PL196372B1 - New 3-methyl-3- (4-methyl-1-cyclohexen-1-yl) butanoic acid ethyl esters and their preparation - Google Patents
New 3-methyl-3- (4-methyl-1-cyclohexen-1-yl) butanoic acid ethyl esters and their preparationInfo
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- PL196372B1 PL196372B1 PL362877A PL36287703A PL196372B1 PL 196372 B1 PL196372 B1 PL 196372B1 PL 362877 A PL362877 A PL 362877A PL 36287703 A PL36287703 A PL 36287703A PL 196372 B1 PL196372 B1 PL 196372B1
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Abstract
1. Nowe estry etylowe kwasu 3-metylo-3-(4- -metylo-1-cykloheksen-1-ylo)butanowego, o wzorach 1 i 2 przedstawionych na rysunku1. New ethyl esters of 3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic acid, of formulas 1 and 2 shown in the figure
Description
(12) OPIS PATENTOWY (19) PL (11) 196372(12) PATENT DESCRIPTION (19) PL (11) 196372
RZECZPOSPOLITAREPUBLIC
POLSKAPOLAND
(21) Numer zgłoszenia: 362877 (13) B1 (51) Int.Cl.(21) Application number: 362877 (13) B1 (51) Int.Cl.
C07C 69/608 (2006.01) C07C 67/00 (2006.01)C07C 69/608 (2006.01) C07C 67/00 (2006.01)
Urząd Patentowy Rzeczypospolitej Polskiej (22) Data zgłoszenia: 15.10.2003Patent Office of the Republic of Poland (22) Date of filing: 15/10/2003
Nowe estry etylowe kwasu 3-metylo-3-(4-metylo-1-cykloheksen-1-ylo)butanowego i sposób ich wytwarzaniaNew ethyl esters of 3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic acid and a method for their preparation
(57) 1. Nowe estry etylowe kwasu 3-metylo-3-(4-metylo-1-cykloheksen-1-ylo)butanowego, o wzorach 1 i 2 przedstawionych na rysunku.(57) 1. New ethyl esters of 3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic acid, of formulas 1 and 2 shown in the drawing.
PL 196 372 B1PL 196 372 B1
Opis wynalazkuDescription of the invention
Przedmiotem wynalazku są nowe estry etylowe kwasu 3-metylo-3-(4-metylo-1-cykloheksen-1-ylo)butanowego, o wzorach 1 i 2 przedstawionych na rysunku, i sposób ich wytwarzania.The subject of the invention are new ethyl esters of 3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic acid, of formulas 1 and 2 shown in the drawing, and a method for their preparation.
Oba estry etylowe mogą znaleźć zastosowanie, jako składniki kompozycji zapachowych, w przemyśle perfumeryjnym lub spożywczym.Both ethyl esters can be used as ingredients of fragrance compositions in the perfume or food industry.
Istotą wynalazku są nowe estry etylowe kwasu 3-metylo-3-(4-metylo-1-cykloheksen-1-ylo)butanowego, o wzorach 1 i 2 przedstawionych na rysunku.The essence of the invention is the new ethyl esters of 3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic acid, of formulas 1 and 2 shown in the drawing.
Sposób, według wynalazku, polega na tym, że (R)-(+)-pulegon albo (S)-(-)-pulegon redukuje się borowodorkiem sodu, a uzyskany w ten sposób cis-(1R, 5R)-pulegol albo cis-(1S, 5S)-pulegol poddaje się reakcji przegrupowania Claisena metodą ortooctanową.The method according to the invention consists in reducing (R)-(+)-pulegon or (S)-(-)-pulegon with sodium borohydride and subjecting the resulting cis-(1R,5R)-pulegol or cis-(1S,5S)-pulegol to a Claisen rearrangement reaction using the orthoacetate method.
Otrzymany ester etylowy kwasu (4R)-(+)-3-metylo-3-(4-metylo-1-cykloheksen-1-ylo)butanowego, o wzorze 1, charakteryzuje się intensywnym zapachem owocowym z nutą dojrzałej gruszki, a ester etylowy kwasu (4S)-(-)-3-metylo-3-(4-metylo-1-cykloheksen-1-ylo)butanowego, o wzorze 2, posiada intensywny zapach owocowo-gruszkowy z nutą drzewną.The obtained (4R)-(+)-3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic acid ethyl ester, of formula 1, is characterized by an intense fruity aroma with a note of ripe pear, and the (4S)-(-)-3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic acid ethyl ester, of formula 2, has an intense fruity-pear aroma with a note of wood.
Przedmiot wynalazku jest bliżej objaśniony w przykładach wykonania.The subject of the invention is explained in more detail in the examples.
P r z y k ł a d 1.Example 1.
Do ochłodzonego do temperatury 0°C roztworu 1,5 g (9,9 mmol) (R)-(+)-pulegonu w 18 cm3 metanolu i 3,6 cm3 wody wkrapla się 0,4 g (10,6 mmol) borowodorku sodu w 21 cm3 etanolu. Mieszanie kontynuuje się przez 2 godziny w temperaturze pokojowej. Po zakończeniu reakcji (TLC, jako eluent stosuje się heksan/aceton w stosunku 20:1), mieszaninę wylewa się do nasyconego roztworu chlorku sodu i produkt ekstrahuje kilkoma porcjami heksanu. Połączone warstwy heksanowe przemywa się wodą aż do uzyskania odczynu obojętnego a następnie suszy odwodnionym siarczanem magnezu (VI). Po oddestylowaniu rozpuszczalnika otrzymuje się 1,5 g surowego cis-(1R, 5R)-pulegolu (96% czystości według GC).To a solution of 1.5 g (9.9 mmol) of (R)-(+)-pulegon in 18 cm3 of methanol and 3.6 cm3 of water, cooled to 0°C, is added dropwise 0.4 g (10.6 mmol) of sodium borohydride in 21 cm3 of ethanol. Stirring is continued for 2 hours at room temperature. After completion of the reaction (TLC, hexane/acetone in a ratio of 20:1 used as the eluent), the mixture is poured into a saturated sodium chloride solution and the product is extracted with several portions of hexane. The combined hexane layers are washed with water until neutral and then dried with dehydrated magnesium sulfate. After distillation of the solvent, 1.5 g of crude cis-(1R,5R)-pulegol (96% purity according to GC) is obtained.
Otrzymany w ten sposób cis-(1R, 5R)-pulegol (1,5 g, 9,7 mmol), razem z 15 cm3 (78,3 mmol) ortooctanu etylu i katalityczną ilością kwasu propionowego (1 kropla), ogrzewa się w temperaturze 138°C przez 8 godzin, równocześnie w sposób ciągły oddestylowując alkohol etylowy z mieszaniny reakcyjnej. Przebieg reakcji kontroluje się za pomocą chromatografii gazowej i cienkowarstwowej. Po zakończeniu reakcji oddestylowuje się, pod zmniejszonym ciśnieniem, nadmiar nieprzereagowanego ortooctanu etylu a surowy produkt poddaje chromatografii kolumnowej (żel krzemionkowy, jako eluent stosuje się heksan/eter dietylowy, 80:1). Otrzymuje się 1,9 g czystego estru etylowego kwasu (4R)-(+)-3-metylo-3-(4-metylo-1-cykloheksen-1-ylo)butanowego (wzór 1), co stanowi 86% wydajności teoretycznej.The cis-(1R,5R)-pulegol thus obtained (1.5 g, 9.7 mmol), together with 15 cm3 (78.3 mmol) of ethyl orthoacetate and a catalytic amount of propionic acid (1 drop), was heated at 138°C for 8 hours, while ethyl alcohol was continuously distilled from the reaction mixture. The course of the reaction was monitored by gas and thin-layer chromatography. After completion of the reaction, the excess unreacted ethyl orthoacetate was distilled off under reduced pressure, and the crude product was subjected to column chromatography (silica gel, hexane/diethyl ether 80:1 as eluent). 1.9 g of pure (4R)-(+)-3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic acid ethyl ester (formula 1) was obtained, which is 86% of the theoretical yield.
Dane spektroskopowe i stałe fizyczne otrzymanego związku są następujące:The spectroscopic data and physical constants of the obtained compound are as follows:
[α]25 =+44,1° (c=5,63, aceton); n ^0=1,4630; 1H NMR (CDCl3): d = 0,91 (d, J=6,1 Hz 3H, CH3 -4), 1,10 i 1,13 (dwa s, 6H, (CH3)3C<), 1,20 (t, J=7,1 Hz, 3H, -OCH3CH3), 1,44-1,66 (m, 4H, CH3-grupy), 1,96-2,10 (m, 3H, CH3-grupa i H-4), 2,29 i 2,32 (układ AB, J=13,2 Hz, 2H, CH3-2), 4,04 (q, J=7,1 Hz, 2H, -OCH.2CH3), 5,41 (m, 1H, H-2);[α]25 =+44,1°(c=5,63,acetone); n ^0=1,4630;1H NMR(CDCl3):d = 0.91 (d, J=6.1 HWith3H, CH3 -4), 1.10 and 1.13 (two s, 6H, (CH3)3C<), 1.20 (t, J=7.1 Hz, 3H, -OCH3CH3), 1.44-1.66 (m, 4H, CH3-groups), 1.96-2.10 (m, 3H, CH3-group and H-4), 2.29 and 2.32 (AB system, J=13.2 Hz, 2H, CH3-2), 4.04 (q, J=7.1 Hz, 2H, -OCH.2CH3), 5.41 (m, 1H, H-2);
IR (film): v = 1748 (s, C=O), 1392 i 1372 (s, (CH3)3C<), 1232 i 1120 (s, C-O-C).IR (film): v = 1748 (s, C=O), 1392 and 1372 (s, (CH 3 ) 3 C<), 1232 and 1120 (s, COC).
P r z y k ł a d 2.Example 2.
Postępuje się tak jak w przykładzie 1, z tym że do przeprowadzenia reakcji stosuje się (S)-(-)-pulegon. Z 1,5 g (9,9 mmol) (S)-(-)-pulegonu otrzymuje się 1,5 g surowego cis-(1S, 5S)-pulegolu (97% czystości według GC).The procedure is as in Example 1, except that (S)-(-)-pulegone is used for the reaction. From 1.5 g (9.9 mmol) of (S)-(-)-pulegone, 1.5 g of crude cis-(1S,5S)-pulegol (97% purity by GC) is obtained.
W wyniku reakcji przegrupowania Claisena metodą ortooctanową surowego cis-(1S, 5S)-pulegolu (1,5 g, 9,7 mmol) otrzymuje się 1,8 g estru etylowego kwasu (4S)-(-)-3-metylo-3-(4-metylo-1-cykloheksen-1-ylo)butanowego (wzór 2), co stanowi 84% wydajności teoretycznej [a] 25 =-44,4° (c=3,87, aceton).As a result of the Claisen rearrangement reaction by the orthoacetate method of crude cis-(1S, 5S)-pulegol (1.5 g, 9.7 mmol), 1.8 g of (4S)-(-)-3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic acid ethyl ester (formula 2) was obtained, which is 84% of the theoretical yield [a] 25 =-44.4° (c=3.87, acetone).
Właściwości spektroskopowe estru (4S)-(-)-3-metylo-3-(4-metylo-1-cykloheksen-1-ylo)butanowego (wzór 2) są analogiczne jak estru (4R)-(+)-3-metylo-3-(4-metylo-1-cykloheksen-1-ylo)butanowego (wzór 1).The spectroscopic properties of (4S)-(-)-3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic ester (formula 2) are analogous to those of (4R)-(+)-3-methyl-3-(4-methyl-1-cyclohexen-1-yl)butanoic ester (formula 1).
PL 196 372 B1PL 196 372 B1
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| PL362877A PL196372B1 (en) | 2003-10-15 | 2003-10-15 | New 3-methyl-3- (4-methyl-1-cyclohexen-1-yl) butanoic acid ethyl esters and their preparation |
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| PL362877A PL196372B1 (en) | 2003-10-15 | 2003-10-15 | New 3-methyl-3- (4-methyl-1-cyclohexen-1-yl) butanoic acid ethyl esters and their preparation |
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