PL234190B1 - Ethyl (2E)-2-[(2R,5R)-2-methyl-5-(prop-1-en-2-yl)cyclohexylidene]butanoate and method for producing it - Google Patents
Ethyl (2E)-2-[(2R,5R)-2-methyl-5-(prop-1-en-2-yl)cyclohexylidene]butanoate and method for producing it Download PDFInfo
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- PL234190B1 PL234190B1 PL423671A PL42367117A PL234190B1 PL 234190 B1 PL234190 B1 PL 234190B1 PL 423671 A PL423671 A PL 423671A PL 42367117 A PL42367117 A PL 42367117A PL 234190 B1 PL234190 B1 PL 234190B1
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- butanoate
- ethyl
- cyclohexylidene
- prop
- methyl
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- 238000004519 manufacturing process Methods 0.000 title claims description 3
- WULJHPLHRZZNGH-QWBYSSASSA-N ethyl (2E)-2-[(2R,5R)-2-methyl-5-prop-1-en-2-ylcyclohexylidene]butanoate Chemical compound C[C@H]1\C(\C[C@@H](CC1)C(=C)C)=C(\C(=O)OCC)/CC WULJHPLHRZZNGH-QWBYSSASSA-N 0.000 title 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 7
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- GYUCVQSNZFRDRL-UHFFFAOYSA-N ethyl 2-diethoxyphosphorylbutanoate Chemical compound CCOC(=O)C(CC)P(=O)(OCC)OCC GYUCVQSNZFRDRL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004809 thin layer chromatography Methods 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000006130 Horner-Wadsworth-Emmons olefination reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- -1 (+) - dihydrocarvone ketone Chemical class 0.000 description 1
- 229930007066 (+)-dihydrocarvone Natural products 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
- Fats And Perfumes (AREA)
- Seasonings (AREA)
Description
Opis wynalazkuDescription of the invention
Przedmiotem wynalazku (2E)-2-[(2R,5R)-2-metylo-5-(prop-1-en-2-ylo)cykloheksylideno]butanian etylu znajdujący zastosowanie w przemyśle kosmetycznym i spożywczym jako związek zapachowy.The subject of the invention is ethyl (2E) -2 - [(2R, 5R) -2-methyl-5- (prop-1-en-2-yl) cyclohexylidene] butanoate] for use in the cosmetics and food industry as a fragrance.
Dotychczas nie jest znany z literatury związek będący przedmiotem wynalazku oraz sposób jego wytwarzania.So far, the compound being the subject of the invention and the method of its production are unknown from the literature.
Istotą rozwiązania według wynalazku jest (2E)-2-[(2R,5R)-2-metylo-5-(prop-1-en-2-ylo)cykloheksylideno]butanian etylu o wzorze 1.The essence of the solution according to the invention is ethyl (2E) -2 - [(2R, 5R) -2-methyl-5- (prop-1-en-2-yl) cyclohexylidene] butanoate of formula 1.
Istotą rozwiązania według wynalazku jest również sposób wytwarzania (2E)-2-[(2R,5R)-2-metylo5-(prop-1-en-2-ylo)cykloheksylideno]butanianu etylu o wzorze 1 polegający na tym, że (+)-dihydrokarown, poddaje się reakcji HWE z użyciem 2-(dietoksyfosforyl)butanianu etylu jako reagenta i tetrahydrofuranu jako środowiska reakcji, przy czym reakcja prowadzona jest w łaźni lodowej, a po zakończeniu procesu odparowuje się rozpuszczalniki, a produkt oczyszcza się przy wykorzystaniu chromatografii kolumnowej, natomiast przebieg reakcji kontroluje się przy wykorzystaniu chromatografii cienkowarstwowej.The essence of the solution according to the invention is also the method for the preparation of ethyl (2E) -2 - [(2R, 5R) -2-methyl-5- (prop-1-en-2-yl) cyclohexylidene] butanoate of formula 1, which consists in the fact that (+ ) -dihydrocarown, reacting with HWE using ethyl 2- (diethoxyphosphoryl) butanoate as the reagent and tetrahydrofuran as the reaction medium, the reaction being carried out in an ice bath, and after completion of the process, the solvents were evaporated and the product purified by column chromatography and the course of the reaction is monitored by thin layer chromatography.
Przedmiot wynalazku został bliżej przedstawiony wzorem, za pomocą schematu reakcji oraz w przykładzie wykonania.The subject of the invention is illustrated in more detail by the formula, the reaction scheme, and the embodiment.
P r z y k ł a d 1P r z k ł a d 1
Ester będący (2E)-2-[(2R,5R)-2-metylo-5-(prop-1-en-2-ylo)cykloheksylideno]butanianem etylu został otrzymany w wyniku reakcji Hornera-Wadswortha-Emmonsa (HWE) (+)-dihydrokarwonu z 2-(dietoksyfosforylo)butanianu etylu wobec wodorkiem sodu. Do dwuszyjnej kolby okrągłodennej umieszczonej w łaźni lodowej, zaopatrzonej w mieszadło magnetyczne, chłodnicę zwrotną i zabezpieczonej przed dostępem wilgoci wsypano 0,45 g (19 mmol) wodorku sodu oraz wkroplono przy jednoczesnym mieszaniu 10 ml tetrahydrofuranu. Następnie 1,5 g (2,0 mmol) 2-(dietoksyfosforyl)butanianu etylu w 10 ml tetrahydrofuranu i całość mieszano przez 15 minut. Po tym czasie zostało wkroplone, przy jednoczesnym mieszaniu, roztwór 0,5 g ketonu, będącego (+)-dihydrokarwonem, w 20 ml tetrahydrofuranu. Po 30 minutach od zakończenia wkraplania łaźnia lodowa została zdjęta. Reakcja przebiegała według schematu (rys. 1).The ethyl (2E) -2 - [(2R, 5R) -2-methyl-5- (prop-1-en-2-yl) cyclohexylidene] butanoate] butanoate was prepared by the Horner-Wadsworth-Emmons (HWE) reaction ( +) - dihydrocarone from ethyl 2- (diethoxyphosphoryl) butanoate in the presence of sodium hydride. 0.45 g (19 mmol) of sodium hydride was poured into a two-necked round bottom flask placed in an ice bath, equipped with a magnetic stirrer, a reflux condenser and protected against moisture, and 10 ml of tetrahydrofuran was added dropwise with stirring. Then 1.5 g (2.0 mmol) of ethyl 2- (diethoxyphosphoryl) butanoate in 10 ml of tetrahydrofuran and the mixture were stirred for 15 minutes. After this time, a solution of 0.5 g of the (+) - dihydrocarvone ketone in 20 ml of tetrahydrofuran was added dropwise while stirring. The ice bath was removed 30 minutes after completion of the dropwise addition. The reaction proceeded according to the scheme (Fig. 1).
Reakcja była kontrolowana za pomocą TLC i prowadzona do momentu całkowitego przereagowania substratu (72 h). Po zakończeniu reakcji do mieszaniny reakcyjnej dodano 45 ml wody destylowanej i całość ekstrahowano trzykrotnie 70 ml porcjami heksanu. Fazę organiczną wysuszono bezwodnym siarczanem magnezu i przesączono. Następnie odparowano nadmiar rozpuszczalnika. Otrzymano 0,21 g surowego produktu, który następnie oczyszczono przy użyciu kolumny chromatograficznej typu „Flash” jako eluent stosując heksan i octan etylu w stosunku 5:3. Uzyskano 0,14 g czystego produktu co stanowi 27% wydajności.The reaction was monitored by TLC and continued until the starting material was completely consumed (72 h). After completion of the reaction, 45 ml of distilled water was added to the reaction mixture, and the mixture was extracted three times with 70 ml portions of hexane. The organic phase was dried over anhydrous magnesium sulfate and filtered. The excess solvent was then evaporated. 0.21 g of crude product was obtained, which was then purified by flash chromatography column using 5: 3 hexane and ethyl acetate as eluent. 0.14 g of pure product was obtained, which is 27% yield.
Produkt otrzymany według przykładu posiada następujące właściwości fizyczne i spektralne:The product obtained according to the example has the following physical and spectral properties:
Wzór sumaryczny: C16H26O2Summary formula: C16H26O2
Masa molowa: 250,37 [α]24 = +15.70 (c = 1.0, CH3OH), n20 = 1.5069Molar mass: 250.37 [α] 24 = +15.70 (c = 1.0, CH3OH), n 20 = 1.5069
HRMS: (TOFMS ES+) obliczone dla [C16H26O2] 250.1855, znaleziono 250.2125.HRMS: (TOFMS ES +) calcd for [C16H26O2] 250.1855, found 250.2125.
1H NMR: (601 MHz, CDCI3, δ, ppm) 1.12-1.20 (m, 3H przy C-16), 1.28 (d, J = 4.5 Hz, 3H przy C-10), 1.59 (dd, J = 17.7 Hz, J = 8.9 Hz, 2H przy C-4), 1.78 (dd, J = 5.0 Hz i J = 2.8 Hz, 1H przy C-17), 1.78 (s, 3H przy C-9), 1.84-1.90 (m, 2H przy C-3), 2.01 (dd, J = 6.0 Hz i J = 3.2 Hz, 2H przy C-6), 2.13 -2.22 (m, 1H przy C-2), 2.60 (q, J = 7.3 Hz i J = 3,4 Hz, 2H przy C-15), 4.19 (q, J = 7.4 Hz i J = 3.5 Hz, 2H przy C-13), 4.72 (s, 1H przy C-8), 4.79 (s, 1H przy C-8) 13C NMR: (151 MHz, CDCh, δ, ppm) 14.21 (C-14), 14.31 (C-16), 19.67 (C-9), 20.69 (C-8), 21.89 (C-15), 30.11 (C-4), 31.34 (C-2), 31.63 (C-3), 34.83 (C-6), 41.24 (C-5), 59.65 (C-13), 109.72 (C-8), 135.31 (C-11), 148.35 (C-1), 154.94 (C-7), 168.38 (C-12)1H NMR: (601 MHz, CDCl3, δ, ppm) 1.12-1.20 (m, 3H at C-16), 1.28 (d, J = 4.5 Hz, 3H at C-10), 1.59 (dd, J = 17.7 Hz , J = 8.9 Hz, 2H @ C-4), 1.78 (dd, J = 5.0 Hz and J = 2.8 Hz, 1H @ C-17), 1.78 (s, 3H @ C-9), 1.84-1.90 (m , 2H at C-3), 2.01 (dd, J = 6.0 Hz and J = 3.2 Hz, 2H at C-6), 2.13-2.22 (m, 1H at C-2), 2.60 (q, J = 7.3 Hz and J = 3.4 Hz, 2H at C-15), 4.19 (q, J = 7.4 Hz and J = 3.5 Hz, 2H at C-13), 4.72 (s, 1H at C-8), 4.79 (s , 1H at C-8) 13 C NMR: (151 MHz, CDCl 2, δ, ppm) 14.21 (C-14), 14.31 (C-16), 19.67 (C-9), 20.69 (C-8), 21.89 (C-15), 30.11 (C-4), 31.34 (C-2), 31.63 (C-3), 34.83 (C-6), 41.24 (C-5), 59.65 (C-13), 109.72 ( C-8), 135.31 (C-11), 148.35 (C-1), 154.94 (C-7), 168.38 (C-12)
PL 234 190 Β1PL 234 190 Β1
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| Application Number | Priority Date | Filing Date | Title |
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| PL423671A PL234190B1 (en) | 2017-12-01 | 2017-12-01 | Ethyl (2E)-2-[(2R,5R)-2-methyl-5-(prop-1-en-2-yl)cyclohexylidene]butanoate and method for producing it |
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| PL423671A PL234190B1 (en) | 2017-12-01 | 2017-12-01 | Ethyl (2E)-2-[(2R,5R)-2-methyl-5-(prop-1-en-2-yl)cyclohexylidene]butanoate and method for producing it |
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| Publication Number | Publication Date |
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| PL423671A1 PL423671A1 (en) | 2019-06-03 |
| PL234190B1 true PL234190B1 (en) | 2020-01-31 |
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