PL213678B1 - 2-thienylanalog of nerolidol - Google Patents
2-thienylanalog of nerolidolInfo
- Publication number
- PL213678B1 PL213678B1 PL389606A PL38960609A PL213678B1 PL 213678 B1 PL213678 B1 PL 213678B1 PL 389606 A PL389606 A PL 389606A PL 38960609 A PL38960609 A PL 38960609A PL 213678 B1 PL213678 B1 PL 213678B1
- Authority
- PL
- Poland
- Prior art keywords
- nerolidol
- formula
- reaction
- thiophen
- thienylanalog
- Prior art date
Links
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 title claims description 10
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 title claims description 9
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NAHPYHZTEDTMLK-UHFFFAOYSA-N 3-methyl-5-thiophen-2-ylpent-1-en-3-ol Chemical compound C=CC(O)(C)CCC1=CC=CS1 NAHPYHZTEDTMLK-UHFFFAOYSA-N 0.000 description 2
- 235000010591 Appio Nutrition 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000208317 Petroselinum Species 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- RMGJCSHZTFKPNO-UHFFFAOYSA-M magnesium;ethene;bromide Chemical compound [Mg+2].[Br-].[CH-]=C RMGJCSHZTFKPNO-UHFFFAOYSA-M 0.000 description 2
- -1 methylfuryl analogue of nerolidol Chemical class 0.000 description 2
- 235000011197 perejil Nutrition 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 244000153885 Appio Species 0.000 description 1
- YARJSVXZBADZGT-UHFFFAOYSA-N CC(C=C)(CCC=C(CCC=1OC(=CC=1)C)C)O Chemical compound CC(C=C)(CCC=C(CCC=1OC(=CC=1)C)C)O YARJSVXZBADZGT-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 229930000062 acyclic sesquiterpene Natural products 0.000 description 1
- 150000000553 acyclic sesquiterpene derivatives Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Description
Przedmiotem wynalazku jest nowy związek, 2-tienyloanalog nerolidolu, o przyjemnym, trwałym warzywnym zapachu, podobnym do zapachu korzenia selera i liści pietruszki.The present invention relates to a new compound, 2-thienyl analogue of nerolidol, with a pleasant, persistent vegetable aroma similar to that of celery root and parsley leaves.
Nerolidol jest acyklicznym seskwiterpenowym alkoholem występującym w przyrodzie, między innymi w olejku cabreuva i jest powszechnie stosowany w kompozycjach zapachowych i aromatach spożywczych.Nerolidol is an acyclic sesquiterpene alcohol found in nature, including in cabreuva oil, and is widely used in fragrance compositions and food flavorings.
Znany jest z opisu patentowego PL nr 198 495 fiiryloanalog nerolidolu, czyli 9-furan-2-ylo-3,7-dimetylonona-1,6-dien-3-ol, o delikatnym, kwiatowym zapachu, podobnym do zapachu nerolidolu.It is known from the Polish patent description PL No. 198,495 of a nerolidol pheryl analog, i.e. 9-furan-2-yl-3,7-dimethylone-1,6-dien-3-ol, with a delicate, floral fragrance similar to that of nerolidol.
Natomiast z opisu patentowego PL nr 198 497 jest znany metylofuryloanalog nerolidolu, czyli 3,7-dimetylo-9-(5-metylofuran-2-ylo)nona-1,6-dien-3-ol, o przyjemnym, delikatnym, kwiatowym zapachu, podobnym do zapachu nerolidolu.On the other hand, the patent PL No. 198,497 describes the methylfuryl analogue of nerolidol, i.e. 3,7-dimethyl-9- (5-methylfuran-2-yl) nona-1,6-diene-3-ol, with a pleasant, delicate, floral fragrance , similar to the smell of nerolidol.
Przedmiotem wynalazku jest nowy związek, 9-tiofen-2-ylo-3,7-dimetylonona-1,6-dien-3-ol o wzorze 1:The subject of the invention is a new compound, 9-thiophen-2-yl-3,7-dimethylone-1,6-dien-3-ol of formula 1:
stanowiący 2-tienyloanalog nerolidolu, w którym reszta izobutenylowa nerolidolu została zastąpiona podstawnikiem tiofenowym.which is the 2-thienyl analogue of nerolidol in which the isobutenyl moiety of the nerolidol has been replaced with the thiophene substituent.
Nowy związek stanowi mieszaninę izomerów geometrycznych E, Z w stosunku 4:3, charakteryzuje się przyjemnym, trwałym warzywnym zapachem, podobnym do zapachu selera i liści pietruszki. Znajduje zastosowanie jako składnik aromatów spożywczych, zwłaszcza typu maggi. Właściwości fizyko-chemiczne i spektralne nowego związku są następujące: temperatura wrzenia 399-410 K przy ciśnieniu 0,63 kPa;The new compound is a mixture of E, Z geometric isomers in the ratio of 4: 3, it is characterized by a pleasant, persistent vegetable smell, similar to the smell of celery and parsley leaves. It is used as a component of food flavors, especially of the maggi type. The physico-chemical and spectral properties of the new compound are as follows: boiling point 399-410 K at a pressure of 0.63 kPa;
MS (izomer trans): 232 (M+-18) (6), 110 (13), 107 (30), 98 (16), 97 (100), 93 (32), 71 (32), 55 (31), 53 (20), 43 (35);MS (trans isomer): 232 (M + -18) (6), 110 (13), 107 (30), 98 (16), 97 (100), 93 (32), 71 (32), 55 (31 ), 53 (20), 43 (35);
MS (izomer cis): 232 (M+-18) (7), 134 (10), 110 (11), 107 (21), 97 (100), 93 (24), 71 (28), 55 (24), 53 (17), 43 (23);MS (cis isomer): 232 (M + -18) (7), 134 (10), 110 (11), 107 (21), 97 (100), 93 (24), 71 (28), 55 (24 ), 53 (17), 43 (23);
1H NMR (CDCl3) (izomeru cis/trans) δ: 7,09 (m, 1H), 6,91 (m, 1H), 6,77 (m, 1H), 5,89 (2dd, J = 17,5, 10,50, 1H), 5,22 (m, 1H), 5,16 (m, 2H), 5,05 (m, 1H), 2,90 (m, 2H), 2,36 (m, 2H), 1,71 i 1,64 (2s, 3H), 1,27 i 1,24 (2s, 3H); 1 H NMR (CDCl3) (cis-isomer / trans) δ: 7.09 (m, 1H), 6.91 (m, 1H), 6.77 (m, 1H), 5.89 (2dd, J = 17 , 5, 10.50, 1H), 5.22 (m, 1H), 5.16 (m, 2H), 5.05 (m, 1H), 2.90 (m, 2H), 2.36 ( m, 2H), 1.71 and 1.64 (2s, 3H), 1.27 and 1.24 (2s, 3H);
13C NMR (CDCl3) (izomeru cis/trans) δ: 144,17, 133,60, 126,23, 126,11, 125,98, 125,04, 123,71, 123,55, 122,45, 41,83, 41,55, 41,21, 33,70, 28,18, 27,82, 27,21, 27,15, 22,83, 22,25, 22,07,15,52. 13 C NMR (CDCl3) (cis-isomer / trans) δ: 144.17, 133.60, 126.23, 126.11, 125.98, 125.04, 123.71, 123.55, 122.45, 41.83, 41.55, 41.21, 33.70, 28.18, 27.82, 27.21, 27.15, 22.83, 22.25, 22.07, 15.52.
Nowy związek, 9-tiofen-2-ylo-3,7-dimetylonona-1,6-dien-3-ol o wzorze 1, w postaci mieszaniny izomerów cis/trans otrzymuje się z 5-tiofen-2-ylo-3-metylopent-1-en-3-olu o wzorze 2:The new compound 9-thiophen-2-yl-3,7-dimethylone-1,6-dien-3-ol of formula 1, in the form of a mixture of cis / trans isomers, is obtained from 5-thiophen-2-yl-3- methylpent-1-en-3-ol of formula 2:
który ogrzewa się z acetylooctanem etylu, powstały w wyniku tej reakcji keton poddaje się reakcji Grignard'a z bromkiem winylomagnezowym w środowisku tetrahydrofuranu i po zakończeniu tej reakcji do środowiska reakcji dodaje się nasycony roztwór chlorku amonowego, produkt ekstrahuje się toluenem, przemywa wodą i po odparowaniu z niego rozpuszczalnika, poddaje się go destylacji pod zmniejszonym ciśnieniem, w wyniku czego otrzymuje się związek o wzorze 1 z wydajnością 63% w przeliczeniu na związek o wzorze 2.which is heated with ethyl acetoacetate, the ketone formed as a result of this reaction is subjected to a Grignard reaction with vinylmagnesium bromide in a medium of tetrahydrofuran, and after completion of this reaction, a saturated solution of ammonium chloride is added to the reaction medium, the product is extracted with toluene, washed with water and after evaporation solvent therefrom, it is subjected to distillation under reduced pressure to afford the compound of formula 1 in a yield of 63% based on the compound of formula 2.
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
Mieszaninę 0,1 mola 5-tiofen-2-ylo-3-metylopent-1-en-3-olu o wzorze 2 i 0,2 mola acetylooctanu etylu ogrzewano do 453 K w czasie 3 godzin. W trakcie reakcji wydzielał się ditlenek węgla i oddestyPL 213 678 B1 lowywał etanol. Po zakończeniu reakcji odparowano nadmiar acetylooctanu etylu i produkt reakcji w postaci ketonu destylowano w temperaturze 396-402 K przy ciśnieniu 0,50 kPa. 0,048 mola otrzymanego ketonu wkroplono w czasie 2 godzin do roztworu 0,05 mola bromku winylomagnezowego w 50 ml tetrahydrofuranu utrzymując temperaturę około 308 K. Po zakończeniu reakcji dodano nasycony roztwór chlorku amonowego i produkt ekstrahowano 3 porcjami toluenu. Po przemyciu wodą i odparowaniu rozpuszczalnika produkt destylowano w temperaturze 399-410 K przy ciśnieniu 0,62 kPa. Otrzymano mieszaninę izomerów cis/trans 9-tiofen-2-ylo-3,7-dimetylonona-1,6-dien-3-olu o wzorze 1 z wydajnością 63% w przeliczeniu na związek wyjściowy o wzorze 2, o wyżej podanych właściwościach fizyko-chemicznych oraz spektralnych.A mixture of 0.1 mol of 5-thiophen-2-yl-3-methylpent-1-en-3-ol of the formula 2 and 0.2 mol of ethyl acetoacetate was heated to 453 K over 3 hours. During the reaction, carbon dioxide was evolved and ethanol was distilled off. After the completion of the reaction, excess ethyl acetoacetate was evaporated and the reaction product, in the form of a ketone, was distilled at 396-402 K under a pressure of 0.50 kPa. 0.048 mol of the obtained ketone was added dropwise over 2 hours to a solution of 0.05 mol of vinylmagnesium bromide in 50 ml of tetrahydrofuran while maintaining the temperature at about 308 K. After the reaction was completed, saturated ammonium chloride solution was added and the product was extracted with 3 portions of toluene. After washing with water and evaporating the solvent, the product was distilled at a temperature of 399-410 K and a pressure of 0.62 kPa. A mixture of cis / trans isomers of 9-thiophen-2-yl-3,7-dimethylone-1,6-dien-3-ol of formula 1 was obtained with the yield of 63% based on the starting compound of formula 2, with the above-mentioned physical properties. -chemical and spectral.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL389606A PL213678B1 (en) | 2009-11-17 | 2009-11-17 | 2-thienylanalog of nerolidol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL389606A PL213678B1 (en) | 2009-11-17 | 2009-11-17 | 2-thienylanalog of nerolidol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL389606A1 PL389606A1 (en) | 2011-05-23 |
| PL213678B1 true PL213678B1 (en) | 2013-04-30 |
Family
ID=44070273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL389606A PL213678B1 (en) | 2009-11-17 | 2009-11-17 | 2-thienylanalog of nerolidol |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL213678B1 (en) |
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2009
- 2009-11-17 PL PL389606A patent/PL213678B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| PL389606A1 (en) | 2011-05-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LICE | Declarations of willingness to grant licence |
Effective date: 20121116 |
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| LAPS | Decisions on the lapse of the protection rights |
Effective date: 20121117 |