PL210544B1 - New (3S)-(+)-3-[(1S, 5R)-6, 6-dimethylbicyclo [3. 1. 0] hex-2-en-2-ylo] butane chiral acid and method of its manufacturing - Google Patents
New (3S)-(+)-3-[(1S, 5R)-6, 6-dimethylbicyclo [3. 1. 0] hex-2-en-2-ylo] butane chiral acid and method of its manufacturingInfo
- Publication number
- PL210544B1 PL210544B1 PL385340A PL38534008A PL210544B1 PL 210544 B1 PL210544 B1 PL 210544B1 PL 385340 A PL385340 A PL 385340A PL 38534008 A PL38534008 A PL 38534008A PL 210544 B1 PL210544 B1 PL 210544B1
- Authority
- PL
- Poland
- Prior art keywords
- dimethylbicyclo
- hex
- ethanol
- new
- extracted
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 14
- 239000002253 acid Substances 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000001273 butane Substances 0.000 title 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 title 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- -1 (3S) - (+) - 3 - [(1S, 5R) -6,6-dimethylbicyclo [3.1.0] -hex-2-en-2-yl] butanoic acid Chemical compound 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000004809 thin layer chromatography Methods 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims 1
- 235000019341 magnesium sulphate Nutrition 0.000 claims 1
- 230000020477 pH reduction Effects 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku jest chiralny kwas (3S)-(+)-3-[(1S,5R)-6,6-dimetylobicyklo[3.1.0]heks-2-en-2-ylo]butanowy przeznaczony do syntezy laktonów terpenoidowych o potencjalnej aktywności biologicznej, głównie deterentnej oraz sposób wytwarzania nowego chiralnego γ,δ-nienasyconego kwasu.The subject of the invention is the chiral (3S) - (+) - 3 - [(1S, 5R) -6,6-dimethylbicyclo [3.1.0] hex-2-en-2-yl] butanoic acid intended for the synthesis of terpenoid lactones with potential biological activity, mainly deterential; and a method for producing a new chiral γ, δ-unsaturated acid.
Znana jest z publikacji Walkowicz M., Walkowicz C, Lochyński S., Polish J. Chem. 1981, 55, 2007-2013, synteza mieszaniny diastereoizomerycznych alkoholi allilowych E,Z z układem gem-dimetylobicyklo[3.1.0]heksanu, z których Z-izomer jest produktem pośrednim w syntezie tego kwasu.It is known from the publications of Walkowicz M., Walkowicz C, Lochyński S., Polish J. Chem. 1981, 55, 2007-2013, synthesis of the mixture of diastereoisomeric allylic alcohols E, Z with the gem-dimethylbicyclo [3.1.0] hexane system, of which the Z-isomer is an intermediate in the synthesis of this acid.
Nowy chiralny kwas (3S)-(+)-3-[(1S,5R)-6,6-dimetylobicyklo[3.1.0]heks-2-en-2-ylo]butanowy, o wzorze 1, ma określoną, jednoznaczną budowę przestrzenną.The new chiral (3S) - (+) - 3 - [(1S, 5R) -6,6-dimethylbicyclo [3.1.0] hex-2-en-2-yl] butanoic acid of formula 1 has a specific, unique spatial structure.
Sposób wytwarzania chiralnego kwasu (3S)-(+)-3-[(1S,5R)-6,6-dimetylobicyklo[3.1.0]heks-2-en-2-ylo]butanowego o wzorze 1, polega na tym, że ester o nazwie (3S)-(+)-3-[(1S,5R)-6,6-dimetylobicyklo[3.1.0]heks-2-en-2-ylo]-butanian etylu poddaje się hydrolizie zasadowej w roztworze KOH w etanolu. Zgodnie ze sposobem, ester w roztworze KOH w etanolu ogrzewa się, korzystnie w temperaturze 70°C, a po zakończeniu reakcji hydrolizy usuwa się etanol na wyparce rotacyjnej pod zmniejszonym ciśnieniem. Następnie pozostałość rozpuszcza się w wodzie i ekstrahuje się eterem dietylowym. Korzystnie fazę wodną po ekstrakcji zakwasza się 0.01 M roztworem HCl aż do otrzymania pH około 4-5 i czterokrotnie ekstrahuje eterem dietylowym. Fazę organiczną przemywa się solanką i suszy nad bezwodnym siarczanem magnezu, a po odparowaniu rozpuszczalnika otrzymuje się czysty produkt.The method of producing the chiral (3S) - (+) - 3 - [(1S, 5R) -6,6-dimethylbicyclo [3.1.0] hex-2-en-2-yl] butanoic acid of formula 1 is as follows: that the ester named (3S) - (+) - 3 - [(1S, 5R) -6,6-dimethylbicyclo [3.1.0] hex-2-en-2-yl] -butanoate is subjected to basic hydrolysis in solution KOH in ethanol. According to the process, the ester in a KOH solution in ethanol is heated, preferably at 70 ° C, and after the end of the hydrolysis reaction, the ethanol is removed by rotary evaporation under reduced pressure. The residue is then dissolved in water and extracted with diethyl ether. Preferably, the aqueous phase after extraction is acidified with 0.01 M HCl solution until the pH is approximately 4-5 and extracted four times with diethyl ether. The organic phase is washed with brine and dried over anhydrous magnesium sulfate to give the pure product after evaporation of the solvent.
Ponadto reakcję hydrolizy kontroluje się za pomocą chromatografii cienkowarstwowej (TLC).In addition, the hydrolysis reaction is monitored by thin layer chromatography (TLC).
Zaletą wynalazku jest uzyskiwanie półproduktu przeznaczonego do wytwarzania substancji o aktywności deterentnej. Deterenty pokarmowe zwane inaczej antyfidantami lub repelentami smakowymi stanowią szeroką grupę selektywnie działających, bioracjonalnych insektycydów, głównie pochodzenia roślinnego, hamujących lub uniemożliwiających żerowanie owadów poprzez oddziaływanie na ich narządy smaku. Wynikiem działania tego typu związku jest zaprzestanie żerowania i w efekcie śmierć głodowa owadów, pozostających w pobliżu pokarmu. Są praktycznie nieszkodliwe dla człowieka i zwierząt stałocieplnych oraz mało szkodliwe dla naturalnych wrogów zwalczanych szkodników.The advantage of the invention is the preparation of an intermediate intended for the production of substances with detecting activity. Food detectors, otherwise known as antifidants or flavor repellants, constitute a wide group of selectively acting, bio-national insecticides, mainly of plant origin, that inhibit or prevent insect feeding by acting on their taste organs. The result of this type of relationship is the cessation of feeding and, as a result, starvation of insects remaining in the vicinity of food. They are practically harmless to humans and warm-blooded animals and not harmful to the natural enemies of the pest to be controlled.
Sposób według wynalazku jest przedstawiony w przykładzie wykonania:The method according to the invention is presented in an embodiment:
P r z y k ł a d:P r z k ł a d:
W kolbie okrągłodennej o pojemności 50 ml zaopatrzonej w chłodnicę zwrotną umieszcza się 0.80 g (3.6 mmola) estru o nazwie (3S)-(+)-3-[(1S,5R)-6,6-dimetylobicyklo[3.1.0]heks-2-en-2-ylo]-butanian etylu oraz 0.29 g (5.17 mmola) KOH w 26.6 ml etanolu. Mieszaninę ogrzewa się w łaźni olejowej w temp. 70°C. Przebieg reakcji kontroluje się metodą chromatografii cienkowarstwowej wykonując co godzinę płytki chromatograficzne z użyciem mieszaniny eluującej heksan:octan etylu (4:1). Mieszaninę ogrzewa się przez 2 godziny. Po zakończeniu reakcji etanol odparowuje się na wyparce obrotowej, a pozostałość rozpuszcza się w wodzie i ekstrahuje fazę wodną eterem dietylowym 4 razy. Fazę wodną po ekstrakcji zakwasza się 0.01 M roztworem HCl, aż do otrzymania pH około 4-5. Następnie fazę wodną ekstrahuje się czterokrotnie eterem dietylowym. Fazę organiczną przemywa się dwa razy solanką i suszy nad bezwodnym siarczanem magnezu. Po odparowaniu rozpuszczalnika otrzymuje się 0.58 g czystego produktu.0.80 g (3.6 mmol) of an ester named (3S) - (+) - 3 - [(1S, 5R) -6,6-dimethylbicyclo [3.1.0] hex are placed in a 50 ml round bottom flask equipped with a reflux condenser. Ethyl -2-en-2-yl] -butanoate and 0.29 g (5.17 mmol) of KOH in 26.6 ml of ethanol. The mixture is heated in an oil bath at 70 ° C. The progress of the reaction is monitored by thin layer chromatography by making hourly chromatography plates with an eluting mixture of hexane: ethyl acetate (4: 1). The mixture is heated for 2 hours. After completion of the reaction, the ethanol is evaporated off on a rotary evaporator, the residue is dissolved in water and the aqueous phase is extracted with diethyl ether 4 times. The aqueous phase after extraction is acidified with 0.01 M HCl solution until a pH of about 4-5 is obtained. The aqueous phase is then extracted four times with diethyl ether. The organic phase is washed twice with brine and dried over anhydrous magnesium sulfate. After evaporating the solvent, 0.58 g of pure product is obtained.
Produkt otrzymany powyższym sposobem posiada następujące właściwości fizyczne i spektralne:The product obtained by the above method has the following physical and spectral properties:
[a]D24 = +112° (1.0 CHCI3); nD 26 =1.4751[α] D 24 = + 112 ° (1.0 CHCl 3 ); n D 26 = 1.4751
IR (film, cm-1): 2926(s), 2679(m), 1709(vs), 1633(w), 1411(ms), 1374(m), 1292(s), 1195(m) 1H NMR (CDCI3, δ, ppm): 0.74, 1.02 (2s, 6H przy C-7 i C-8); 1.05 (d, J=6.9 4C Hz, 3H przy C10); 1.27 (t, J=7.1 Hz, 1H przy C-5); 1.55 (dd, J=6.4, 2.9 Hz, 1H przy C-1); 2.00 (d, J=18.0 Hz, 1H przy C-4); 2.27 (dd, J=15.6, 8.5 Hz, 1H przy C-11); 2.38 (dd, J=18.1, 7.7 Hz, H przy C-4); 2.52 (dd, J=15.5, 6.2 Hz, 1H przy C-11); 2.73 (q, J=6.9, 1 H przy C-9); 5.14 (s, 1H przy C-3) 13C NMR (CDCI3, δ, ppm): 13.18 (C-8); 19.17 (C-7); 19.42 (C-6); 26.37 (C-10); 28.99 (C-5); 31.81 (C-4); 31.94 (C-9); 38.00 (C-1); 39.91 (C-11); 122.21 (C-3); 147.43 (C-2); 179.37 (C-12).IR (film, cm -1): 2926 (s), 2679 (m), 1709 (vs), 1633 (w), 1411 (ms), 1374 (m), 1292 (s), 1195 (m) 1H NMR (CDCl3, δ, ppm): 0.74, 1.02 (2s, 6H at C-7 and C-8); 1.05 (d, J = 6.94C Hz, 3H at C10); 1.27 (t, J = 7.1 Hz, 1H at C-5); 1.55 (dd, J = 6.4, 2.9 Hz, 1H at C-1); 2.00 (d, J = 18.0 Hz, 1H at C-4); 2.27 (dd, J = 15.6, 8.5 Hz, 1H at C-11); 2.38 (dd, J = 18.1, 7.7 Hz, H at C-4); 2.52 (dd, J = 15.5,6.2 Hz, 1H at C-11); 2.73 (q, J = 6.9, 1H at C-9); 5.14 (s, 1H at C-3). 13 C NMR (CDCl 3, δ, ppm): 13.18 (C-8); 19.17 (C-7); 19.42 (C-6); 26.37 (C-10); 28.99 (C-5); 31.81 (C-4); 31.94 (C-9); 38.00 (C-1); 39.91 (C-11); 122.21 (C-3); 147.43 (C-2); 179.37 (C-12).
PL 210 544 B1PL 210 544 B1
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| Application Number | Priority Date | Filing Date | Title |
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| PL385340A PL210544B1 (en) | 2008-06-02 | 2008-06-02 | New (3S)-(+)-3-[(1S, 5R)-6, 6-dimethylbicyclo [3. 1. 0] hex-2-en-2-ylo] butane chiral acid and method of its manufacturing |
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| Application Number | Priority Date | Filing Date | Title |
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| PL385340A PL210544B1 (en) | 2008-06-02 | 2008-06-02 | New (3S)-(+)-3-[(1S, 5R)-6, 6-dimethylbicyclo [3. 1. 0] hex-2-en-2-ylo] butane chiral acid and method of its manufacturing |
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| Publication Number | Publication Date |
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| PL385340A1 PL385340A1 (en) | 2009-12-07 |
| PL210544B1 true PL210544B1 (en) | 2012-01-31 |
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| PL385340A PL210544B1 (en) | 2008-06-02 | 2008-06-02 | New (3S)-(+)-3-[(1S, 5R)-6, 6-dimethylbicyclo [3. 1. 0] hex-2-en-2-ylo] butane chiral acid and method of its manufacturing |
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- 2008-06-02 PL PL385340A patent/PL210544B1/en not_active IP Right Cessation
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| PL385340A1 (en) | 2009-12-07 |
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