PL197214B1 - New carane chiral iodospiro lactone and method of its manufacture - Google Patents

Abstract

1. A new chiral karan iodospyrolactone named (3R, 4R) - (-) - 4-iodo-spiro [norkaran-3,5'-tetrahydrofuran] -2'-one, of formula 1 shown in the drawing.

Description

(12) PATENT DESCRIPTION (19) PL (11) 197214 (13) B1 ( ²¹ ) Application number: ^{354222 51)} ) Int-CI.

C07D 307/94 (2006.01) (22) Date of notification: 03/06/2002 (54) New chiral iodospyrolactoncaran and its preparation

(73) The right holder of the patent: Wrocław University of Technology, Wrocław, PL (43) Application was announced: (72) Inventor (s): 15.12.2003 BUP 25/03 Stanisław Lochyński, Wrocław, PL (45) The grant of the patent was announced: 31.03.2008 WUP 03/08 Bożena Frąckowiak, Trzebnica, PL Teresa Olejniczak, Smolec, PL Czesław Wawrzeńczyk, Wrocław, PL (74) Representative: J. Halina Winohradnik, Wroclaw University of Science and Technology, Office for Invention and Patent Protection

(57) 1. A new chiral karane iodospyrolactone named (3R, 4R) - (-) - 4-iodo-spiro [norkaran-3,5'-tetrahydrofuran] -2'-one, with the formula 1 shown in the figure.

PL 197 214 B1

Description of the invention

The subject of the invention is a new chiral karan iodospyrolactone and a method of its preparation.

This compound is an intermediate product in the synthesis of a compound with the desired fragrance properties.

The new chiral karane iodospyrolactone named (3R, 4R) - (-) - 4-iodo-spiro [norcaran-3,5'-tetrahydrofuran] -2'-one, with the formula 1 shown in the figure, has a specific, confirmed by crystallographic tests , spatial structure.

The method of producing the new (3R, 4R) - (-) - 4-iodo-spiro [norkarate-3,5'-tetrahydroturan] -2'-one, of the formula 1 shown in the figure, consists in the reaction of the acid (+) - (3 -caren-10-yl) acetic acid with iodine and potassium iodide in 0.5 M aqueous sodium bicarbonate solution.

According to the method, the acid is reacted with iodine and potassium iodide for at least 14 hours. at room temperature, while stirring constantly and controlling its course by thin-layer chromatography. When the substrate is completely converted, the reaction mixture is diluted with diethyl ether, the layers are separated and the organic layer is shaken with an aqueous sodium thiosulfate solution, then washed with sodium bicarbonate solution, brine and dried with anhydrous magnesium sulfate. After evaporation of the organic solvent on a rotary evaporator, crude (3R, 4R) - (-) - 4-iodo-spiro [norkarate-3,5'-tetrahydrofuran] -2'-one is obtained, which is recrystallized from hexane.

The new chemical compound is a diastereoisomeric karan iodospirolactone useful in the synthesis of unsaturated karene spirolactone with the desired fragrance properties.

The method according to the invention is presented in an exemplary embodiment:

P r z k ł a d

To a solution of 1.25 g, i.e. 6.40 mmol of (+) - (3-karen-10-yl) acetic acid in 25 ml of diethyl ether, 25 ml of 0.5 M sodium bicarbonate solution are added. The whole is stirred with a magnetic stirrer for 30 minutes at room temperature. A solution of 5.12 g, i.e. 30.80 mmol of potassium iodide and 2.56 g, i.e. 10.12 mmol of iodine in 30 ml of distilled water, is then added. The reaction mixture is left for 14 h while stirring is continued and the course is monitored by thin layer chromatography. When the substrate is completely converted, the reaction mixture is diluted with diethyl ether, the layers are separated, and the organic layer is shaken with an aqueous sodium thiosulfate solution, then washed with sodium bicarbonate solution, brine and dried with anhydrous magnesium sulfate. After evaporation of the organic solvent on a rotary evaporator, 2.0 g of crude (3R, 4R) - (-) - 4-iodo-spiro [norkaran-3,5'-tetrahydrofuran] -2'-one are obtained, which is recrystallized from hexane yielding 1.35 g, i.e. 4.22 mmol, which is 66% of theory. The crystalline product obtained according to the example has the following physical and spectral properties: Temp. top. 86-88 ° C. [α] ο ^{26 =} -76.5 ° (c = 2.9, CHCl ₃ );

IR (KBr, cm ^-1 ): 2935w, 2864w, 1772vs, 1456w, 1375w, 1203w, 1189s, 1047m.

¹ H NMR (CDCl) δ: 0.62 (ddd, J = 9.9, 9.2, 1.7 Hz, 1 H at C-6); 0.87 (td, J = 9.6, 4.2 Hz, 1H at C-1); 1.00 and 1.01 (two s, 6H at C-8 and C-9); 1.71 (dd, J = 14.8, 4.2 Hz, 1H and _xx at C-2); 2.17-2.75 (m, 6H at C-5, C-3 ', C-4' and 1Heq at C-2); 4.29 (dd, J = 10.9, 7.1 Hz, 1H at C-4);

⁵ C NMR (CDCl3), δ: 15.17 (q, C-8 or C-9), 18.05 (s, C-7), 18.93 (d, C-1), 21.90 ( d, C-6), 28.50 (q, C-8 or C-9), 28.64 (t, C-2), 29.10 (t, C-5), 30.03 (t, C-4 '), 32.94 (t, C-3'), 38.23 (d, C-4), 85.19 (s, C-3), 175.53 (s, C-2 ' ).

Claims (3)

Patent claims 1. A new chiral karan iodospyrolactone named. (3R, 4R) - (-) - 4-iodo-spiro [norcaran-3,5'-tetrahydrofuran] -2'-one, having the formula 1 shown in the drawing. 2. The method for the production of a new karan iodoospyrolactone named (3R, 4R) - (-) - 4-iodospco [norkarate-3,5'-tetrahydrofuran] -2'-one, with the formula 1 shown in the figure, characterized by the fact that on the reaction of (+) - (3-karen-10-yl) acetic acid with iodine and potassium iodide in 0.5 M aqueous sodium bicarbonate solution for at least 14 hours. in room temperature. 3. The method according to p. 2. The process of claim 2, characterized in that the reaction of (+) - (3-karen-10-yl) acetic acid with iodine and potassium iodide is carried out under constant stirring and its course is monitored by thin-layer chromatography, and after confirming complete conversion of the substrate, the reaction mixture After diluting with diethyl ether, the layers are separated, then the organic layer is shaken with an aqueous sodium thiosulfate solution, then washed with sodium bicarbonate solution, brine and dried with anhydrous magnesium sulfate, after evaporation of the organic solvent, the crude (3R, 4F? ) - (-) - 4-iodo-spiro [norkaran-3,5'-tetrahydrofuran] -2'-one which is recrystallized from hexane.