosynthesis inhibitors. Journal «AgroXXI», №4, 2002, pp. 14-15.
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