PL217516B1 - (-)-(1R)-(ethoxyimine)fenchone and process for the preparation thereof - Google Patents
(-)-(1R)-(ethoxyimine)fenchone and process for the preparation thereofInfo
- Publication number
- PL217516B1 PL217516B1 PL398494A PL39849412A PL217516B1 PL 217516 B1 PL217516 B1 PL 217516B1 PL 398494 A PL398494 A PL 398494A PL 39849412 A PL39849412 A PL 39849412A PL 217516 B1 PL217516 B1 PL 217516B1
- Authority
- PL
- Poland
- Prior art keywords
- reaction
- ethoxyimino
- fenchone
- formula
- fenchane
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 11
- LHXDLQBQYFFVNW-UHFFFAOYSA-N Fenchone Chemical compound C1CC2(C)C(=O)C(C)(C)C1C2 LHXDLQBQYFFVNW-UHFFFAOYSA-N 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 3
- LHXDLQBQYFFVNW-XCBNKYQSSA-N (+)-Fenchone Natural products C1C[C@]2(C)C(=O)C(C)(C)[C@H]1C2 LHXDLQBQYFFVNW-XCBNKYQSSA-N 0.000 title 1
- 229930006735 fenchone Natural products 0.000 title 1
- 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
- HINAOCRDJFBYGD-UHFFFAOYSA-N fenchane Chemical compound C1CC2C(C)(C)CC1(C)C2 HINAOCRDJFBYGD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- -1 ethoxyimino Chemical group 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 238000010992 reflux Methods 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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 3
- 238000004508 fractional distillation Methods 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 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
- 229930006738 fenchane Natural products 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012047 saturated solution Substances 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 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
- 238000001035 drying 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
- 238000005259 measurement Methods 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)
- Indole Compounds (AREA)
Description
Opis wynalazkuDescription of the invention
Przedmiotem wynalazku jest (-)-(1 R,4S)-(etoksyimino)fenchan znajdujący zastosowanie jako związek zapachowy oraz sposób jego wytwarzania.The present invention relates to (-) - (1R, 4S) - (ethoxyimino) fenchan for use as a fragrance and a method for its preparation.
Dotychczas (-)-(1R,4S)-(etoksyimino)fenchan nie został opisany w literaturze.So far, (-) - (1R, 4S) - (ethoxyimino) fenchan has not been described in the literature.
Wynalazek dotyczy (-)-(1 R,4S)-(etoksyimino)fenchanu o wzorze 1. Wynalazek przedstawia również sposób wytwarzania (-)-(1R,4S)-(etoksyimino)fenchanuo wzorze I polegający na tym, że sól sodową oksymu (-)-fenchonu poddaje się reakcji O-alkilowania jodkiem etylu w obecności toluenu jako rozpuszczalnika, przy czym reakcję prowadzi się pod refluksem.The invention relates to (-) - (1R, 4S) - (ethoxyimino) fenchan of the formula 1. The invention also provides a method for the preparation of (-) - (1R, 4S) - (ethoxyimino) fenchan of the formula I, wherein the sodium salt of oxime (-) - fenchone is subjected to an O-alkylation reaction with ethyl iodide in the presence of toluene as a solvent, the reaction being carried out under reflux.
Korzystnie po zakończeniu procesu dodaje się nasyconego roztworu wodorowęglanu sodu, po czym oddziela się warstwę organiczną od wodnej, którą następnie ekstrahuje się dwukrotnie eterem dietylowym, a połączone warstwy organiczne suszy się nad bezwodnym siarczanem magnezu, następnie odfiltrowuje się środek suszący i odparowuje się rozpuszczalniki, a surowy produkt oczyszcza się za pomocą frakcyjnej destylacji próżniowej.Preferably, after completion of the process, saturated sodium bicarbonate solution is added, then the organic layer is separated from the aqueous layer, which is then extracted twice with diethyl ether, and the combined organic layers are dried over anhydrous magnesium sulfate, then the drying agent is filtered off and the solvents are evaporated, and the crude product is purified by vacuum fractional distillation.
Korzystnie kontroluje się przebieg reakcji przy użyciu chromatografii gazowej.Preferably, the course of the reaction is monitored by gas chromatography.
Sposób według wynalazku jest przedstawiony w przykładzie wykonania oraz na schemacie reakcji.The process of the invention is illustrated in the embodiment and in the reaction scheme.
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 1.43 g (35.8 mmol) 60% wodorku sodu. Po całkowitym wydzieleniu się wodoru do mieszaniny reakcyjnej wkrapla się 13.94 g (89.4 mmol, 7.2 ml) jodku etylu. Reakcję prowadzi się pod refluksem. Przebieg reakcji monitoruje się za pomocą chromatografii gazowej. Po upływie 47 h stwierdza się brak ubytku substratu w porównaniu z wcześniejszym pomiarem zawartości oksymu (na poziomie 10%). 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 30 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 4.75 g surowego produktu. Surowy produkt oczyszcza się za pomocą frakcyjnej destylacji próżniowej w wyniku której otrzymuje się 1.80 g czystego (-)-(1R,4S)-(etoksyimino)fenchanu, co stanowi 30.5% wydajności.5.0 g (29.8 mmol) of (-) - fenchone oxime, 50 ml of toluene and 1.43 g (35.8 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, 13.94 g (89.4 mmol, 7.2 ml) of ethyl iodide 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 47 h, no loss of substrate was found as compared to the previous measurement of the oxime content (at the level of 10%). 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 30 ml of diethyl ether. The combined organic layers are dried over anhydrous magnesium sulfate. After drying, the drying agent is filtered off and the solvents are evaporated on a rotary evaporator. 4.75 g of crude product are obtained. The crude product is purified by vacuum fractional distillation which gives 1.80 g of pure (-) - (1R, 4S) - (ethoxyimino) fenchate, representing a yield of 30.5%.
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 = 70-70.5°C (2mbar); [a]D25 = -47.1T = 70-70.5 ° C (2mbar); [a] D 25 = -47.1
HRMS (TOFMS EI+) obliczone dla [C12H21NO] 195.1623, znaleziono 195.1785HRMS (TOFMS EI +) calcd for [C 12 H 21 NO] 195.1623, found 195.1785
IR (KBr, cm-1): 2968 (vs), 2868 (s), 1741 (m), 1654 (w), 1467 (m); 1085 (s), 1066 (s), 880 (s) 1H NMR (CDCl3, δ, ppm): 1.23 (t, 3H, przy C-12, 2J=7.02 Hz), 1.24 (s, 3H, przy C-10), 1.26 i 1.28 (2s, 6H, przy C-8 i C-9), 1.34 (d, 1H, przy C-7, 2J= 10.4 Hz), 1.42-1.47 (m, 1H, przy C-5), 1.52-1.61 (m, 2H przy C-5 i C- 6), 1.70-1.74 (m, 1H, przy C-7), 1.78-1.83 (m, 2H przy C-6 i C-4), 3.99 (q, 2H, przy C-11, 2J=7.02 Hz) 13C NMR (CDCl3, δ, ppm): 14.51 (C-12), 17.22 (C-10), 22.58 i 23.38 (C-8 i C-9), 25.20 (C-6), 34.48 (C-5), 43.39 (C-7), 44.35 (C-3), 48.58 (C-4), 49.93 (C-1), 68.56 (C-11), 172.47 (C-2).IR (KBr, cm -1 ): 2968 (v), 2868 (s), 1741 (m), 1654 (w), 1467 (m); 1085 (s), 1066 (s), 880 (s) 1 H NMR (CDCl3, δ, ppm): 1.23 (t, 3H, at C-12, 2 J = 7.02 Hz), 1.24 (s, 3H, by C-10), 1.26 and 1.28 (2s, 6H, at C-8 and C-9), 1.34 (d, 1H, at C-7, 2 J = 10.4 Hz), 1.42-1.47 (m, 1H, at C-5), 1.52-1.61 (m, 2H at C-5 and C- 6), 1.70-1.74 (m, 1H, at C-7), 1.78-1.83 (m, 2H at C-6 and C- 4), 3.99 (q, 2H, at C-11, 2 J = 7.02 Hz) 13 C NMR (CDCl3, δ, ppm): 14.51 (C-12), 17.22 (C-10), 22.58 and 23.38 (C -8 and C-9), 25.20 (C-6), 34.48 (C-5), 43.39 (C-7), 44.35 (C-3), 48.58 (C-4), 49.93 (C-1), 68.56 (C-11), 172.47 (C-2).
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL398494A PL217516B1 (en) | 2012-03-19 | 2012-03-19 | (-)-(1R)-(ethoxyimine)fenchone and process for the preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL398494A PL217516B1 (en) | 2012-03-19 | 2012-03-19 | (-)-(1R)-(ethoxyimine)fenchone and process for the preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL398494A1 PL398494A1 (en) | 2012-12-17 |
| PL217516B1 true PL217516B1 (en) | 2014-07-31 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL398494A PL217516B1 (en) | 2012-03-19 | 2012-03-19 | (-)-(1R)-(ethoxyimine)fenchone and process for the preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL217516B1 (en) |
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2012
- 2012-03-19 PL PL398494A patent/PL217516B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PL398494A1 (en) | 2012-12-17 |
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