PL213612B1 - New compound 7.7-dimethyl-3 ,4-epoxy-8-oxybicyclo [4.3.0] nonane-9-one and process for the preparation thereof - Google Patents
New compound 7.7-dimethyl-3 ,4-epoxy-8-oxybicyclo [4.3.0] nonane-9-one and process for the preparation thereofInfo
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- PL213612B1 PL213612B1 PL392579A PL39257910A PL213612B1 PL 213612 B1 PL213612 B1 PL 213612B1 PL 392579 A PL392579 A PL 392579A PL 39257910 A PL39257910 A PL 39257910A PL 213612 B1 PL213612 B1 PL 213612B1
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- oxabicyclo
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Description
Przedmiotem wynalazku jest nowy związek 7,7-dimetylo-3,4-epoksy-8-oksabicyklo[4.3.0]nonan-9-on, o wzorze 2 przedstawiony na rysunku i sposób jego otrzymywania.The subject of the invention is a new compound of 7,7-dimethyl-3,4-epoxy-8-oxabicyclo [4.3.0] nonan-9-one, of the formula II shown in the drawing and the method of its preparation.
Związek ten ma aktywność grzybobójczą wobec Fusarium oxysporum (IC50=95 μg/ml) oraz Aspergillus ochraceus (IC50=142 μg/ml), fitopatogenów wytwarzających mikotoksyny groźne dla zdrowia ludzi i zwierząt.This compound has fungicidal activity against Fusarium oxysporum (IC 50 = 95 µg / ml) and Aspergillus ochraceus (IC 50 = 142 µg / ml), phytopathogens producing mycotoxins dangerous to human and animal health.
Otrzymane związki mogą znaleźć zastosowanie w przemyśle rolno-spożywczym.The obtained compounds can be used in the agricultural and food industry.
Aktywność grzybobójcza naturalnych i syntetycznych laktonów została opublikowana w przykładowych pracach: Skaltsa H., Lazari D., Panagouleas C., Georgiaddou E., Garcia B., Sokvic M., „Sesquiterpene lactones from Centaurea thessala and Centaurea attica. Antifungal activity”, Phytochemistry 2000, 55, ss. 91-94; Erasto P., Grierson D. S, Afllayan A. J., „Bioactive sesquiterpene lactones from leaves of Vernonia amygdalina”, Journal of Ethnopharmacology 2006, 106, ss. 117-120.The fungicidal activity of natural and synthetic lactones has been published in the following works: Skaltsa H., Lazari D., Panagouleas C., Georgiaddou E., Garcia B., Sokvic M., "Sesquiterpene lactones from Centaurea thessala and Centaurea attica. Antifungal activity ”, Phytochemistry 2000, 55, pp. 91-94; Erasto P., Grierson D. S, Afllayan A. J., "Bioactive sesquiterpene lactones from leaves of Vernonia amygdalina", Journal of Ethnopharmacology 2006, 106, pp. 117-120.
Znany jest sposób otrzymywania bicyklicznych laktonów, w tym 7,7-dimetylo-8-oksabicyklo[4.3.0]non-3-en-9-onu, o wzorze 1, który jest substratem do otrzymywania 7,7-dimetylo-3,4-epoksy-8-oksabicyklo[4.3.0]nonan-9-onu, o wzorze 2, (Canonne P., Lemay G., Belanger D., „Reaction of di(bromomagnesio) alkanes with unsymmetrically substituted cyclic anhydrides”, Tetrahedron Lett, 1980, 21, ss. 4167-4170).There is a known method for the preparation of bicyclic lactones, including 7,7-dimethyl-8-oxabicyclo [4.3.0] non-3-en-9-one, of formula 1, which is a substrate for the preparation of 7,7-dimethyl-3, 4-epoxy-8-oxabicyklo [4.3.0] nonan-9-one, with formula 2, (Canonne P., Lemay G., Belanger D., "Reaction of di (bromomagnesio) alkanes with unsymmetrically substituted cyclic anhydrides", Tetrahedron Lett, 1980, 21, pp. 4167-4170).
Substrat, 7,7-dimetylo-8-oksabicyklo[4.3.0]non-3-en-9-on, wykazuje słabą aktywność fungistatyczną wobec Fusarium oxysporum i Aspergillus ochraceus.The substrate, 7,7-dimethyl-8-oxabicyclo [4.3.0] non-3-en-9-one, shows poor fungistatic activity against Fusarium oxysporum and Aspergillus ochraceus.
Modyfikacja struktury substratu, polegająca na utlenieniu wiązania podwójnego do epoksydu, zwiększa aktywność grzybostatyczną.Modification of the substrate structure, consisting in the oxidation of the double bond to the epoxide, increases the fungistatic activity.
Brak jest doniesień literaturowych o otrzymywaniu 7,7-dimetylo-3,4-epoksy-8-oksabicyklo[4.3.0]nonan-9-onu, o wzorze 2, poprzez utlenianie kwasem m-chloronadbenzoesowym, podwójnego wiązania w cząsteczce laktonu.There are no reports in the literature on the preparation of 7,7-dimethyl-3,4-epoxy-8-oxabicyclo [4.3.0] nonan-9-one of the formula 2 by oxidation with m-chloroperbenzoic acid, a double bond in the lactone molecule.
Wynalazkiem jest nowy związek 7,7-dimetylo-3,4-epoksy-8-oksabicyklo[4.3.0]nonan-9-on, o wzorze 2 przedstawionym na rysunku.The invention is a novel compound of 7,7-dimethyl-3,4-epoxy-8-oxabicyclo [4.3.0] nonan-9-one of the formula 2 shown in the drawing.
Sposób otrzymywania nowego 7,7-dimetylo-3,4-epoksy-8-oksabicyklo[4.3.0]nonan-9-onu, o wzorze 2, polega na tym, że 7,7-dimetylo-8-oksabicyklo[4.3.0]-non-3-en-9-on, o wzorze 1, utlenia się kwasem m-chloronadbenzoesowym rozpuszczonym w dichlorometanie.The method of obtaining the new 7,7-dimethyl-3,4-epoxy-8-oxabicyclo [4.3.0] nonan-9-one of formula 2 is that 7,7-dimethyl-8-oxabicyclo [4.3. The O] -non-3-en-9-one of formula 1 is oxidized with m-chloroperbenzoic acid dissolved in dichloromethane.
Korzystnie jest, gdy proces utleniania prowadzi się przy ciągłym mieszaniu, w temperaturzePreferably, the oxidation process is carried out under continuous stirring at temperature
291 - 303 K.291 - 303 K.
Postępując zgodnie z wynalazkiem, w wyniku działania nadkwasu na wiązanie podwójne laktonu 7,7-dimetylo-8-oksabicyklo[4.3.0]non-3-en-9-onu, o wzorze 1, powstaje epoksylakton, zwiększający aktywność fungistatyczną 7,7-dimetyIo-3,4-epoksy-8-oksabicyklo[4.3.0]nonan-9-onu, o wzorze 2.In accordance with the invention, epoxylactone is formed as a result of the action of peracid on the double bond of the 7,7-dimethyl-8-oxabicyclo [4.3.0] non-3-en-9-one lactone, of the formula 1, which increases the fungistatic activity 7.7 - dimethyl-3,4-epoxy-8-oxabicyclo [4.3.0] nonan-9-one, of formula 2.
Zasadniczą zaletą metody wytwarzania wspomnianego epoksylaktonu jest to, że otrzymuje się go w łagodnych warunkach, z 76%-ową wydajnością.The main advantage of the method of producing said epoxylactone is that it is obtained under mild conditions, with a yield of 76%.
Wynalazek jest bliżej objaśniony na przykładzie wykonania.The invention is explained in more detail using an exemplary embodiment.
P r z y k ł a d.P r z k ł a d.
W kolbie okrągłodennej, umieszczonej na mieszadle magnetycznym, rozpuszcza się 0,7234 g -3 3 (4,35 10-3 mola) 7,7-dimetylo-8-oksabicyklo[4.3.0]non-3-en-9-onu w 15 cm3 dichlorometanu. Następ-3 nie, porcjami dodaje się 1,18 g (4,8 10-3 mola) 70% kwasu m-chloronadbenzoesowego. Po ośmiu 3 godzinach do mieszaniny dodaje się 15 cm3 20% siarczanu (IV) sodu i ekstrahuje się eterem etylo3 wym (3 x 50 cm3). Warstwę organiczną przemywa się 10% wodorowęglanem sodu, następnie solanką, aż do uzyskania odczynu obojętnego i osusza się siarczanem (VI) magnezu. Rozpuszczalnik odparowuje się a uzyskaną mieszaninę reakcyjną oczyszcza się za pomocą chromatografii kolumnowej (eluent heksan:aceton, 4:1 v/v).0.7234 g -3 3 (4.35 10 -3 mol) 7.7-dimethyl-8-oxabicyclo [4.3.0] non-3-en-9-one is dissolved in a round bottom flask placed on a magnetic stirrer. in 15 cm 3 of dichloromethane. The pedal-3 not added portionwise 1.18 g (4.8 10 -3 mole) of 70% m-chloroperbenzoic acid. After eight 3 hours the mixture is added 15 cm3 of 20% sulfate (IV) solution and extracted with ethyl 3 acid (3 x 50 cm 3). The organic layer is washed with 10% sodium bicarbonate then brine until neutral and dried with magnesium sulfate. The solvent is evaporated off and the resulting reaction mixture is purified by column chromatography (eluent hexane: acetone, 4: 1 v / v).
Otrzymuje się 0,6024 g produktu w postaci oleistej cieczy (wydajność 76%).0.6024 g of the product are obtained in the form of an oily liquid (76% yield).
Uzyskany produkt charakteryzuje się następującymi danymi spektroskopowymi:The obtained product is characterized by the following spectroscopic data:
1H NMR (500 MHz, CDCI3), δ (ppm): 1,22 (s, 1H, jeden z -5CH2-); 1,31 - 1,40 (2s, 6H, >C(CH3)2); 1,56 - 1,74 (m, 1H, jeden z -5CH2-); 2,10 - 2,25 (m, 1H, jeden z-2CH2-); 2,31 - 2,47 (m, 1H, jeden z-2CH2-); 2,75 - 2,97 (m, 1H, >1CH-); 3,00 - 3,21 (m, 1H, >6CH-) i 3,25 (t, J= 4,0 Hz, 2H, -H3C(O)-, -(O)4CH-). 1 H NMR (500 MHz, CDCl 3), δ (ppm): 1.22 (s, 1H, one of - 5 CH 2 -); 1.31 - 1.40 (2s, 6H,> C (CH3) 2); 1.56 - 1.74 (m, 1H, one of - 5 CH2-); 2.10-2.25 (m, 1H, one of - 2 CH2-); 2.31 - 2.47 (m, 1H, one of - 2 CH2-); 2.75 - 2.97 (m, 1H,> 1 CH-); 3.00 - 3.21 (m, 1H,> 6 CH-) and 3.25 (t, J = 4.0 Hz, 2H, -H 3 C (O) -, - (O) 4 CH-) .
13C NMR (151 Mz), δ (ppm): 20,9, (-5CH2-); 22,5, (CH3-7C); 23,5 (CH3-7C); 26,7 (-2CH2-); 35,4(>1CH-); 38,8(>6CH-); 49,7 (-H4C-); 51,6(-3CH-); 84,0, (->7C(O)-); 178,1(>9C=O). 13 C NMR (151 MHz), δ (ppm): 20.9, (- 5 CH 2 -); 22.5 (CH 3 C 7); 23.5 (CH 3 C 7); 26.7 (- 2 CH2-); 35.4 (> 1 CH-); 38.8 (> 6 CH-); 49.7 (-H 4 C-); 51.6 (- 3 CH-); 84.0 (-> 7 C (O) -); 178.1 (> 9 C = O).
IR (fiIm, cm-1): 3019 (w), 2399 (w), 1773 (s), 1215 (m), i 756 (s); GC-EIMS: 183 (M+1).IR (µm, cm -1 ): 3019 (w), 2399 (w), 1773 (s), 1215 (m), and 756 (s); GC-EIMS: 183 (M + 1).
PL 213 612 B1PL 213 612 B1
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| PL392579A PL213612B1 (en) | 2010-10-04 | 2010-10-04 | New compound 7.7-dimethyl-3 ,4-epoxy-8-oxybicyclo [4.3.0] nonane-9-one and process for the preparation thereof |
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| PL392579A PL213612B1 (en) | 2010-10-04 | 2010-10-04 | New compound 7.7-dimethyl-3 ,4-epoxy-8-oxybicyclo [4.3.0] nonane-9-one and process for the preparation thereof |
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| PL213612B1 true PL213612B1 (en) | 2013-04-30 |
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