PL222194B1 - 3a,7,7-trimethyl-8-propyl-hexahydro-,cyclopropa[1,1]benzofuran-2(3H)-one with the antifidant activity and a method for its preparation - Google Patents

Description

(12) PATENT DESCRIPTION (19) PL (11) 222194 (13) B1 (21) Application number: ^{406432 (51) Int.Cl.}

C07D 311/02 (2006.01) A01N 43/16 (2006.01) A01P 7/00 (2006.01) (22) Date of notification: 09/12/2013

3a, 7,7-trimethyl-8-propyl-hexahydro, cyclopropa [1,2] benzofuran-2 (3H) -one with antifreeze activity and the method of its preparation (73) The right holder of the patent:

UNIVERSITY OF NATURE IN WROCŁAW, Wrocław, PL (43) Application was announced:

04.08.2014 BUP 16/14 (45) The following was announced about the grant of the patent:

29.07.2016 WUP 07/16 (72) Inventor (s):

ANNA GLISZCZYŃSKA,

Piotrków Trybunalski, PL MARYLA SZCZEPANIK, Głogowo, PL MAKSYMILIAN HNATEJKO, Toruń, PL KATARZYNA DANCEWICZ, Zielona Góra, PL BEATA GABRYŚ, Zielona Góra, PL (74) Plenipotentiary:

item. stalemate. Anna Olszewska

PL 222 194 B1

Description of the invention

The subject of the invention is saturated lactone 3a, 7,7-trimethyl-8-propyl-hexahydro, cyclopropa [1,2] benzofuran-2 (3H) -one with antifungal activity and the method of its preparation.

The invention may find application in the chemical industry and agriculture, for the production of plant protection products, food retailers in relation to harmful insect species.

So far, there is no known 3a, 7,7-trimethyl-8-propyl-hexahydro, cyclopropa [1,2] benzofuran-2 (3H) -one or a method of its preparation in a one-step reaction.

From the description of the invention P.405748 there is known the lactone 7a-bromo-3a, 7,7-trimethyl-8-propylactahydroisochromen-3-one with antifidency activity.

The essence of the invention is 3a, 7,7-trimethyl-8-propyl-hexahydro, cyclopropa [1,2] benzofuran-2 (3H) -one. The essence of the method of obtaining this compound is that the known 7a-bromo-3a, 7,7-trimethyl-8-propylactahydroisochromen-3-one is subjected to a one-step dehydrohalogenation reaction, which leads to the production of 3a, 7,7-trimethyl-8-propyl- hexahydro, cyclopropa [1,2] benzofuran-2 (3H) -one.

The saturated bicyclic lactone of formula I has antifidus activity against the peach potato aphid (Myzus persicae Sulz).

The results of biological tests against the peach potato aphid (Myzus persicae Sulz), carried out according to the method described by K. Dancewicz et al. (Journal of Chemical Ecology, 2008, 34, 530-538), are presented in Table 1.

T a b e l a 1. Results of deterential activity of the lactone of formula 1 in relation to the peach-potato aphid (Myzus persicae Sulz)

lactone Peach potato aphid (Myzus persicae Sulz) K. T. P. Formula 1 11.5 6.25 0.001

K - the average number of aphids located on a half of a leaf moistened with a 70% ethanol solution

T - the average number of aphids on a half of the leaf moistened with 0.1% ethanol solution of the tested compound P - significance level of the statistical difference

The saturated bicyclic lactone, formula 1, also has antifidus activity against Alphitobius diaperinus Panzer beetles.

The results of biological tests against black mildew beetles (Alphitobius diaperinus Panzer), carried out according to the method described by M. Szczepanik et al. (Journal of Plant Protection Research, 2003, 43, 2, 87-96), are presented in Table 2.

T a b e l a 2. The results of lactone deterential activity of the formula 1 in relation to the lesser thrush beetles (Alphitobius diaperinus Panzer)

lactone Glossy midge (Alphitobius diaperinus Panzer) Beetles AND R T. Formula 1 72.24 81.27 153.5

A - absolute detecting activity coefficient R - relative detecting activity coefficient T - total detecting activity coefficient

The subject of the invention is explained in more detail in an exemplary embodiment.

Example 1: To the bromolactone 7α-bromo-3a, 7,7-trimethyl-8-propylactahydroisochromen-3-one, 0.95 g (3 mmol) dissolved in 20 mL of methylene chloride is added 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) 0.48 mL (6 mmol) and refluxed at the reflux temperature of the solvent. After completion of the reaction (GC, TLC, not more than 3 hours), methylene chloride was distilled off under reduced pressure and the residue was diluted with diethyl ether (30 mL). The organic fraction was separated and the aqueous layer was further extracted with diethyl ether (3 x 20 mL). The combined ethereal solutions were washed with saturated NaHCO3 solution, brine until neutral, and then dried with anhydrous MgSO4. After evaporation of the solvent, the product was subjected to column chromatography eluting with a mixture of hexane and acetone in the ratio of 6: 1 by volume to obtain 0.37 g of 3α, 7,7-trimethyl-8-propyl-hexahydro, cyclopropa [1,2] benzofuran-2, respectively. (3H) -one at a yield of 53%.

PL 222 194 B1

The spectroscopic data of the obtained 3a, 7,7-trimethyl-8-propyl-hexahydro, cyclopropa [1,2] -benzofuran-2 (3H) -one of formula 1 are as follows:

¹ H NMR (CDCl3), δ: 0.96 (t, J = 7.3 Hz, 1 H, CH 3 II), 1.14 and 1.18 (two s, 6H, (CH3hC <), 1.21 (s, 3H, CH3-3), 1.29-2.11 (three m, 11H, CH3-6, CH3-5, CH3-4, CH3-9, CH3-10 and H-3), 4.25 (d, J = 10.9 Hz, 1H, H-8).

¹³ C NMR (CDCl3), δ: 13.92 (C-11), 17.73 (C-10), 17.86 (C-14), 20.45 (C-5), 26.13 (C-12), 28.04 (C-3a) , 29.50 (C-13), 30.52 (C-7), 33.11 (C-9), 34.12 (C-3), 37.27 (C-6), 41.51 (C-4), 45.59 (C-7a), 82.73 (C-8), 175.13 (C-2).

IR (movie, cm ^-1 ): 2936 (s), 2873 (s), 1762 (s), 1466 (m), 1327 (m), 1188 (s), 976 (s).

Claims (2)

Patent claims 1. 3 [alpha], 7,7-trimethyl-8-propyl-hexahydro, cyclopropa [1,2] benzofuran-2 (3H) -one saturated lactone with an antifidant activity of formula 1. 2. The method of obtaining 3a, 7,7-trimethyl-8-propyl-hexahydro, cyclopropa [1,2] benzofuran-2 (3H) -one, with antifungal activity, characterized in that the known 7a-bromo-3a, 7, 7-trimethyl-8-propylactahydroisochromen-3-one is subjected to a one-step dehydrohalogenation reaction, which gives 3α, 7,7-trimethyl-8-propyl-hexahydro, cyclopropa [1,2] benzofuran-2 (3H) -one, of formula 1.