PL212024B1 - New δ-iodo-γ-lactones with trans p-menthane system of antifidant activity and the method of obtaining them - Google Patents
New δ-iodo-γ-lactones with trans p-menthane system of antifidant activity and the method of obtaining themInfo
- Publication number
- PL212024B1 PL212024B1 PL393488A PL39348810A PL212024B1 PL 212024 B1 PL212024 B1 PL 212024B1 PL 393488 A PL393488 A PL 393488A PL 39348810 A PL39348810 A PL 39348810A PL 212024 B1 PL212024 B1 PL 212024B1
- Authority
- PL
- Poland
- Prior art keywords
- isopropyl
- iodo
- methylcyclohex
- acetic acid
- cis
- Prior art date
Links
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 title claims description 16
- 230000000694 effects Effects 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 16
- 125000004494 ethyl ester group Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- CXDOATCUMSZSFT-OHBODLIOSA-N (3aR,6S,7S,7aS)-7-iodo-3a-methyl-6-propan-2-yl-3,4,5,6,7,7a-hexahydro-1-benzofuran-2-one Chemical compound I[C@H]1[C@@H](CC[C@@]2(CC(O[C@H]12)=O)C)C(C)C CXDOATCUMSZSFT-OHBODLIOSA-N 0.000 claims description 4
- CXDOATCUMSZSFT-YJQGPUDQSA-N (3as,6r,7r,7ar)-7-iodo-3a-methyl-6-propan-2-yl-3,4,5,6,7,7a-hexahydro-1-benzofuran-2-one Chemical compound I[C@@H]1[C@@H](C(C)C)CC[C@@]2(C)CC(=O)O[C@H]21 CXDOATCUMSZSFT-YJQGPUDQSA-N 0.000 claims description 4
- 238000005821 Claisen rearrangement reaction Methods 0.000 claims description 2
- 238000005657 iodolactonization reaction Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 35
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- 238000004611 spectroscopical analysis Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 241000721621 Myzus persicae Species 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 241001124203 Alphitobius diaperinus Species 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- 241000254173 Coleoptera Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 238000004458 analytical method Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000007273 lactonization reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 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
- 239000007858 starting material Substances 0.000 description 2
- 241000238876 Acari Species 0.000 description 1
- 241000256135 Chironomus thummi Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 241000962544 Turdus infuscatus Species 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku są nowe δ-jodo-y-laktony z układem trans p-mentanu o aktywności antyfidantnej oraz sposób ich otrzymywania.The subject of the invention are new δ-iodo-γ-lactones with the trans p-menthane system with antifungal activity and the method of their preparation.
δ-Jodo-y-laktony z układem trans p-mentanu, o wzorach 1,2 i 3 przedstawionych na rysunku, mogą znaleźć zastosowanie jako deterenty pokarmowe w stosunku do szkodliwych gatunków owadów.The δ-iodo-γ-lactones with the trans p-menthane system, with formulas 1,2 and 3 shown in the figure, can be used as food detectors against harmful insect species.
Wynalazkiem są nowe δ-jodo-y-laktony z układem trans p-mentanu, o wzorach 1, 2 i 3 przedstawionych na rysunku, o aktywności antyfidantnej.The invention relates to new δ-iodo-γ-lactones with the trans p-menthane system, of the formulas 1, 2 and 3 shown in the drawing, with antifidus activity.
Sposób otrzymywania nowych δ-jodo-y-laktony z układem trans p-mentanu, o wzorach 1, 2 i 3 przedstawionych na rysunku, polega na tym, że (±)-cis-piperytol albo (-)-(3S,4R)-piperytol, albo (+)(3R,4S)-piperytol poddaje się ortooctanowej modyfikacji przegrupowania Claisena. Otrzymany w ten sposób ester etylowy kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego albo ester etylowy kwasu (-)-(1'S,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego, albo ester etylowy kwasu (+)-(1'R,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego hydrolizuje się, do kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego albo do kwasu (-)-(1'S,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-r-1'-ylo)octowego, albo do kwasu (+)-(1'R,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego.The method of obtaining new δ-iodo-y-lactones with the trans p-menthane system, with the formulas 1, 2 and 3 shown in the figure, is that (±) -cis-piperitol or (-) - (3S, 4R) - piperitole or (+) (3R, 4S) -pipererythole undergoes an orthoacetate modification of the Claisen rearrangement. The thus obtained ethyl ester of (±) -cis- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid or ethyl ester of (-) - (1'S, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid, or (+) - (1'R, 4'S) - (4'-isopropyl-1'-methylcyclohex) -2'-en-1'-yl) acetic acid is hydrolyzed to (±) -cis- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid or to (- ) - (1'S, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-r-1'-yl) acetic acid, or to (+) - (1'R, 4'S) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic.
Jodolaktonizacja odpowiedniego kwasu, w środowisku zasadowym, prowadzi do otrzymania (±)-c-5-jodo-t-4-izopropylo-r-1-metylo-7-oksa-cis-bicyklo-[4.3.0]nonan-8-onu, o wzorze 1, albo (+)-(1S,4R, 5R,6R)-5-jodo-4-izopropylo-1-metylo-7-oksabicyklo[4.3.0]nonan-8-onu, o wzorze 2, albo (-)-(1R,4S,5S,6S)-5-jodo-4-izo-propylo-1-metylo-7-oksabicyklo[4.3.0]nonan-8-onu, o wzorze 3.Iodolactonization of the corresponding acid, in basic medium, gives (±) -c-5-iodo-t-4-isopropyl-r-1-methyl-7-oxa-cis-bicyclo- [4.3.0] nonan-8- one of formula 1, or (+) - (1S, 4R, 5R, 6R) -5-iodo-4-isopropyl-1-methyl-7-oxabicyclo [4.3.0] nonan-8-one of formula 2 or (-) - (1R, 4S, 5S, 6S) -5-iodo-4-iso-propyl-1-methyl-7-oxabicyclo [4.3.0] nonan-8-one, of formula 3.
δ-Jodo-y-laktony z układem trans p-mentanu posiadają aktywność antyfidantną w stosunku do mszycy brzoskwiniowo ziemniaczanej (Myzus persicae Sulz).δ-iodo-γ-lactones with the trans p-menthane system have antifidus activity against the peach potato aphid (Myzus persicae Sulz).
Wyniki testów biologicznych w stosunku do mszycy brzoskwiniowo ziemniaczanej (Myzus persicae Sulz), przeprowadzonych według metody opisanej przez K. Dancewicz i współpracowników (Journal of Chemical Ecology, 2008, 34, s. 530-538), przedstawiono w tabeli 1.The results of biological tests against the peach potato aphid (Myzus persicae Sulz), carried out according to the method described by K. Dancewicz et al. (Journal of Chemical Ecology, 2008, 34, pp. 530-538), are presented in Table 1.
T a b e l a 1T a b e l a 1
K - średnia liczba mszyc znajdująca się na polowie liścia zwilżonej 70% roztworem etanolu.K - the average number of aphids located on a half of a leaf moistened with a 70% ethanol solution.
T - średnia liczba mszyc znajdująca się na połowie liścia zwilżonej 0,1% etanolowym roztworem badanego związku.T - the average number of aphids on a half of a leaf moistened with 0.1% ethanolic solution of the test compound.
P - poziom istotności różnicy statystycznej.P - significance level of the statistical difference.
δ-Jodo-y-lakton, o wzorze 1, ogranicza żerowanie larw pleśniakowca lśniącego (Alphitobius diaperinus Panzer).The δ-iodo-y-lactone, formula 1, reduces the feeding of the larvae of Alphitobius diaperinus Panzer.
Stwierdzono również, że δ-jodo-y-laktony, o wzorze 2, posiada aktywność deterentną wobec chrząszczy pleśniakowca lśniącego (Alphitobius diaperinus Panzer).It was also found that δ-iodo-γ-lactones, of the formula 2, have deterential activity against the lesser mites (Alphitobius diaperinus Panzer) beetles.
Wyniki testów biologicznych w stosunku do larw i chrząszczy pleśniakowca lśniącego (Alphitobius diaperinus Panzer), przeprowadzonych według metody opisanej przez M. Szczepanik i współpracowników (Journal of Plant Protection Research, 2003, 43, 2, s. 87-96), przedstawiono w tabeli 2.The results of biological tests in relation to the larvae and beetles of black thrush (Alphitobius diaperinus Panzer), carried out according to the method described by M. Szczepanik et al. (Journal of Plant Protection Research, 2003, 43, 2, pp. 87-96), are presented in 2.
T a b e l a 2T a b e l a 2
PL 212 024 B1 cd. Tabeli 2PL 212 024 B1 cont. Table 2
A - bezwzględny współczynnik aktywności deterentnej. R - względny współczynnik aktywności deterentnej.A - absolute retail activity coefficient. R - relative retail activity coefficient.
T - sumaryczny współczynnik aktywności deterentnej.T - total retail activity coefficient.
Przedmiot wynalazku jest bliżej objaśniony w przykładach wykonania.The subject of the invention is explained in more detail in the working examples.
P r z y k ł a d 1P r z k ł a d 1
Do 1,00 g racemicznego (±)-cis-piperytolu (6,49 mmola) dodaje się 9.0 cm3 (47,25 mmola) ortooctanu trietylowego oraz katalityczną ilości kwasu propionowego (1 kropla) i ogrzewa się w temperaturze 411K, oddestylowując w sposób ciągły tworzący się etanol. Po zakończeniu reakcji, potwierdzonym przez analizę GC i TLC (heksan:eter dietylowy 2:1), oddestylowuje się nadmiar nieprzereagowanego ortooctanu trietylowego. Surowy produkt poddaje się chromatografii kolumnowej (żel krzemionkowy, heksan:chlorek metylenu:eter dietylowy 6:2:2). 9.0 cm 3 (47.25 mmol) of triethyl orthoacetate and a catalytic amount of propionic acid (1 drop) are added to 1.00 g of racemic (±) -cis-piperitole (6.49 mmol) and the mixture is heated at 411K, distilled in continuously forming ethanol. Upon completion of the reaction, as confirmed by GC and TLC analysis (hexane: diethyl ether 2: 1), excess unreacted triethyl orthoacetate is distilled off. The crude product is subjected to column chromatography (silica gel, hexane: methylene chloride: diethyl ether 6: 2: 2).
Otrzymuje się 1,13 g (5,04 mmola) czystego estru etylowego kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego, co stanowi 78% wydajności teoretycznej.1.13 g (5.04 mmol) of pure (±) -cis- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester were obtained, which is 78% of the yield. theoretical.
Dane spektroskopowe otrzymanego estru etylowego kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są następujące:The spectroscopic data of the obtained (±) -cis- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester are as follows:
1H NMR (600 MHz, CDCl3) δ: 0,87 i 0,89 (dwa d, J = 6,8 Hz, 6H, (CH3)2CH-), 1,08 (s, 3H, CH3-1'), 1,25 (t, J = 7,1 Hz, 3H, -OCH2CH3), 1,32-1.41 (m, 2H, jeden z CH2-5' i jeden z CH2-6'), 1,54-1,63 (m, 2H, jeden z CH2-5' i (CH3)2CH-), 1,80 (m, 1H, jeden z CH2-6'), 1,86 (m, 1H, H-4'), 2,25 (s, 2H, CH2-2), 4,10 (q, J = 7,1 Hz, 2H, -OCH2CH3), 5,49-5,54 (m, 2H, H-2' i H-3'); 1 H NMR (600 MHz, CDCl 3 ) δ: 0.87 and 0.89 (two d, J = 6.8 Hz, 6H, (CH3) 2 CH-), 1.08 (s, 3H, CH 3 -1 '), 1.25 (t, J = 7.1 Hz, 3H, -OCH 2 CH 3 ), 1.32-1.41 (m, 2H, one from CH 2 -5' and one from CH 2 - 6 '), 1.54-1.63 (m, 2H, one of CH 2 -5' and (CH 3 ) 2 CH-), 1.80 (m, 1H, one of CH 2 -6 '), 1.86 (m, 1H, H-4 '), 2.25 (s, 2H, CH 2 -2), 4.10 (q, J = 7.1 Hz, 2H, -OCH2CH3), 5.49 -5.54 (m, 2H, H-2 'and H-3');
13C NMR (600 MHz, CDCl3) δ: 14,30 (-OCH2CH3), 19,40 i 19,76 ((CH3)2CH-), 21,80 (C-5'), 27,90 (CH3-1'), 31,92 ((CH3)2CH-), 34,13 (C-1'), 34,53 (C-6'), 41,59 (C-4'), 45,55 (C-2), 59,93 (-OCH2CH3), 129,70 (C-2'), 135,54 (C-3'), 171,98 (C-1); 13 C NMR (600 MHz, CDCl 3 ) δ: 14.30 (-OCH 2 CH 3 ), 19.40 and 19.76 ((CH 3 ) 2 CH-), 21.80 (C-5 '), 27.90 (CH 3 -1 '), 31.92 ((CH 3 ) 2 CH-), 34.13 (C-1'), 34.53 (C-6 '), 41.59 (C- 4 '), 45.55 (C-2), 59.93 (-OCH 2 CH 3 ), 129.70 (C-2'), 135.54 (C-3 '), 171.98 (C- 1);
IR (film, cm-1): 2958 (s), 2871 (m), 1734 (s), 1462 (m), 1368 (m), 1245 (m).IR (film, cm -1 ): 2958 (s), 2871 (m), 1734 (s), 1462 (m), 1368 (m), 1245 (m).
Otrzymany ester etylowy kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego (1,13 g, 5.04 mmola) rozpuszcza się w 15 cm3 2,5% metanolowego roztworu wodorotlenku potasu i 1 cm3 wody, a następnie ogrzewa się pod chłodnicą zwrotną. Po zakończeniu reakcji, potwierdzonym analizą GC i TLC (heksan:eter dietylowy 4:1), metanol oddestylowuje się pod zmniejszonym ciśnieniem. Pozostałość rozpuszcza się w wodzie (30 cm3), zakwasza się 0,5 M roztworem kwasu solnego (do pH około 4) i ekstrahuje się 30 cm3 eteru dietylowego. Frakcję organiczną oddziela się, a warstwę wodną ekstrahuje się trzykrotnie eterem dietylowym (3 x 20 cm3). Połączone roztwory eterowe przemywa się solanką do odczynu obojętnego i suszy bezwodnym MgSO4. Po oddestylowaniu rozpuszczalnika surowy produkt poddaje się chromatografii kolumnowej (żel krzemionkowy, heksan:eter dietylowy 2:1).The resulting ethyl ester of (±) cis- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid (1.13 g, 5.04 mmol) is dissolved in 15 cm 3 of 2,5 % methanolic potassium hydroxide solution and 1 cm 3 of water, then heated to reflux. After completion of the reaction as confirmed by GC and TLC analysis (hexane: diethyl ether 4: 1), methanol was distilled off under reduced pressure. The residue was dissolved in water (30 cm 3), acidified with 0.5 M hydrochloric acid (to pH 4) and extracted with 30 cm 3 of diethyl ether. The organic fraction was separated and the aqueous layer was extracted three times with diethyl ether (3 x 20 cm 3 ). The combined ethereal solutions were washed with brine until neutral and dried with anhydrous MgSO4. After distilling off the solvent, the crude product was subjected to column chromatography (silica gel, hexane: diethyl ether 2: 1).
Otrzymuje się 0,90 g (4,59 mmola) kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego, co stanowi 91% wydajności teoretycznej.0.90 g (4.59 mmol) of (±) -cis- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid were obtained, representing 91% of theory.
Dane spektroskopowe otrzymanego kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są następujące:The spectroscopic data of the obtained (±) -cis- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid are as follows:
1H NMR (600 MHz, CDCl3) δ: 0,87 i 0,90 (dwa d, J = 6,8 Hz, 6H, (CH3)2CH-), 1,12 (s, 3H, CH3-1'), 1,35-1,43 (m, 2H, jeden z CH2-5' i jeden z CH2-6'), 1,55-1,66 (m, 2H, jeden z CH2-5' i (CH3)2CH-), 1,83 (m, 1H, jeden z CH2-6'), 1,89 (m, 1H, H-4'), 2,30 i 2,32 (dwa d, J = 13,5 Hz, 2H, CH2-2, układ AB), 5,55 i 5,57 (dwa d, J = 10,8 Hz, 2H, H-2' i H-3', układ AB); 1 H NMR (600 MHz, CDCl3) δ: 0.87 and 0.90 (two d, J = 6.8 Hz, 6H, (CH 3) 2 CH-), 1.12 (s, 3H, CH3-1 ' ), 1.35-1.43 (m, 2H, one CH 2 -5 'and one CH 2 -6'), 1.55-1.66 (m, 2H, one CH 2 -5 ' and (CH 3 ) 2 CH-), 1.83 (m, 1H, one of CH 2 -6 '), 1.89 (m, 1H, H-4'), 2.30 and 2.32 (two d, J = 13.5 Hz, 2H, CH 2 -2, AB system), 5.55 and 5.57 (two d, J = 10.8 Hz, 2H, H-2 'and H-3', AB system);
13C NMR (600 MHz, CDCl3) δ: 19,36 i 19,74 ((CH3)2CH-), 21,78 (C-5'), 27,86 (CH3-1'), 31,91 ((CH3)2CH-), 34,04 (C-1'), 34,63 (C-6'), 41,59 (C-4'), 45,32 (C-2), 130,08 (C-2'), 135,18 (C-3'), 178,28 (C-1); 13 C NMR (600 MHz, CDCl 3 ) δ: 19.36 and 19.74 ((CH 3 ) 2 CH-), 21.78 (C-5 '), 27.86 (CH 3 -1'), 31.91 ((CH 3 ) 2 CH-), 34.04 (C-1 '), 34.63 (C-6'), 41.59 (C-4 '), 45.32 (C-2 ), 130.08 (C-2 '), 135.18 (C-3'), 178.28 (C-1);
IR (film, cm-1): 2600-3200 (b, s), 1705 (s), 1462 (m), 1408 (m).IR (film, cm -1 ): 2600-3200 (b, s), 1705 (s), 1462 (m), 1408 (m).
Uzyskany kwas (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowy (0,90 g, 4,59 mmo33 la) rozpuszcza się w 30 cm3 eteru dietylowego i dodaje się 0,5 M roztwór NaHCO3 (30 cm3) a następnie ogrzewa się pod chłodnicą zwrotną. Do wrzącej mieszaniny dodaje się kroplami roztwór zawiera3 jący w 22 cm3 wody 2,79 g jodu (11 mmoli) i 5,48 g jodku potasu (33 mmole). Po zakończeniu reakcji (GC, TLC - heksan:eter dietylowy 2:1) mieszaninę poreakcyjną rozcieńcza się eterem dietylowym 3 (30 cm3) i przemywa roztworem Na2S2O3 w celu zredukowania nadmiaru jodu. Warstwę organicznąThe obtained (±) -cis- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid (0.90 g, 4.59 mmol) is dissolved in 30 cm 3 of diethyl ether. and 0.5 M NaHCO3 solution (30 cm 3) and heated to reflux. To the boiling mixture is added dropwise a solution containing 3 which in a 22 cm 3 of water, 2.79 g of iodine (11 mmol) and 5.48 g of potassium iodide (33 mmol). After completion of the reaction (GC, TLC - hexane: diethyl ether 2: 1) mixture is diluted with diethyl ether 3 (30 cm 3) and washed with Na2S2O3 solution to reduce the excess iodine. Organic layer
PL 212 024 B1 3 oddziela się a fazę wodną ekstrahuje eterem dietylowym (3 x 20 cm3). Połączone warstwy eterowe przemywa się roztworem NaHCO3 a następnie solanką, do uzyskania odczynu obojętnego, i suszy bezwodnym MgSO4. Po odparowaniu rozpuszczalnika surowy produkt oczyszcza się metodą chromatografii kolumnowej (żel krzemionkowy, heksan:eter dietylowy:chlorek metylenu 6:1:1). Otrzymuje się 1,26 g (3,91 mmola) (±)-c-5-jodo-t-4-izopropylo-r-1-metylo-7-oksa-cis-bicyklo[4.3.0]nonan-8-onu, o wzorze 1, z wydajnością 85%.GB 212 024 B1 3 is separated and the aqueous phase extracted with diethyl ether (3 x 20 cm 3). The combined ether layers were washed with NaHCO3 solution followed by brine until neutral and dried with anhydrous MgSO4. After evaporating off the solvent, the crude product is purified by column chromatography (silica gel, hexane: diethyl ether: methylene chloride 6: 1: 1). 1.26 g (3.91 mmol) of (±) -c-5-iodo-t-4-isopropyl-1-methyl-7-oxa-cis-bicyclo [4.3.0] nonane-8- is obtained. onu, formula I, in 85% yield.
Wydajność tej trzyetapowej syntezy, w przeliczeniu na ilość użytego (±)-cis-piperytolu, wynosi 60%.The yield of this three-step synthesis, based on the amount of (±) -cis-piperythol used, is 60%.
Dane spektroskopowe otrzymanego (±)-c-5-jodo-t-4-izopropylo-r-1-metylo-7-oksa-cis-bicyklo[4.3.0]nonan-8-onu są następujące:The spectroscopic data of the obtained (±) -c-5-iodo-t-4-isopropyl-r-1-methyl-7-oxa-cis-bicyclo [4.3.0] nonan-8-one are as follows:
1H NMR (600 MHz, CDCI3) δ: 0,67 i 0,94 (dwa d, J = 6,9 Hz, 6H, (CHshCH-), 1,12 (m, 1H, H-3, aksjalny), 1,20 (s, 3H, CH3-1), 1,46 (ddd, J = 14,2, 13,5 i 4.2 Hz, 1H, H-2. aksjalny), 1,48 (tt, J = 11,9 i 3,1 Hz, 1H, H-4), 1,63 (m wyglądający jak dq J = 14,2 i 3,5 Hz, 1H, H-3, ekwatorialny), 1,87 (dt, J = 14,2 i 3,5 Hz, 1H, H-2, ekwatorialny), 1,98 i 2,62 (dwa d, J = 17,1 Hz, 2H, CH2-9), 2,20 (septet d, J = 6,9 i 3,1 Hz, 1H, (CHshCH-), 3,72 (dd, J = 11,9 i 9,2 Hz, 1H, H-5), 4,48 (d, J = 9,2 Hz, 1H. H-6); 1 H NMR (600 MHz, CDCl 3) δ: 0.67 and 0.94 (two d, J = 6.9 Hz, 6H, (CHshCH-), 1.12 (m, 1H, H-3, axial) , 1.20 (s, 3H, CH3-1), 1.46 (ddd, J = 14.2, 13.5 and 4.2 Hz, 1H, H -2.axial), 1.48 (mp, J = 11.9 and 3.1 Hz, 1H, H-4), 1.63 (m looking like dq J = 14.2 and 3.5 Hz, 1H, H-3, equatorial), 1.87 (dt, J = 14.2 and 3.5 Hz, 1H, H-2, equatorial), 1.98 and 2.62 (two d, J = 17.1 Hz, 2H, CH2-9), 2.20 (septet d, J = 6.9 and 3.1 Hz, 1H, (CHshCH-), 3.72 (dd, J = 11.9 and 9.2 Hz, 1H, H-5), 4.48 (d, J = 9.2 Hz, 1H, H-6);
13C NMR (600 MHz, CDCh) δ: 14.56 i 21,50 (CHs^CH-), 19,98 (C-3), 28,49 (CH3-1), 31,97 (CH3)2CH-), 32,65 (C-2), 37,69 (C-9), 40,57 (C-5), 41,33 (C-1), 47,30 (C-4), 92,85 (C-6), 175,14 (C-8); 13 C NMR (600 MHz, CDCl 3) δ: 14.56 and 21.50 (CHs2CH-), 19.98 (C-3), 28.49 (CH3-1), 31.97 (CH3) 2CH-) , 32.65 (C-2), 37.69 (C-9), 40.57 (C-5), 41.33 (C-1), 47.30 (C-4), 92.85 ( C-6), 175.14 (C-8);
IR (KBr, cm-1): 2955 (m), 2872 (w), 1779 (s), 1390 (w), 1374 (w), 1281 (w), 1004 (m), 990 (m), 493 (w);IR (KBr, cm -1 ): 2955 (m), 2872 (w), 1779 (s), 1390 (w), 1374 (w), 1281 (w), 1004 (m), 990 (m), 493 (in);
analiza elementarna: C12H19O2 (322,17); obliczono: C 44,74, H 5,94;elemental analysis: C12H19O2 (322.17); calcd: C 44.74, H 5.94;
znaleziono: C 45,17, H 6,29.Found: C 45.17, H 6.29.
P r z y k ł a d 2P r z k ł a d 2
Postępuje się jak w przykładzie 1, z tym że związkiem wyjściowym w syntezie jest (-)-(3S,4R)-piperytol.The procedure is as in Example 1, except that the starting material in the synthesis is (-) - (3S, 4R) -piperiteol.
Z 0,8 g (5,19 mmola) (-)-(3S,4R)-piperytolu otrzymuje się 0,82 g (3,66 mmola) estru etylowego kwasu (-)-(1'S,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego (= -34,4° (c = 1,05,From 0.8 g (5.19 mmol) of (-) - (3S, 4R) -pipererythole, 0.82 g (3.66 mmol) of ethyl ester of (-) - (1'S, 4'R) - ( 4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid (= -34.4 ° (c = 1.05,
CHCl3); ee = 98%) z 71% wydajnością.CHCl3); ee = 98%) in 71% yield.
Dane spektroskopowe estru etylowego kwasu (-)-(1'S,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są takie same jak estru etylowego kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego.The spectroscopic data of (-) - (1'S, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester is the same as (±) - acid ethyl ester cis- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic.
W reakcji hydrolizy 0,82 g (3,66 mmola) estru etylowego kwasu (-)-(1'S,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego otrzymuje się, z 90% wydajnością, 0,64 g, (3,29 mmola) kwasu (-)-(1'S,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego (|i/|” = -23,8° (c = 0,79, CHCl3)).By hydrolysis, 0.82 g (3.66 mmol) of (-) - (1'S, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester obtained, in 90% yield, 0.64 g (3.29 mmol) of the acid (-) - (1'S, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-1 ' -yl) acetic acid (| i / | "= -23.8 ° (c = 0.79, CHCl 3)).
Dane spektroskopowe kwasu (-)-(1'S,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są takie same jak kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego.Spectroscopic data for (-) - (1'S, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid is the same as for (±) -cis- (4 '-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic.
W wyniku laktonizacji 0,64 g (3,29 mmola) kwasu (-)-(1'S,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego otrzymuje się, z 92% wydajnością, 0,97 g (3,02 mmola) (+)(1S,4R,5R,6R)-5-jodo-4-izopropylo-1-metylo-7-oksabicyklo[4.3.0]nonan-8-onu, o wzorze 2, i następujących stałych fizycznych: [u]3' = +46,3° (c = 0,96, CHCl3); ee = 97%.Lactonization of 0.64 g (3.29 mmol) of (-) - (1'S, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid gives , in 92% yield, 0.97 g (3.02 mmol) of (+) (1S, 4R, 5R, 6R) -5-iodo-4-isopropyl-1-methyl-7-oxabicyclo [4.3.0] nonane -8-one, of formula 2, and the following physical constants: [u] 3 '= + 46.3 ° (c = 0.96, CHCl 3 ); ee = 97%.
Dane spektroskopowe (+)-(1S,4R,5R,6R)-5-jodo-4-izopropylo-1-metylo-7-oksabicyklo[4.3.0]nonan-8-onu są takie same jak (±)-c-5-jodo-t-4-izopropylo-r-1-metylo-7-oksa-cis-bicyklo[4.3.0]nonan-8-onu.The spectroscopic data of (+) - (1S, 4R, 5R, 6R) -5-iodo-4-isopropyl-1-methyl-7-oxabicyclo [4.3.0] nonan-8-one is the same as (±) -c -5-iodo-t-4-isopropyl-r-1-methyl-7-oxa-cis-bicyclo [4.3.0] nonan-8-one.
Wydajność tej trzyetapowej syntezy, w przeliczeniu na ilość użytego (-)-(3S,4R)-piperytolu, wynosi 58%.The yield of this three-step synthesis, based on the amount of (-) - (3S, 4R) -piperiteol used, is 58%.
P r z y k ł a d 3P r z k ł a d 3
Postępuje się jak w przykładzie 1, z tym że związkiem wyjściowym w syntezie jest (+)-(3R,4S)-piperytol.The procedure is as in Example 1, except that the starting material in the synthesis is (+) - (3R, 4S) -piperiteol.
Z 0,75 g (4,87 mmola) (+)-(3R,4S)-piperytolu otrzymuje się 0,80 g (3,57 mmola) estru etylowego kwasu (+)-(1'R,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-yIo)octowego (= +28,15° (c = 1,00, CHCl3); ee = 94%). Wydajność reakcji wynosi 73%.From 0.75 g (4.87 mmol) of (+) - (3R, 4S) -pipererythole, 0.80 g (3.57 mmol) of ethyl ester of (+) - (1'R, 4'S) - ( 4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid (= + 28.15 ° (c = 1.00, CHCl3); ee = 94%). The reaction yield is 73%.
Dane spektroskopowe estru etylowego kwasu (+)-(1'R,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są takie same jak estru etylowego kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego.The spectroscopic data of (+) - (1'R, 4'S) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester is the same as (±) - acid ethyl ester cis- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic.
PL 212 024 B1PL 212 024 B1
W reakcji hydrolizy 0,80 g (3,57 mmola) estru etylowego kwasu (+)-(1'R,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego otrzymuje się, z 92% wydajnością, 0,65 g (3,30 mmola) kwasu (+)-(1'R,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego (\a^ = +25,4° (c = 0,82,By hydrolysis of 0.80 g (3.57 mmol) of (+) - (1'R, 4'S) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester obtained, in 92% yield, 0.65 g (3.30 mmol) of the acid (+) - (1'R, 4'S) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'- yl) acetic (\ a ^ = + 25.4 ° (c = 0.82,
CHCl3)).CHCl3)).
Dane spektroskopowe kwasu (+)-(1'R,4'S)-(4'-izopropylo-1'metylocykloheks-2'-en-1'-ylo)octowego są takie same jak kwasu (±)-cis-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego.The spectroscopic data of (+) - (1'R, 4'S) - (4'-isopropyl-1'methylcyclohex-2'-en-1'-yl) acetic acid is the same as for (±) -cis- (4 ' -isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic.
W wyniku laktonizacji 0,65 g (3,30 mmola) kwasu (+)-(1'R,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego otrzymuje się, z 86% wydajnością, 0,91 g (2,83 mmola) (-)-(1R,4S,5S,6S)-5-jodo-4-izopropylo-1-metylo-7-oksabicyklo[4.3.0]nonan-8-onu, o wzorze 3, i następujących stałych fizycznych: [a]32 = -42,4° (c = 1,02, CHCl3); ee = 96%.Lactonization of 0.65 g (3.30 mmol) of (+) - (1'R, 4'S) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid gives , in 86% yield, 0.91 g (2.83 mmol) (-) - (1R, 4S, 5S, 6S) -5-iodo-4-isopropyl-1-methyl-7-oxabicyclo [4.3.0] nonan-8-one, of formula 3, and the following physical constants: [a] 3 2 = -42.4 ° (c = 1.02, CHCl 3 ); ee = 96%.
Dane spektroskopowe (-)-(1R,4S,5S,6S)-5-jodo-4-izopropylo-1-metylo-7-oksabicyklo[4.3.0]nonan-8-onu są takie same jak (±)-c-5-jodo-t-4-izopropylo-r-1-metylo-7-oksa-cis-bicyklo[4.3.0]nonan-8-onu.The spectroscopic data of (-) - (1R, 4S, 5S, 6S) -5-iodo-4-isopropyl-1-methyl-7-oxabicyclo [4.3.0] nonan-8-one are the same as (±) -c -5-iodo-t-4-isopropyl-r-1-methyl-7-oxa-cis-bicyclo [4.3.0] nonan-8-one.
Wydajność tej trzyetapowej syntezy, w przeliczeniu na ilość użytego (+)-(3R,4S)-piperytolu, wynosi 58%.The yield of this three-step synthesis, based on the amount of (+) - (3R, 4S) -piperiteol used, is 58%.
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