PL221469B1 - (-)-O-isoamyloximinofenchane and its preparation method - Google Patents
(-)-O-isoamyloximinofenchane and its preparation methodInfo
- Publication number
- PL221469B1 PL221469B1 PL405307A PL40530713A PL221469B1 PL 221469 B1 PL221469 B1 PL 221469B1 PL 405307 A PL405307 A PL 405307A PL 40530713 A PL40530713 A PL 40530713A PL 221469 B1 PL221469 B1 PL 221469B1
- Authority
- PL
- Poland
- Prior art keywords
- reaction
- formula
- preparation
- isoamyloxyiminophenchane
- crude product
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 5
- 239000002904 solvent Substances 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
- 239000012043 crude product Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- LHXDLQBQYFFVNW-OIBJUYFYSA-N (-)-Fenchone Chemical compound C1C[C@@]2(C)C(=O)C(C)(C)[C@@H]1C2 LHXDLQBQYFFVNW-OIBJUYFYSA-N 0.000 claims description 3
- 229930006729 (1R,4S)-fenchone Natural products 0.000 claims description 3
- CZHLPWNZCJEPJB-UHFFFAOYSA-N 1-chloro-3-methylbutane Chemical compound CC(C)CCCl CZHLPWNZCJEPJB-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- LHXDLQBQYFFVNW-UHFFFAOYSA-N alpha-fenchone Natural products C1CC2(C)C(=O)C(C)(C)C1C2 LHXDLQBQYFFVNW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 238000010934 O-alkylation reaction Methods 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 3
- 235000011293 Brassica napus Nutrition 0.000 description 2
- 240000008100 Brassica rapa Species 0.000 description 2
- 235000000540 Brassica rapa subsp rapa Nutrition 0.000 description 2
- 235000016954 Ribes hudsonianum Nutrition 0.000 description 2
- 240000001890 Ribes hudsonianum Species 0.000 description 2
- 235000001466 Ribes nigrum Nutrition 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- -1 (-) - O-isoamyloxyimino Chemical group 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Description
Przedmiotem wynalazku jest (-)-O-izoamyloksyiminofenchan znajdujący zastosowanie jako związek zapachowy scharakteryzowany jako rzepa i czarna porzeczka.The subject of the invention is (-) - O-isoamyloxyiminofenchane for use as a fragrance compound characterized as turnip and black currant.
Przedmiotem wynalazku jest również sposób wytwarzania(-)-O-izoamyloksyiminofenchanu.The invention also relates to a process for the preparation of (-) - O-isoamyloxyiminofenchane.
(-)-O-izoamyloksyiminofenchan oraz sposób jego wytwarzania nie zostały dotychczas opisane w literaturze.(-) - O-isoamyloxyiminophenchane and the method of its preparation have not been described in the literature so far.
Istotą rozwiązania według wynalazku jest (-)-O-izoamyloksyiminofenchan o wzorze 1.The essence of the invention is the (-) - O-isoamyloxyiminophenchane of the formula I.
Istotą wynalazku jest również sposób wytwarzania (-)-O-izoamyloksyiminofenchanu o wzorze 1 polegający na tym, że sól sodową oksymu (-)-fenchonu poddaje się reakcji O-alkilowania chlorkiem izoamylu, przy czym reakcję prowadzi się pod refluksem w obecności toluenu jako rozpuszczalnika przez 24 godziny, a następnie po zakończeniu reakcji do kolby z mieszaniną reakcyjną wlewa się nasycony roztwór wodorowęglanu sodu, całość umieszcza się w rozdzielaczu, oddziela się warstwę organiczną od wodnej, a tę ostatnią ekstrahuje się dwukrotnie eterem dietylowym i połączone warstwy organiczne suszy się nad bezwodnym siarczanem magnezu, następnie odfiltrowuje się środek suszący i odparowuje się rozpuszczalniki.The essence of the invention is also a process for the preparation of (-) - O-isoamyloxyiminophenchane of the formula I, which consists in subjecting the sodium salt of (-) - fenchone oxime to an O-alkylation reaction with isoamyl chloride, the reaction being carried out under reflux in the presence of toluene as a solvent for 24 hours, and then after completion of the reaction, saturated sodium bicarbonate solution is poured into the flask with the reaction mixture, the whole is placed in a separating funnel, the organic layer is separated from the aqueous layer, the latter is extracted twice with diethyl ether and the combined organic layers are dried over anhydrous with magnesium sulfate, then the drying agent is filtered off and the solvents are evaporated off.
Korzystnie surowy produkt oczyszcza się za pomocą frakcyjnej destylacji próżniowej.Preferably, the crude product is purified by vacuum fractional distillation.
Korzystnie przebieg reakcji kontroluje się przy użyciu chromatografii gazowej.Preferably the course of the reaction is monitored by gas chromatography.
Wynalazek został bliżej przedstawiony w przykładzie jego wykonania oraz określony wzorem 1.The invention is described in more detail in an embodiment thereof and is defined by formula 1.
P r z y k ł a d 1P r z k ł a d 1
W dwuszyjnej, okrągłodennej kolbie o pojemności 100 ml, zaopatrzonej w kosz grzejny, chłodnicę zwrotną oraz zabezpieczonej przed dostępem wilgoci umieszcza się 5.0 g (29.8 mmol) oksymu (-)-fenchonu, 50 ml toluenu i 2 g (50 mmol) 60% wodorku sodu. Po całkowitym wydzieleniu się wodoru do mieszaniny reakcyjnej wkrapla się 3.51 g (32.9 mmol, 4.0 ml) chlorku izoamylu. Reakcję prowadzi się pod refluksem. Przebieg reakcji monitoruje się za pomocą chromatografii gazowej. Po upływie 24 h stwierdza się całkowite przereagowanie substratu. Mieszaninę poreakcyjną chłodzi się do temperatury pokojowej i dodaje 50 ml nasyconego roztworu wodorowęglanu sodu. Zawartość kolby umieszcza się w rozdzielaczu, oddziela warstwę organiczną od wodnej, a tę drugą ekstrahuje się dwukrotnie 20 ml eteru dietylowego. Połączone warstwy organiczne suszy się nad bezwodnym siarczanem magnezu. Po osuszeniu, środek suszący odfiltrowuje się, a rozpuszczalniki odparowuje na wyparce rotacyjnej. Otrzymuje się 4.70 g surowego produktu o czystości 87.5%. Surowy produkt oczyszcza się za pomocą frakcyjnej destylacji próżniowej w wyniku której otrzymuje się 3.50 g (-)-O-izoamyloksyimino-fenchan, co stanowi 49.3% wydajności.5.0 g (29.8 mmol) of (-) - fenchone oxime, 50 ml of toluene and 2 g (50 mmol) of 60% hydride are placed in a 100 ml two-necked round-bottom flask equipped with a heating basket, a reflux condenser and protected against the ingress of moisture. sodium. After complete evolution of hydrogen, 3.51 g (32.9 mmol, 4.0 ml) of isoamyl chloride are added dropwise to the reaction mixture. The reaction is carried out under reflux. The course of the reaction is monitored by gas chromatography. After 24 h, complete conversion of the substrate is noted. The reaction mixture is cooled to room temperature and 50 ml of saturated sodium bicarbonate solution are added. The contents of the flask were placed in a separating funnel, the organic and aqueous layers were separated, and the latter was extracted twice with 20 ml of diethyl ether. The combined organic layers were dried over anhydrous magnesium sulfate. After drying, the drying agent is filtered off and the solvents are evaporated on a rotary evaporator. 4.70 g of crude product with a purity of 87.5% are obtained. The crude product is purified by fractional vacuum distillation which gives 3.50 g of (-) - O-isoamyloxyimino fenchate, representing a yield of 49.3%.
Produkt otrzymany według przykładu posiada następujące właściwości fizyczne i spektralne:The product obtained according to the example has the following physical and spectral properties:
Tw= 130°C (2 mbar); [a] |s = -27.8°, zapach rzepy, czarnej porzeczki.T w = 130 ° C (2 mbar); [a] | s = -27.8 °, smell of turnips, black currant.
HRMS (TOFMS EI+) obliczone dla [C15H27NO] 237.2093, znaleziono 237.2094 IR (KBr, cm-1): 2957 (vs), 2868 (vs), 1654 (w), 1467 (vs); 1381 (s), 1360 (s), 1068 (s), 944 (m) 1H NMR (CDCI3, δ, ppm): 0.95 (d, 6H, przy C-14 i C-15, 2J=6.0 Hz), 1.24 (s, 3H, przy C-10), 1.25 i 1.28 (2s, 6H, przy C-8 i C-9), 1.34 (d, 1H, 2J=6.0 Hz przy C-7), 1.43-1.49 (m, 1H, przy C-5), 1.53-1.69 (m, 4H, przy C-5, C-6 i C-12), 1.71-1.75 (m, 1H, przy C-7 i C-13), 1.79-1.82 (m, 2H przy C-4 i C-6), 3.98 (t, 2H, przy C-11, 2J=6.0 Hz) 13C NMR (CDCI3, δ, ppm): 17.23 (C-10), 22.58 i 23.38 (C-8 i C-9), 22.73 (C-14 i C-15), 25.19 (C-13), 25.31 (C-6), 34.49 (C-5), 38.01 (C-12) 43.40 (C-7), 44.33 (C-3), 48.59 (C-4), 49.91 (C-1), 71.78 (C-11), 172.02 (C-2).HRMS (TOFMS EI +) calculated for [C15H27NO] 237.2093, found 237.2094 IR (KBr, cm -1 ): 2957 (vs), 2868 (vs), 1654 (w), 1467 (vs); 1381 (s), 1360 (s), 1068 (s), 944 (m) 1H NMR (CDCl3, δ, ppm): 0.95 (d, 6H, at C-14 and C-15, 2 J = 6.0 Hz ), 1.24 (s, 3H, at C-10), 1.25 and 1.28 (2s, 6H, at C-8 and C-9), 1.34 (d, 1H, 2 J = 6.0 Hz at C-7), 1.43 -1.49 (m, 1H, at C-5), 1.53-1.69 (m, 4H, at C-5, C-6 and C-12), 1.71-1.75 (m, 1H, at C-7 and C- 13), 1.79-1.82 (m, 2H at C-4 and C-6), 3.98 (t, 2H, at C-11, 2 J = 6.0 Hz) 13 C NMR (CDCl3, δ, ppm): 17.23 ( C-10), 22.58 and 23.38 (C-8 and C-9), 22.73 (C-14 and C-15), 25.19 (C-13), 25.31 (C-6), 34.49 (C-5), 38.01 (C-12) 43.40 (C-7), 44.33 (C-3), 48.59 (C-4), 49.91 (C-1), 71.78 (C-11), 172.02 (C-2).
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL405307A PL221469B1 (en) | 2013-09-11 | 2013-09-11 | (-)-O-isoamyloximinofenchane and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL405307A PL221469B1 (en) | 2013-09-11 | 2013-09-11 | (-)-O-isoamyloximinofenchane and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL405307A1 PL405307A1 (en) | 2014-04-14 |
| PL221469B1 true PL221469B1 (en) | 2016-04-29 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL405307A PL221469B1 (en) | 2013-09-11 | 2013-09-11 | (-)-O-isoamyloximinofenchane and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL221469B1 (en) |
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2013
- 2013-09-11 PL PL405307A patent/PL221469B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PL405307A1 (en) | 2014-04-14 |
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