PL189921B1 - Novel acetate and method of obtaining same - Google Patents
Novel acetate and method of obtaining sameInfo
- Publication number
- PL189921B1 PL189921B1 PL99335313A PL33531399A PL189921B1 PL 189921 B1 PL189921 B1 PL 189921B1 PL 99335313 A PL99335313 A PL 99335313A PL 33531399 A PL33531399 A PL 33531399A PL 189921 B1 PL189921 B1 PL 189921B1
- Authority
- PL
- Poland
- Prior art keywords
- acetate
- dimethylbicyclo
- hept
- propanol
- formula
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims abstract description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005821 Claisen rearrangement reaction Methods 0.000 claims abstract description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012346 acetyl chloride Substances 0.000 claims abstract description 4
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000010933 acylation Effects 0.000 claims abstract 2
- 238000005917 acylation reaction Methods 0.000 claims abstract 2
- -1 (1S) -3- (7,7-dimethylbicyclo [4.1.0] hept-3-en-3-yl) propanol acetate Chemical compound 0.000 claims description 9
- VCHFNXRLVMAXMT-DTIOYNMSSA-N CC1(C)[C@@H]2C1CC=C(CCCO)C2 Chemical compound CC1(C)[C@@H]2C1CC=C(CCCO)C2 VCHFNXRLVMAXMT-DTIOYNMSSA-N 0.000 claims description 4
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VCHFNXRLVMAXMT-UHFFFAOYSA-N C1C=C(CCCO)CC2C(C)(C)C21 Chemical compound C1C=C(CCCO)CC2C(C)(C)C21 VCHFNXRLVMAXMT-UHFFFAOYSA-N 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Przedmiotem wynalazku jest nowy octan, o wzorze przedstawionym na rysunku, oraz sposób jego wytwarzania.The subject of the invention is a novel acetate having the formula shown in the drawing and a method of its preparation.
Związek ten, ze względu na swoje interesujące właściwości zapachowe, może znaleźć zastosowanie jako dodatek zapachowy w przemyśle spożywczym, głównie mięsnym.Due to its interesting aroma properties, this compound can be used as a fragrance additive in the food industry, mainly meat.
Surowcem do otrzymywania nowego octanu, będącego przedmiotem wynalazku, jest znany (-)-(1S)-3(10)-karen-trans-4-ol (K. Gollnick i inni, Ann. Chem., 687, s. 14, 1965.The raw material for the production of the new acetate, which is the subject of the invention, is the known (-) - (1S) -3 (10) -carene-trans-4-ol (K. Gollnick et al., Ann. Chem., 687, p. 14, 1965.
Istotą wynalazku jest nowy octan (lS)-3-(7,7-dimetylobicyklo[4.1.0]-hept-3-en-3-ylo)propanolu.The essence of the invention is the novel (1S) -3- (7,7-dimethylbicyclo [4.1.0] -hept-3-en-3-yl) propanol acetate.
W sposobie wytwarzania, według wynalazku, znany (-)-(1S)-3(10)-karen-trans-4-ol poddaje się przegrupowaniu Claisena metodą ortooctanową, korzystnie za pomocą ortooctanu trietylowego. Następnie, utworzony y,5-nienasycony ester redukuje się glinowodorkiem litu do (1S)-3-(7,7-dimetylobicyklo[4.1.0]-hept-3-en-3-ylo)propanolu, który przeprowadza się w reakcji z chlorkiem acetylu lub bezwodnikiem octowym w octan (1S)-3-(7,7-dimetylobicyclo[4.1,0]hept-3-en-3-ylo)-propanolu.In the production method according to the invention, the known (-) - (1S) -3 (10) -carene-trans-4-ol is subjected to a Claisen rearrangement by the orthoacetate method, preferably with triethyl orthoacetate. Then, the γ, 5-unsaturated ester formed is reduced with lithium aluminum hydride to (1S) -3- (7,7-dimethylbicyclo [4.1.0] -hept-3-en-3-yl) propanol which is reacted with acetyl chloride or acetic anhydride into (1S) -3- (7,7-dimethylbicyclo [4.1.0] hept-3-en-3-yl) propanol acetate.
Otrzymany w ten sposób związek charakteryzuje się średnio intensywnym zapachem drzewno-dymnym, z nutą wędzonkową.The compound obtained in this way is characterized by a moderately intense woody-smoky scent with a smoky note.
Przedmiotem wynalazku jest bliżej objaśniony w przykładach wykonania.The subject of the invention is explained in more detail in the working examples.
Przykład 1.Example 1.
Mieszaninę (1S)-3(10)-karen-trans-4-olu (7,6 g 0,05 mola), ortooctanu trietylowego (64 cm3, 0,37 mola) i kwasu propionowego (0,2 cm3) ogrzewa się w temperaturze 138°C przez 4 godziny. Po tym czasie oddestylowuje się pod normalnym ciśnieniem nadmiar ortooctanu, a pozostałość, pod zmniejszonym ciśnieniem, otrzymując 9,4 g (+)-(1S)-3-(7,7-dimetylobicyklo[4.1.0]hepten-3-en-3-ylo)propionianu etylu. Ester ten poddaje się redukcji glinowodorkiem litu (1,7 g, 0,042 mola) w eterze etylowym (100 cm3) uzyskując 7,0 g (+)-(1R)-3-(7,7-dimetylobicyclo[4.1.0]hept-3-en-3-ylo)propanolu. Alkohol ten rozpuszcza się w eterze etylowym (150 cm3) z rozpuszczoną w nim bezwodną pirydyną (4,0 ™, 0,046 mola). Do tego roztworu dodaje się chlorek acetylu (3,0 cm3, 0,043 mola) i mieszaninę reakcyjną pozostawia się w temperaturze pokojowej przez 24 godziny. Następnie rozcieńcza się ją eterem etylowym (100 cm3) i dodaje 10% roztwór kwasu solnego aż do uzyskania odczynu kwasowego, po czym oddziela się frakcję organiczną a wodną ekstrahuje się eterem etylowym (3 x 50 cm3). Połączone roztwory eterowe przemywa się rozcieńczonym (5%) roztworem kwasu siarkowego i solanką oraz suszy bezwodnym siarczanem miedzi. Surowy produkt, poA mixture of (1S) -3 (10) -caren-trans-4-ol (7.6 g 0.05 mol), triethyl orthoacetate (64 cm 3 , 0.37 mol) and propionic acid (0.2 cm 3 ) heated at 138 ° C for 4 hours. After this time, excess orthoacetate was distilled off under normal pressure and the residue was distilled under reduced pressure to give 9.4 g of (+) - (1S) -3- (7,7-dimethylbicyclo [4.1.0] heptene-3-en- Ethyl 3-yl) propionate. This ester is reduced with lithium aluminum hydride (1.7 g, 0.042 mol) in ethyl ether (100 cm 3 ) to give 7.0 g of (+) - (1R) -3- (7.7-dimethylbicyclo [4.1.0] hept-3-en-3-yl) propanol. This alcohol is dissolved in diethyl ether (150 cm 3 ) with anhydrous pyridine (4.0 ™, 0.046 mol) dissolved therein. To this solution was added acetyl chloride (3.0 cm 3 , 0.043 mol) and the reaction mixture was allowed to stand at room temperature for 24 hours. It is then diluted with diethyl ether (100 cm 3 ) and 10% hydrochloric acid solution is added until acidic, then the organic fraction is separated and the aqueous portion is extracted with diethyl ether (3 x 50 cm 3 ). The combined ethereal solutions were washed with dilute (5%) sulfuric acid solution and brine and dried with anhydrous copper sulfate. Raw product, after
189 921 oddestylowaniu rozpuszczalnika, oczyszcza się za pomocą chromatografii kolumnowej (żel krzemionkowy, heksan-octan etylu 14:1). Otrzymuje się w ten sposób 7,7 g czystego (powyżej 97% według GC) (+)-(1S)-octanu 3-(7,7-dimetylobicyklo[4.1.0]hept-3-en-3-ylo)propanolu, co stanowi 90% wydajności teoretycznej, liczonej w stosunku do użytego (+)-(1S)3-(7,7-dimetylobicyklo[4.1.0]hept-3-en-3-ylo)propanolu oraz 70% - w przeliczeniu na (-)-(1S)-3(10)karen-trans-4-ol.After distilling off the solvent, the purification is carried out by column chromatography (silica gel, hexane-ethyl acetate 14: 1). 7.7 g of pure (more than 97% according to GC) (+) - (1S) -acetate 3- (7,7-dimethylbicyclo [4.1.0] hept-3-en-3-yl) propanol are obtained. , which is 90% of theoretical efficiency, calculated on the used (+) - (1S) 3- (7,7-dimethylbicyclo [4.1.0] hept-3-en-3-yl) propanol and 70% - calculated na (-) - (1S) -3 (10) karen-trans-4-ol.
Właściwości fizyczne i spektroskopowe otrzymanego związku są następujące: temp. wrzenia 132-136°C/6 mm Hg; [α]ο2θ = +18,1334 (c, 0,6; CHCI3); nD 20 = 1,4785;The physical and spectroscopic properties of the obtained compound are as follows: boiling point 132-136 ° C / 6 mm Hg; [α] ο 2θ = +18.1334 (c, 0.6; CHCl3); n D 20 = 1.4785;
*H NMR (CDCb, δ): 0,63 (t, J = 8,8 Hz, 1H, H-6), 0,70 (m, 1H, H-1), 0,76 i 1,02 (dwa s, 6H, -C(CHs)2-4), 2,04 (s, 3H, -C(0)CH3), 1,69-2,38 (m, 8H, CH2-U. CH2-10, CH2-2, CH2-5), 4,02 (t, J = 6,7 Hz, 2H, -CH-O), 5,28 (s, 1H, H-4); IR (film, cm’1): 2941 (s), 1743 (vs), 1365 (m), 1240 (vs), 1043 (m).* H NMR (CDClb, δ): 0.63 (t, J = 8.8 Hz, 1H, H-6), 0.70 (m, 1H, H-1), 0.76 and 1.02 ( two s, 6H, -C (CHs) 2-4), 2.04 (s, 3H, -C (O) CH3), 1.69-2.38 (m, 8H, CH2-U. CH2-10 , CH2-2, CH2-5), 4.02 (t, J = 6.7 Hz, 2H, -CH-O), 5.28 (s, 1H, H-4); IR (film, cm- 1 ): 2941 (s), 1743 (v), 1365 (m), 1240 (v), 1043 (m).
Przykład 2.Example 2.
Do otrzymanego, tak jak w przykładzie 1, (+)-(1S)-3-(7,7-dimetylobicyclo[4.1.0]hept-3-en-3-ylo)propanolu (1,0 g, 0,0056 mola) i pirydyny (0,5 cm3, 0,0066 mola) w bezwodnym eterze etylowym (25 cm3) dodaje się świeżo destylowanego bezwodnika kwasu octowego (0,7 cm3, 0,007 mola) w eterze etylowym (15 cm3) oraz ogrzewa się do wrzenia pod chłodnicą zwrotną przez pięć godzin. Następnie, mieszaninę reakcyjną przemywa się 10% roztworem węglanu sodu, 5% roztworem siarczanu miedzi i solanką oraz suszy bezwodnym siarczanem magnezu. Surowy produkt, po odparowaniu rozpuszczalnika, oczyszcza się przez chromatografię kolumnową w warunkach analogicznych jak w przykładzie 1. Otrzymuje się 0,95 g czystego (+)-(1S)-octanu-3-(7,7-dimetylobicyklo[4.1.0]hept-3-en-3-ylo)propanolu, co stanowi 76% wydajności teoretycznej. Właściwości fizyczne i spektroskopowe otrzymanego produktu są identyczne jak otrzymanego w przykładzie 1.For the (+) - (1S) -3- (7,7-dimethylbicyclo [4.1.0] hept-3-en-3-yl) propanol (1.0 g, 0.0056) prepared as in example 1 mol) and pyridine (0.5 cm 3 , 0.0066 mol) in anhydrous ethyl ether (25 cm 3 ), freshly distilled acetic anhydride (0.7 cm 3, 0.007 mol) in ethyl ether (15 cm 3) was added and heated boil under reflux for five hours. Then, the reaction mixture was washed with 10% sodium carbonate solution, 5% copper sulfate solution and brine, and dried with anhydrous magnesium sulfate. The crude product, after evaporating off the solvent, is purified by column chromatography in the same conditions as in Example 1. 0.95 g of pure (+) - (1S) -acetate-3- (7,7-dimethylbicyclo [4.1.0] are obtained. hept-3-en-3-yl) propanol corresponding to 76% of theory. The physical and spectroscopic properties of the product obtained are identical to that obtained in Example 1.
189 921189 921
Departament Wydawnictw UP RP. Nakład 50 egz. Cena 2,00 zł.Publishing Department of the UP RP. Circulation of 50 copies. Price PLN 2.00.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL99335313A PL189921B1 (en) | 1999-09-06 | 1999-09-06 | Novel acetate and method of obtaining same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL99335313A PL189921B1 (en) | 1999-09-06 | 1999-09-06 | Novel acetate and method of obtaining same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL335313A1 PL335313A1 (en) | 2000-02-28 |
| PL189921B1 true PL189921B1 (en) | 2005-10-31 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| PL99335313A PL189921B1 (en) | 1999-09-06 | 1999-09-06 | Novel acetate and method of obtaining same |
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| Country | Link |
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| PL (1) | PL189921B1 (en) |
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1999
- 1999-09-06 PL PL99335313A patent/PL189921B1/en not_active IP Right Cessation
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| Publication number | Publication date |
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| PL335313A1 (en) | 2000-02-28 |
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| LAPS | Decisions on the lapse of the protection rights |
Effective date: 20060906 |