PL194471B1 - Novel bicyclic hydroxylactone and method of obtaining same - Google Patents
Novel bicyclic hydroxylactone and method of obtaining sameInfo
- Publication number
- PL194471B1 PL194471B1 PL342504A PL34250400A PL194471B1 PL 194471 B1 PL194471 B1 PL 194471B1 PL 342504 A PL342504 A PL 342504A PL 34250400 A PL34250400 A PL 34250400A PL 194471 B1 PL194471 B1 PL 194471B1
- Authority
- PL
- Poland
- Prior art keywords
- hydroxylactone
- acid
- trimethyl
- formula
- bicyclic
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 12
- 125000002619 bicyclic group Chemical group 0.000 title claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 12
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 6
- 238000007273 lactonization reaction Methods 0.000 claims abstract description 6
- 150000004967 organic peroxy acids Chemical class 0.000 claims abstract description 5
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 235000019568 aromas Nutrition 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- JRMGKNJMSAIUBB-UHFFFAOYSA-N 7-hydroxy-3a,5,5-trimethyl-4,6,7,7a-tetrahydro-3h-1-benzofuran-2-one Chemical compound OC1CC(C)(C)CC2(C)C1OC(=O)C2 JRMGKNJMSAIUBB-UHFFFAOYSA-N 0.000 description 1
- MSRUCYZKSSTIMH-UHFFFAOYSA-N CC1(C2C(CC(C1)(C)C)O2)CC(=O)OCC Chemical compound CC1(C2C(CC(C1)(C)C)O2)CC(=O)OCC MSRUCYZKSSTIMH-UHFFFAOYSA-N 0.000 description 1
- 241000212322 Levisticum officinale Species 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000001645 levisticum officinale Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
Abstract
1. Nowy bicykliczny hydroksylakton, o wzo- rze 1 przedstawionym na rysunku. 2. Sposób otrzymywania nowego bicyklicz- nego hydroksylaktonu, o wzorze 1 przedsta- wionym na rysunku, znamienny tym, ze ester alkilowy kwasu 1,5,5-trimetylo-2-cykloheksen-1- -ylooctowego poddaje sie epoksydacji nadkwa- sem organicznym, a nastepnie utworzony epo- ksyestr poddaje sie w kolejnym etapie, laktoni- zacji kwasowej. PL PL PL1. A new bicyclic hydroxylactone of formula 1 as shown in the drawing. 2. The method of obtaining a new bicyclic hydroxylactone of formula 1 shown in the figure, characterized in that the 1,5,5-trimethyl-2-cyclohexene-1-ylacetic acid alkyl ester is epoxidized with organic peracid, and the epoxester formed is then subjected to acid lactonization in a subsequent step. PL PL PL
Description
Opis wynalazkuDescription of the invention
Przedmiotem wynalazku jest nowy bicykliczny hydroksylakton i sposób jego otrzymywaniaThe subject of the invention is a new bicyclic hydroxylactone and a method for its preparation
Laktony zawierające od 10 do 15 atomów węgla są obdarzone zazwyczaj interesującymi zapachami i to im właśnie wiele kwiatów zawdzięcza swój aromat. Nadają one również smak i zapach wielu produktom żywnościowym. Mniej natomiast rozpoznane są właściwości osmiczne hydroksylaktonów.Lactones containing 10 to 15 carbon atoms usually have interesting aromas and it is from them that many flowers have their aromas. They also impart flavor and aroma to many foods. On the other hand, the osmic properties of hydroxylactones are less recognized.
Surowcem do otrzymywania nowego bicyklicznego hydroksylaktonu, będącego przedmiotem wynalazku, jest znany ester alkilowy kwasu 1,5,5-trimetylo-2-cykloheksen-1-ylooctowego (G.B. Jones i inni, Tetrahedron, 1993, 49, 369).The raw material for the preparation of the novel bicyclic hydroxylactone of the invention is the known 1,5,5-trimethyl-2-cyclohexene-1-ylacetic acid alkyl ester (G.B. Jones et al., Tetrahedron, 1993, 49, 369).
Istotą wynalazku jest nowy bicykliczny hydroksylakton, o wzorze 1 przedstawionym na rysunku.The essence of the invention is the novel bicyclic hydroxylactone of the formula I shown in the drawing.
Sposób otrzymywania nowego bicyklicznego hydroksylaktonu, o wzorze 1 przedstawionym na rysunku, polega na tym, że ester alkilowy kwasu 1,5,5-trimetylo-2-cykloheksen-1-ylooctowego poddaje się epoksydacji nadkwasem organicznym, a następnie utworzony epoksyester, poddaje się w kolejnym etapie, laktonizacji kwasowej.The method of obtaining the new bicyclic hydroxylactone of formula 1 shown in the figure consists in that the 1,5,5-trimethyl-2-cyclohexene-1-ylacetic acid alkyl ester is epoxidized with an organic peracid, and then the formed epoxyester is subjected to the next step, acid lactonization.
Korzystnie jest, gdy estrem alkilowym kwasu 1,5,5-trimetylo-2-cykloheksen-1-ylooctowego jest ester etylowy, a nadkwasem organicznym - kwas m-chloronadbenzoesowy.Preferably, the 1,5,5-trimethyl-2-cyclohexene-1-ylacetic acid alkyl ester is ethyl ester and the organic peracid is m-chloroperbenzoic acid.
Korzystnie też jest, gdy laktonizację kwasową prowadzi się w obecności kwasu chlorowego (VII).It is also preferred that the acid lactonization is carried out in the presence of chloric acid (VII).
Uzyskany w ten sposób hydroksylakton charakteryzuje się średnio intensywnym zapachem warzywnym przypominającym zapach korzenia lubczyka i może znaleźć zastosowanie w przemyśle spożywczym jako komponent zapachowy.The hydroxylactone obtained in this way is characterized by a medium-intense vegetable scent resembling the smell of lovage root and can be used in the food industry as a fragrance component.
Sposób według wynalazku objaśniony jest bliżej w przykładzie wykonania.The method according to the invention is explained in more detail in an exemplary embodiment.
PrzykładExample
Roztwór 7,4 g (0,043 mola) kwasu m-chloronadbenzoesowego w 50 cm chlorku metylenu wkrapla się przy mieszaniu i chłodzeniu do 3,9 g (0,019 mola) estru etylowego kwasu 1,5,5-trimetylo-2-cykloheksen-1-ylooctowego w 100 cm3 chlorku metylenu. Reakcję prowadzi się do całkowitego przereagowania estru (24 godz.). Po tym czasie mieszaninę reakcyjną przemywa się kolejno roztworami siarczanu (IV) sodu, węglanu sodu i solanką, a następnie suszy się nad bezwodnym siarczanem (VI) sodu. Surowy produkt poddaje się chromatografii kolumnowej na żelu krzemionkowym, stosując jako eluent mieszaninę heksanu i acetonu w stosunku objętościowym 9:1. Otrzymuje się 2,6 g (wydajność 62%) estru etylowego kwasu 1,5,5-trimetylo-2,3-epoksycykloheks-1-ylooctowego o następujących stałych fizycznych i spektroskopowych: nD20 =1,4600; 1H NMR (CDCl3)d: 0,87 i 0,91 (dwa s, 6H, -C(CH3)2-), 1,22 (s, 3H, CH3-1), 1,24 (t, J=7,1 Hz, 3H, -OCH2CH3), 1,63-1,67 (m, 2H, CH2-6), 2,32 i 2,47 (dwa d, J=14,2 Hz, 2H, układ AB,-CI±CO2-), 2,97 (d, J-3,9 Hz, 1H, H-2), 3,23 (t,d, J=3,9 i 1,8 Hz, 1H, H-3), 4,12 (kw, J=7,1 Hz, 2H, -OCH^CHs),A solution of 7.4 g (0.043 mol) of m-chloroperbenzoic acid in 50 ml of methylene chloride is added dropwise with stirring and cooling to 3.9 g (0.019 mol) of 1,5,5-trimethyl-2-cyclohexene-1-acid ethyl ester. in 100 cm 3 of methylene chloride. The reaction is carried out until the ester is completely converted (24 hours). After this time, the reaction mixture was washed successively with sodium sulfate, sodium carbonate and brine solutions, and then dried over anhydrous sodium sulfate. The crude product was column chromatographed on silica gel using a 9: 1 v / v mixture of hexane and acetone as eluent. There were obtained 2.6 g (62% yield) of 1,5,5-trimethyl-2,3-epoxycyclohex-1-ylacetic acid ethyl ester having the following physical and spectroscopic constants: nD 20 = 1.4600; 1 H NMR (CDCl3) d: 0.87 and 0.91 (two s, 6H, -C (CH 3) 2 -), 1.22 (s, 3H, CH3-1), 1.24 (t, J = 7.1 Hz, 3H, -OCH 2 CH 3 ), 1.63-1.67 (m, 2H, CH2-6), 2.32 and 2.47 (two d, J = 14.2 Hz , 2H, AB system, -Cl ± CO 2 -), 2.97 (d, J-3.9 Hz, 1H, H-2), 3.23 (t, d, J = 3.9 and 1, 8 Hz, 1H, H-3), 4.12 (q, J = 7.1 Hz, 2H, -OCH ^ CHs),
IR(cm-1); 1748(s), 1372(w), 1156(m), 1036(m).IR (cm -1 ); 1748 (s), 1372 (w), 1156 (m), 1036 (m).
W drugim etapie syntezy 2,6 g (0,011 mola) epoksyestru dodaje się do mieszaniny składającej się z 20 cm tetrahydrofuranu, 10 cm wody i 7 kropli kwasu chlorowego (VII), a następnie całość miesza się przez 4 dni. Po zakończeniu reakcji oddziela się warstwę organiczną od wodnej, a tą ostatnią ekstrahuje eterem etylowym (3x50 cm3). Ekstrakty eterowe przemywa się roztworem wodorowęglanu sodu i solanką a następnie suszy bezwodnym siarczanem magnezu. Surowy produkt poddaje się chromatografii kolumnowej na żelu krzemionkowym, stosując jako eluent mieszaninę heksanu i acetonu w stosunku objętościowym 2:1. Otrzymuje się w ten sposób 2,0 g czystego 4,4,6-trimetylo-2-hydroksy-9-oksabicyklo[4.3.0]nonan-8-onu, co stanowi 87% wydajności teoretycznej dla laktonizacji i 54% wydajności całej syntezy.In the second stage of the synthesis, 2.6 g (0.011 mol) of epoxyester are added to a mixture consisting of 20 cm of tetrahydrofuran, 10 cm of water and 7 drops of chloric acid (VII), and then the mixture is stirred for 4 days. After completion of the reaction, the organic layer is separated from the aqueous layer, and the latter is extracted with diethyl ether (3 × 50 cm 3 ). The ether extracts were washed with sodium bicarbonate solution and brine, and then dried with anhydrous magnesium sulfate. The crude product was column chromatographed on silica gel using a 2: 1 v / v mixture of hexane and acetone as eluent. 2.0 g of pure 4,4,6-trimethyl-2-hydroxy-9-oxabicyclo [4.3.0] nonan-8-one are thus obtained, which is 87% of the theoretical yield for lactonization and 54% of the total synthesis yield .
Stałe fizyczne i spektroskopowe uzyskanego związku są następujące:The physical and spectroscopic constants of the obtained compound are as follows:
temp. top=109-110°C; 1H NMR (CDCl3)d, 1,04 i 1,06 (dwa s, 6H,- C(CH3)2-), 1,18 (s, 3H, CH3-6), 1,64 (m, 2H, CH2-3), 2,15 i 2,62 (dwa d, J=17,5 Hz, 2H, CH2-7), 3,85-3,92 (dwa m, 2H, H-1 i H-2);mp = 109-110 ° C; 1 H NMR (CDCl 3 ) d, 1.04 and 1.06 (two s, 6H, - C (CH 3 ) 2 -), 1.18 (s, 3H, CH3-6), 1.64 (m , 2H, CH2-3), 2.15 and 2.62 (two d, J = 17.5 Hz, 2H, CH2-7), 3.85-3.92 (two m, 2H, H-1 and H-2);
IR: 3408(s,b), 1784(s), 1164(m), 1220(m), 1076(m).IR: 3408 (s, b), 1784 (s), 1164 (m), 1220 (m), 1076 (m).
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL342504A PL194471B1 (en) | 2000-09-11 | 2000-09-11 | Novel bicyclic hydroxylactone and method of obtaining same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL342504A PL194471B1 (en) | 2000-09-11 | 2000-09-11 | Novel bicyclic hydroxylactone and method of obtaining same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL342504A1 PL342504A1 (en) | 2001-03-12 |
| PL194471B1 true PL194471B1 (en) | 2007-06-29 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL342504A PL194471B1 (en) | 2000-09-11 | 2000-09-11 | Novel bicyclic hydroxylactone and method of obtaining same |
Country Status (1)
| Country | Link |
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| PL (1) | PL194471B1 (en) |
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2000
- 2000-09-11 PL PL342504A patent/PL194471B1/en unknown
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| Publication number | Publication date |
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| PL342504A1 (en) | 2001-03-12 |
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