PL221614B1 - Carene-tetrahydrofuran derivative - Google Patents
Carene-tetrahydrofuran derivativeInfo
- Publication number
- PL221614B1 PL221614B1 PL405975A PL40597513A PL221614B1 PL 221614 B1 PL221614 B1 PL 221614B1 PL 405975 A PL405975 A PL 405975A PL 40597513 A PL40597513 A PL 40597513A PL 221614 B1 PL221614 B1 PL 221614B1
- Authority
- PL
- Poland
- Prior art keywords
- formula
- carene
- tetrahydrofuran
- tetrahydrofuran derivative
- mixture
- Prior art date
Links
- -1 2 - [(E) -3- (4,7,7-trimethylbicyclo [4.1.0] - hept-4-en-3-yl) -but-2-enyloxy] tetrahydrofuran Chemical compound 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 2
- 241000207199 Citrus Species 0.000 description 2
- 240000000560 Citrus x paradisi Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000020971 citrus fruits Nutrition 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WTOYNNBCKUYIKC-JMSVASOKSA-N (+)-nootkatone Chemical compound C1C[C@@H](C(C)=C)C[C@@]2(C)[C@H](C)CC(=O)C=C21 WTOYNNBCKUYIKC-JMSVASOKSA-N 0.000 description 1
- RQOKOSIDJPMJPY-QZPOHEPASA-N CC=1[C@@H](CC2C([C@H]2C=1)(C)C)C(C)(C=C)O Chemical compound CC=1[C@@H](CC2C([C@H]2C=1)(C)C)C(C)(C=C)O RQOKOSIDJPMJPY-QZPOHEPASA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WTOYNNBCKUYIKC-UHFFFAOYSA-N dl-nootkatone Natural products C1CC(C(C)=C)CC2(C)C(C)CC(=O)C=C21 WTOYNNBCKUYIKC-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- HEKJOMVJRYMUDB-UHFFFAOYSA-N octahydro-6-isopropyl-2(1h)-naphthalenone Chemical compound C1C(=O)CCC2CC(C(C)C)CCC21 HEKJOMVJRYMUDB-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 125000004084 sesquiterpene group Chemical group 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Fats And Perfumes (AREA)
Description
Opis wynalazkuDescription of the invention
Przedmiotem wynalazku jest pochodna karenowo-tetrahydrofuranowa, przeznaczona do zastosowania jako składnik o zapachu cytrusowo-grejpfrutowym kompozycji zapachowych.The present invention relates to a cararene-tetrahydrofuran derivative intended for use as a citrus-grapefruit flavored component in perfume compositions.
Zapach cytrusowy, w tym grejpfrutowy, jest jednym z najbardziej pożądanych zapachów, zarówno w perfumerii, jak i w aromatach spożywczych. Naturalnym związkiem odpowiedzialnym za charakterystyczny zapach owocu grejpfruta jest seskwiterpenowy, bicykliczny keton o nazwie nootkaton, jednak zarówno jego izolacja z surowca naturalnego, jak i totalna synteza są nieopłacalne dla celów komercyjnych.Citrus scent, including grapefruit, is one of the most desirable fragrances, both in perfumery and in food flavors. The natural compound responsible for the characteristic aroma of grapefruit fruit is sesquiterpene, bicyclic ketone called nootkaton, but both its isolation from natural raw material and total synthesis are unprofitable for commercial purposes.
Znane są także inne związki o zapachu cytrusowym, jak naturalny cytral, czy związek syntetyczny o nazwie handlowej Decatone (opisany w czasopiśmie Angewandte Chemie Int. Ed. 2000, 39, 2980-3010), które są stosowane w przemyśle, lecz ich trwałość zapachowa jest niekiedy niezadowalająca.There are also other compounds with a citrus scent, such as natural citral or a synthetic compound with the trade name Decatone (described in the journal Angewandte Chemie Int. Ed. 2000, 39, 2980-3010), which are used in industry, but their fragrance stability is sometimes unsatisfactory.
Przedmiotem wynalazku jest pochodna karenowo-tetrahydrofuranowa, którą stanowi 2-[(E)-3-(4,7,7-trimetylobicyklo[4.1.0.]hept-4-en-3-ylo)-but-2-enyloksy]tetrahydrofuran o wzorze 1:The subject of the invention is a carne-tetrahydrofuran derivative, which is 2 - [(E) -3- (4,7,7-trimethylbicyclo [4.1.0.] Hept-4-en-3-yl) -but-2-enyloxy] tetrahydrofuran of formula 1:
charakteryzujący się intensywnym, cytrusowo-grejpfrutowym zapachem o trwałości zapachowej przynajmniej dwukrotnie wyższej od trwałości zapachu naturalnego nootkatonu, trwały w środowisku o neutralnym i podwyższonym pH. Związek ten stanowi mieszaninę dwóch diastereomerów w proporcji 1:1. Dane spektralne nowego 20 związku są następujące:characterized by an intense, citrus-grapefruit scent with an aromatic durability at least twice as high as that of the natural nootcatone, durable in an environment with a neutral and increased pH. This compound is a 1: 1 mixture of two diastereomers. The spectral data of the new compound are as follows:
1H NMR (CDCI3, δ): 3,50 (s, 1H), 5,27 (t, J = 7,5 Hz, 1H), 5,08 (m, 1H), 4,11 (m, 1H), 3,96 (m, 1H), 3,80 (m, 2H), 1,59 (s, 3H), 1,50 (s, 3H), 0,99 (s, 3H), 0,78 (s, 1H); 1 H NMR (CDCl 3 , δ): 3.50 (s, 1H), 5.27 (t, J = 7.5 Hz, 1H), 5.08 (m, 1H), 4.11 (m, 1H), 3.96 (m, 1H), 3.80 (m, 2H), 1.59 (s, 3H), 1.50 (s, 3H), 0.99 (s, 3H), 0, 78 (s. 1H);
13C NMR(CDCl3, δ): 142,0 (s), 136,1 (2s), 122,0 (2d), 103,1 (d), 66,8 (t), 64,2 (t), 47,1 (d), 32,5 (t), 28,2 (t), 24,22 (t), 23,57 (t), 23,50 (d), 22,5 (q), 18,1 (q), 15,5 (q), 13,8 (q), 13,3 (q); 13 C NMR (CDCl3, δ): 142.0 (s), 136.1 (2s), 122.0 (2d), 103.1 (d), 66.8 (t), 64.2 (t) , 47.1 (d), 32.5 (t), 28.2 (t), 24.22 (t), 23.57 (t), 23.50 (d), 22.5 (q), 18.1 (q), 15.5 (q), 13.8 (q), 13.3 (q);
MS (m/z, %): 216 (M+, 0), 188 (8), 146 (9), 145 (75), 131 (10), 105 (14), 91 (13), 71 (100), 43 (37), 41 (19).MS (m / z,%): 216 (M + 0), 188 (8), 146 (9), 145 (75), 131 (10), 105 (14), 91 (13), 71 (100) , 43 (37), 41 (19).
Sposób otrzymywania związku o wzorze 1 polega na tym, że 2-((3R,6S)-4,7,7-trimetylobicyklo[4.1.0]hept-4-en-3-ylo)but-3-en-2-ol o wzorze 2:The method for the preparation of the compound of formula 1 is that 2 - ((3R, 6S) -4,7,7-trimethylbicyclo [4.1.0] hept-4-en-3-yl) but-3-en-2- ol of formula 2:
poddaje się izomeryzacji w środowisku mieszaniny tetrahydrofuranu i wody, w obecności kwasu metanosulfonowego, w temperaturze 50°C w czasie 3 godzin, po czym otrzymany w wyniku izomeryzacji 2-((3R,6S)-4,7,7-trimetylobicyklo-[4.1.0]hept-4-enylo)but-2-en-1-ol o wzorze 3:isomerized in a mixture of tetrahydrofuran and water, in the presence of methanesulfonic acid, at 50 ° C for 3 hours, and then the 2 - ((3R, 6S) -4,7,7-trimethylbicyclo- [4.1 .0] hept-4-enyl) but-2-en-1-ol of formula 3:
PL 221 614 B1 stanowiący mieszaninę izomerów cis/trans o stosunku ilościowym 1:6, poddaje się reakcji z 2,3-dihydrofuranem w środowisku mieszaniny chlorku metylenu i kwasu p-toluenosulfonowego, w temperaturze 0°C w czasie 2 godzin.A mixture of cis / trans isomers with a ratio of 1: 6 is reacted with 2,3-dihydrofuran in a mixture of methylene chloride and p-toluenesulfonic acid at 0 ° C for 2 hours.
Przedmiot wynalazku ilustruje poniższy przykład.The following example illustrates the subject of the invention.
P r z y k ł a dP r z k ł a d
W kolbie umieszczono 2 g (0,0097 mola) trzeciorzędowego alkoholu o wzorze 2, w postaci roztworu w 20 cm mieszaniny tetrahydrofuranu i wody zmieszanych w stosunku objętościowym 4:1 i w trakcie mieszania wkroplono 2,52 cm (0,0388 mola) kwasu metanosulfonowego. Mieszanie kontynuowano w temperaturze 50°C w czasie do 3 godzin. Po tym czasie do mieszaniny poreakcyjnej do3 dano nasycony roztwór wodny NaHCO3 i ekstrahowano produkt trzema porcjami po 10 cm octanu etylu. Połączone warstwy organiczne przemyto wodą do odczynu obojętnego. Po oddestylowaniu rozpuszczalnika otrzymano alkohol o wzorze 3 w ilości 1,76 g, którego strukturę potwierdziło widmo 1H NMR (CDCI3, δ): 5,55 (s, 1H), 5,42 (t, J = 6,2 Hz, 1H), 4,20 (d, J = 8 Hz, 2H), 1,71 (2s, 3H), 1,57 (2s, 3H), 1,05 (2s, 3H), 0,79 (2s, 3H). Następnie, do surowego alkoholu o wzorze 3 dodano 50 cm3 chlorku metylenu, 15 mg kwasu p-toluenosulfonowego i zawartość kolby schłodzono do temperatury 0°C, po czym w trakcie mieszania wkroplono 0,63 g (0,009 mola) 2,3-dihydrofuranu. Mieszanie kontynuowano w tej temperaturze w czasie 2 godzin. Po tym czasie do mieszaniny poreakcyjnej dodano 3 nasycony roztwór wodny NaHCO i ekstrahowano produkt trzema porcjami po 15 cm octanu etylu. Połączone warstwy organiczne przemyto wodą do odczynu obojętnego. Po oddestylowaniu rozpuszczalnika otrzymano pochodną o wzorze 1 z 94% wydajnością.2 g (0.0097 mol) of the tertiary alcohol of formula 2 were placed in the flask as a solution in 20 cm of a mixture of tetrahydrofuran and water mixed in a 4: 1 ratio, and 2.52 cm (0.0388 mol) of methanesulfonic acid was added dropwise while stirring. . Stirring was continued at 50 ° C for up to 3 hours. At this time, a saturated aqueous solution of NaHCO 3 was added to the reaction mixture to 3 and the product was extracted with three 10 cm portions of ethyl acetate. The combined organic layers were washed neutral with water. After distilling off the solvent to give an alcohol of formula 3 in an amount of 1.76 g, whose structure is confirmed by 1 H NMR spectrum (CDCl3, δ): 5.55 (s, 1H), 5.42 (t, J = 6.2 Hz, 1H), 4.20 (d, J = 8Hz, 2H), 1.71 (2s, 3H), 1.57 (2s, 3H), 1.05 (2s, 3H), 0.79 (2s, 3H). Then, the crude alcohol of formula 3 was added 50 cm 3 of methylene chloride, 15 mg of p-toluenesulfonic acid and the batch was cooled to 0 ° C and then added dropwise with stirring 0.63 g (0.009 mole) 2,3-dihydrofuran . Stirring was continued at this temperature for 2 hours. At this time, 3 saturated NaHCO aqueous solution was added to the reaction mixture and the product was extracted with three 15 cm portions of ethyl acetate. The combined organic layers were washed neutral with water. After distilling off the solvent, the derivative of formula 1 was obtained in 94% yield.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL405975A PL221614B1 (en) | 2013-11-08 | 2013-11-08 | Carene-tetrahydrofuran derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL405975A PL221614B1 (en) | 2013-11-08 | 2013-11-08 | Carene-tetrahydrofuran derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL405975A1 PL405975A1 (en) | 2015-05-11 |
| PL221614B1 true PL221614B1 (en) | 2016-05-31 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL405975A PL221614B1 (en) | 2013-11-08 | 2013-11-08 | Carene-tetrahydrofuran derivative |
Country Status (1)
| Country | Link |
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| PL (1) | PL221614B1 (en) |
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2013
- 2013-11-08 PL PL405975A patent/PL221614B1/en unknown
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| Publication number | Publication date |
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| PL405975A1 (en) | 2015-05-11 |
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