PL212023B1 - New δ-iodo-γ-lactones with cis p-menthane system of antifidant activity and the method of obtaining them - Google Patents
New δ-iodo-γ-lactones with cis p-menthane system of antifidant activity and the method of obtaining themInfo
- Publication number
- PL212023B1 PL212023B1 PL393486A PL39348610A PL212023B1 PL 212023 B1 PL212023 B1 PL 212023B1 PL 393486 A PL393486 A PL 393486A PL 39348610 A PL39348610 A PL 39348610A PL 212023 B1 PL212023 B1 PL 212023B1
- Authority
- PL
- Poland
- Prior art keywords
- isopropyl
- methylcyclohex
- iodo
- 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
- 238000000034 method Methods 0.000 title claims description 8
- 230000000694 effects Effects 0.000 title description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 63
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004494 ethyl ester group Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- CXDOATCUMSZSFT-SASUGWTJSA-N (3aR,6R,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](C(C)C)CC[C@]2(C)CC(=O)O[C@@H]21 CXDOATCUMSZSFT-SASUGWTJSA-N 0.000 claims description 3
- CXDOATCUMSZSFT-IELRGYKMSA-N (3aS,6S,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-IELRGYKMSA-N 0.000 claims description 3
- 230000000843 anti-fungal effect Effects 0.000 claims description 3
- HPOHAUWWDDPHRS-UHFFFAOYSA-N trans-piperitol Natural products CC(C)C1CCC(C)=CC1O HPOHAUWWDDPHRS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005821 Claisen rearrangement reaction Methods 0.000 claims description 2
- 238000005657 iodolactonization reaction Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 37
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000004611 spectroscopical analysis Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 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
- 238000006243 chemical reaction Methods 0.000 description 6
- 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
- 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
- 230000015572 biosynthetic process Effects 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
- 239000010410 layer 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
- 238000003786 synthesis reaction Methods 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
- 241000238631 Hexapoda 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
- 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 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
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 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
- 238000007245 halolactonization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium 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
- 230000001105 regulatory effect Effects 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
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
Przedmiotem wynalazku są nowe δ-jodo-y-laktony z układem cis p-mentanu aktywności antyfidantnej oraz sposób ich otrzymywania.The subject of the invention is new δ-iodo-γ-lactones with the cis p-menthane system of antifungal activity and the method of their preparation.
δ-Jodo-y-laktony z układem cis p-mentanu, o wzorach 1,2 i 3 przedstawionych na rysunku, mogą znaleźć zastosowanie jako deterenty pokarmowe owadów, a tym samym, jako czynniki regulujące populację szkodliwych gatunków owadów.The δ-iodo-γ-lactones with the cis p-menthane system, with the formulas 1,2 and 3 shown in the figure, can be used as food detectors of insects and thus as factors regulating the population of harmful insect species.
Wynalazkiem są nowe δ-jodo-y-laktony z układem cis 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 cis p-menthane system, of the formulas 1, 2 and 3 shown in the figure, with antifidus activity.
Sposób otrzymywania nowych δ-jodo-y-laktonów z układem cis p-mentanu, o wzorach 1, 2 i 3 przedstawionych na rysunku, o aktywności antyfidantnej, polega na tym, że (±)-trans-piperytol albo (-)(3S,4S)-piperitol, albo (+)-(3R,4R)-piperytol poddaje się ortooctanowej modyfikacji przegrupowania Claisena. Otrzymany w ten sposób ester etylowy kwasu (±)-trans-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego albo ester etylowy kwasu (+)-(1'S,4'S)-(4'-izopropylo-1'-metylo-cykloheks-2'-en-1'-ylo)octowego, albo ester etylowy kwasu (-)-(1'R,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego hydrolizuje się do kwasu (±)-trans-(4'-izopropylu-1'-metylocykloheks-2'-en-1'-ylo)octowego albo do kwasu (+)-(1'S,4'S)-(4'-izopropylu-1'-metylocykloheks-2'-en-1'-ylo)octowego, albo do kwasu (-)-(1'R,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego.The method of obtaining new δ-iodo-y-lactones with the cis p-menthane system, with formulas 1, 2 and 3 shown in the figure, with antifungal activity, consists in the fact that (±) -trans-piperitol or (-) (3S , 4S) -piperitol or (+) - (3R, 4R) -piperitol undergoes an orthoacetate modification of the Claisen rearrangement. The thus obtained ethyl ester of (±) -trans- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid or ethyl ester of (+) - (1'S, 4'S) - ( 4'-isopropyl-1'-methyl-cyclohex-2'-en-1'-yl) acetic acid, or (-) - (1'R, 4'R) - (4'-isopropyl-1 'acid ethyl ester -methylcyclohex-2'-en-1'-yl) acetic acid is hydrolyzed to (±) -trans- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid or to ( +) - (1'S, 4'S) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid, or to (-) - (1'R, 4'R) - ( 4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic.
Otrzymane wspomniane kwasy poddaje się reakcji halolaktonizacji, w środowisku zasadowym, w wyniku czego otrzymuje się odpowiednio: (±)-c-5-jodo-c-4-izo-propylo-r-1-metylo-7-oksa-cis-bicyklo[4.3.0]nonan-8-on, o wzorze 1, albo (+)-(1S,4S,5R,6R)-5-jodo-4-izopropylo-1-metylo-7-oksa-bicyklo[4.3.0]nonan-8-on, o wzorze 2, albo (-)-(1R,4R,5S,6S)-5-jodo-4-izopropylo-1-metylo-7-oksa-bicyklo[4.3.0]nonan-8-on, o wzorze 3.The obtained acids are subjected to a halolactonization reaction in a basic medium, which gives the following, respectively: (±) -c-5-iodo-c-4-iso-propyl-r-1-methyl-7-oxa-cis-bicyclo [4.3.0] nonan-8-one, of formula 1, or (+) - (1S, 4S, 5R, 6R) -5-iodo-4-isopropyl-1-methyl-7-oxa-bicyclo [4.3. O] nonan-8-one, of formula 2, or (-) - (1R, 4R, 5S, 6S) -5-iodo-4-isopropyl-1-methyl-7-oxa-bicyclo [4.3.0] nonane -8-one, of formula 3.
δ-Jodo-y-laktony z układem cis p-mentanu, posiadają aktywność antyfidantną w stosunku do mszycy brzoskwiniowo ziemniaczanej (Myzus persicae Sulz).δ-iodo-γ-lactones with the cis p-menthane system have antifidant 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 połowie 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. P - poziom istotności różnicy statystycznej.T - the average number of aphids on a half of a leaf moistened with 0.1% ethanolic solution of the test compound. P - significance level of the statistical difference.
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 1 3 Example 1 3
Do 2,00 g racemicznego (±)-trans-piperytolu (12,98 mmola) dodaje się 17.0 cm3 (89,25 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 (GC, 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). Otrzymuje się 2,18 g (9,73 mmola) czystego estru etylowego kwasu (±)-cis(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego, co stanowi 75% wydajności teoretycznej.To 2.00 g of racemic (±) -trans-piperitole (12.98 mmol) are added 17.0 cm 3 (89.25 mmol) of triethyl orthoacetate and a catalytic amount of propionic acid (1 drop) and heated at 411K, distilled in continuously forming ethanol. After completion of the reaction (GC, TLC - 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). 2.18 g (9.73 mmol) of pure (±) -cis (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester were obtained, which is 75% of theory .
Dane spektroskopowe otrzymanego estru etylowego kwasu (±)-trans-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są następujące:The spectroscopic data of the obtained (±) -trans- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester are as follows:
1H NMR (600 MHz, CDCfe) δ: 0,86 i 0,89 (dwa d, J = 6,8 Hz, 6H, (CH^CH-), 1,06 (s, 3H, CH3-1'), 1 H NMR (600 MHz, CDCl 2) δ: 0.86 and 0.89 (two d, J = 6.8 Hz, 6H, (CH 2 CH-), 1.06 (s, 3H, CH 3 -1 '),
1,24 (t, J = 7,1 Hz, 3H, -OCH2CH3), 1,38 (m, 1H, jeden z CH3-5'), 1,54-1,69 (m, 4H, jeden z CH3-5'1.24 (t, J = 7.1 Hz, 3H, -OCH2CH3), 1.38 (m, 1H, one of CH 3 -5 '), 1.54-1.69 (m, 4H, one of CH 3 -5 '
CH2-6' i (CHshCH-), 1,88 (m, 1H, H-4'), 2,24 (s, 2H, CH2-2), 4,10 i 4,11 (dwa q, J = 7,1 Hz, 2H,CH2-6 'i (CHshCH-), 1.88 (m, 1H, H-4'), 2.24 (s, 2H, CH2-2), 4.10 and 4.11 (two q, J = 7.1 Hz, 2H,
-OCH2CH3), 5,50-5,56 (m, 2H, H-2' i H-3');-OCH2CH3), 5.50-5.56 (m, 2H, H-2 'and H-3');
PL 212 023 B1 13C NMR (600 MHz, CDCfe) δ: 14,31 (-OCH2CH3), 19,22 i 19,59 ((CH^CH-), 21,90 (C-5'), 26,68 (CH3-I'), 31,90 ((CH3)2CH-), 34,55 (C-1'), 34,66 (C-6'), 41,60 (C-4'), 47,60 (C-2), 59,92 (-OCH2CH3), 129,64 (C-2'), 135,10 (C-3'), 171,88 (C-1); 13 C NMR (600 MHz, CDCfe) δ: 14.31 (-OCH2CH3), 19.22 and 19.59 ((CH2CH-), 21.90 (C-5 '), 26, 68 (CH3-I '), 31.90 ((CH3) 2CH-), 34.55 (C-1'), 34.66 (C-6 '), 41.60 (C-4'), 47 , 60 (C-2), 59.92 (-OCH2CH3), 129.64 (C-2 '), 135.10 (C-3'), 171.88 (C-1);
IR (film, cm-1): 2959 (s), 1734 (s), 1461 (m), 1367 (m), 1254 (m), 1158 (m), 1034 (m);IR (film, cm -1 ): 2959 (s), 1734 (s), 1461 (m), 1367 (m), 1254 (m), 1158 (m), 1034 (m);
Otrzymany ester etylowy kwasu (±)-trans-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octo3 wego (2,18 g, 9,73 mmola) rozpuszcza się w 30 cm3 2,5% metanolowego roztworu wodorotlenku po3 tasu i 1 cm3 wody, a następnie ogrzewa się pod chłodnicą zwrotną. Po zakończeniu reakcji (GC, TLCThe resulting ethyl ester of (±) -trans (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid 3 (2.18 g, 9.73 mmol) is dissolved in 30 cm 3 of 2.5% methanolic hydroxide solution of 3 potassium each and 1 cm 3 of water, and then heated to reflux. After completion of the reaction (GC, TLC
- heksan:eter dietylowy 4:1) metanol oddestylowuje się pod zmniejszonym ciśnieniem. Pozostałość 3 rozpuszcza się w wodzie (40 cm3), zakwasza się 0,5 M roztworem kwasu solnego (do pH około 4) 3 i ekstrahuje się 40 cm3 eteru dietylowego. Frakcję organiczną oddziela się a warstwę wodną ponownie 3 ekstrahuje eterem dietylowym (3 x 20 cm3). Połączone warstwy 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). Otrzymuje się 1,81 g (9,24 mmola) kwasu (±)-trans-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego, co stanowi 95% wydajności teoretycznej.- hexane: diethyl ether 4: 1) methanol was distilled off under reduced pressure. The residue 3 is dissolved in water (40 cm 3 ), acidified with 0.5 M hydrochloric acid solution (to about pH 4) 3 and extracted with 40 cm 3 of diethyl ether. The organic fraction was separated and the aqueous layer was re-extracted with diethyl ether 3 (3 x 20 cm 3). The combined ether layers 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). 1.81 g (9.24 mmol) of (±) -trans- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid were obtained, representing 95% of theory.
Dane spektroskopowe otrzymanego kwasu (±)-trans-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są następujące:The spectroscopic data of the obtained (±) -trans- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid are as follows:
1H NMR (600 MHz, CDCl3) δ: 0,87 i 0,89 (dwa d, J = 6,8 Hz, 6H, (CH3)2CH-), 1,10 (s, 3H, CH3-1'), 1,40 (m, 1H, jeden z CH2-5'), 1,56-1,64 (m, 4H, jeden z CH2-5', CH2-6' i (CH^CH-), 1,90 (m, 1H, H-4'), 2,29 (s, 2H, CH2-2), 5,54 (d, J = 10,5 Hz, 1H, H-2'), 5,57 (dd, J = 10,5 i 1,7 Hz. 1H, H-3'); 1 H NMR (600 MHz, CDCl3) δ: 0.87 and 0.89 (two d, J = 6.8 Hz, 6H, (CH 3) 2 CH-), 1.10 (s, 3H, CH3-1 ' ), 1.40 (m, 1H, one of CH 2 -5 '), 1.56-1.64 (m, 4H, one of CH 2 -5', CH 2 -6 'and (CH 2 CH- ), 1.90 (m, 1H, H-4 '), 2.29 (s, 2H, CH 2 -2), 5.54 (d, J = 10.5 Hz, 1H, H-2') , 5.57 (dd, J = 10.5 and 1.7 Hz, 1H, H-3 ');
13C NMR (600 MHz, CDCfe) δ: 19,21 i 19,59 ((CH^CH-), 21,79 (C-5'), 26,56 (CH3-1'), 31,87 ((CH3)2CH-), 34,45 (C-1'), 34,61 (C-6'), 41,50 (C-4'), 47,35 (C-2), 130,02 (C-2'), 134,72 (C-3'), 178,35 (C-1); 13 C NMR (600 MHz, CDCl?) Δ: 19.21 and 19.59 ((CH2CH-), 21.79 (C-5 '), 26.56 (CH3-1'), 31.87 ( (CH3) 2CH-), 34.45 (C-1 '), 34.61 (C-6'), 41.50 (C-4 '), 47.35 (C-2), 130.02 ( C-2 '), 134.72 (C-3'), 178.35 (C-1);
IR (film, cm-1): 2888-3500 (b, s), 2934 (s), 1705 (s), 1410 (m), 1368 (m), 1280 (m).IR (film, cm -1 ): 2888-3500 (b, s), 2934 (s), 1705 (s), 1410 (m), 1368 (m), 1280 (m).
Uzyskany kwas (±)-trans-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowy (1,81 g, 9,24 33 mmola) rozpuszcza się w 40 cm3 eteru dietylowego i dodaje się 0,5 M roztwór NaHCO3 (40 cm3) a następnie ogrzewa się pod chłodnicą zwrotną. Do wrzącej mieszaniny dodaje się kroplami roztwór 3 zawierający w 43 cm3 wody 5,58 g jodu (22 mmole) i 10,96 g jodku potasu (66 mmoli). Po zakończeniu reakcji (GC, TLC - heksan:eter dietylowy 2:1) mieszaninę poreakcyjną rozcieńcza się eterem diety3 lowym (40 cm3) i przemywa roztworem Na2S2O3 w celu zredukowania nadmiaru jodu. Warstwę orga3 niczną oddziela się, a fazę wodną ekstrahuje eterem dietylowym (3 x 20 cm3). Połączone warstwy eterowe przemywa się roztworem NaHCO3, a następnie solanką (do 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 2,40 g (7,45 mmola) (±)-c-5-jodo-c-4-izopropylo-r-1-metylo-7-oksa-cis-bicyklo[4.3.0]nonan-8-onu, o wzorze 1, z wydajnością 81%.The obtained (±) -trans- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid (1.81 g, 9.24 of 33 mmol) is dissolved in 40 cm 3 of diethyl ether. and 0.5 M NaHCO3 solution (40 cm 3) and heated to reflux. To the boiling mixture is added dropwise a solution 3 containing in 43 cm 3 of water 5.58 g of iodine (22 mmol) and 10.96 g of potassium iodide (66 mmol). After completion of the reaction (GC, TLC - hexane: diethyl ether 2: 1) mixture is diluted with diethyl ether 3 (40 cm 3) and washed with Na2S2O3 solution to reduce the excess iodine. 3-border organic layer was separated, and the aqueous phase extracted with diethyl ether (3 x 20 cm 3). The combined ether layers were washed with NaHCO3 solution, then with 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). 2.40 g (7.45 mmol) of (±) -c-5-iodo-c-4-isopropyl-r-1-methyl-7-oxa-cis-bicyclo [4.3.0] nonan-8- is obtained. onu, formula I, in 81% yield.
Wydajność tej trzyetapowej syntezy, liczona w stosunku do wyjściowego (±)-trans-piperytolu, wynosi 57%.The yield of this three-step synthesis, relative to the starting (±) -trans-piperitol, is 57%.
Dane spektroskopowe otrzymanego (±)-c-5-jodo-c-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-c-4-isopropyl-r-1-methyl-7-oxa-cis-bicyclo [4.3.0] -nonan-8-one are as follows:
1H NMR (600 MHz, CDCh) δ: 0,28 (m, 1H, H-4), 0,86 i 0,96 (dwa d, J = 6,6 Hz, 6H, (CH3)2CH-), 1,24-1,37 (m, 2H, (CH3)2CH- i jeden z CH2-3), 1,42 (m, 1H, jeden z CH2-2), 1,46 (s, 3H, CH3-1), 1,61-1,67 (m, 2H, jeden z CH2-3 i jeden z CH2-2), 2,25 i 2,43 (dwa d, J = 16,7 Hz, 2H, CH2-9, układ AB), 4,63 (m, 1H, H-5), 4,69 (m, 1H, H-6); 1 H NMR (600 MHz, CDCl 3) δ: 0.28 (m, 1H, H-4), 0.86 and 0.96 (two d, J = 6.6 Hz, 6H, (CH3) 2 CH- ), 1.24-1.37 (m, 2H, (CH3) 2 CH- and one of CH 2 -3), 1.42 (m, 1H, one of CH 2 -2), 1.46 (s , 3H, CH3-1), 1.61-1.67 (m, 2H, one of CH 2 -3, and one of the CH 2 -2), 2.25 and 2.43 (two d, J = 16. 7 Hz, 2H, CH 2 -9, AB system), 4.63 (m, 1H, H-5), 4.69 (m, 1H, H-6);
13C NMR (600 MHz, CDCh) δ: 19,46 i 20,22 (CH^CH-), 21,74 (C-3), 25,26 (CH3-1), 33,54 (CH3)2CH-), 34,21 (C-2), 34,24 (C-5), 38,22 (C-1), 43,19 (C-4), 46,42 (C-9), 87,88 (C-6); 174,00 (C-8); 13 C NMR (600 MHz, CDCl 3) δ: 19.46 and 20.22 (CH2CH-), 21.74 (C-3), 25.26 (CH3-1), 33.54 (CH3) 2 CH-), 34.21 (C-2), 34.24 (C-5), 38.22 (C-1), 43.19 (C-4), 46.42 (C-9), 87 , 88 (C-6); 174.00 (C-8);
IR (KBr, cm-1): 2960 (m), 1775 (s), 1373 (w), 1229 (m), 633 (m); analiza elementarna: C12H19O2 (322,17); obliczono: C 44,74, H 5,94;IR (KBr, cm -1 ): 2960 (m), 1775 (s), 1373 (w), 1229 (m), 633 (m); elemental analysis: C12H19O2 (322.17); calcd: C 44.74, H 5.94;
znaleziono: C 45,73, H 6,18.found: C 45.73, H 6.18.
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 do przeprowadzenia reakcji stosuje się (-)-(3S,4S)-piperitol.The procedure is as in Example 1, except that (-) - (3S, 4S) -piperitol is used to carry out the reaction.
Z 1,5 g (9,74 mmola) (-)-(3S,4S)-piperitolu otrzymuje się 1,60 g (7,16 mmola) estru etylowego kwasu (+)-(1'S,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego (\a^ = +24,9° (c = 0,83,From 1.5 g (9.74 mmol) of (-) - (3S, 4S) -piperitol, 1.60 g (7.16 mmol) of ethyl ester of (+) - (1'S, 4'S) - (4 ') are obtained -isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid (\ a ^ = + 24.9 ° (c = 0.83,
CHCl3); ee = 95%). Stanowi to 74% wydajności teoretycznej.CHCl3); ee = 95%). This is 74% of the theoretical amount.
PL 212 023 B1PL 212 023 B1
Dane spektroskopowe estru etylowego kwasu (+)-(1'S,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są takie same jak estru etylowego kwasu (±)-trans-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego.The spectroscopic data of (+) - (1'S, 4'S) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester is the same as (±) -trans- ethyl ester (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic.
W reakcji hydrolizy 1,60 g (7,16 mmola) estru etylowego kwasu (+)-(1'S,4'S)-t-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego otrzymuje się, z 92% wydajnością, 1,29 g, (6,58 mmola) kwasu (+)-(1'S,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego ([a]} = +31,7° (c = 1,25, CHCl3)).By hydrolysis of 1.60 g (7.16 mmol) of (+) - (1'S, 4'S) -t- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester obtained, in 92% yield, 1.29 g (6.58 mmol) of (+) - (1'S, 4'S) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acid ) acetic ([a]} = + 31.7 ° (c = 1.25, CHCl 3 )).
Dane spektroskopowe kwasu (+)-(1'S,4'S)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są takie same jak kwasu (±)-trans-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego.The spectroscopic data of (+) - (1'S, 4'S) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid is the same as for (±) -trans- (4'- isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic.
W wyniku laktonizacji 1,29 g (6,58 mmola) kwasu (+)-(1'S,4'S)-(4'-izopropylo-1'-metylocykloheks2'-en-1'-ylo)octowego otrzymuje się, z 81% wydajnością, 1,71 g (5,31 mmola) (+)-(1S,4S, 5R,6R)-5-jodo-4-izopropylo-1-metylo-7-oksabicyklo[4.3.0]nonan-8-onu, o wzorze 2, i następujących stałych fizycznych: [a]31 = +24,5° (c = 1,05, CHCl3); ee = 98%.After lactonization, 1.29 g (6.58 mmol) of (+) - (1'S, 4'S) - (4'-isopropyl-1'-methylcyclohex2'-en-1'-yl) acetic acid were obtained, with 81% yield, 1.71 g (5.31 mmol) (+) - (1S, 4S, 5R, 6R) -5-iodo-4-isopropyl-1-methyl-7-oxabicyclo [4.3.0] nonan-8- one, of formula 2, and the following physical constants: [a] 31 = + 24.5 ° (c = 1.05, CHCl 3 ); ee = 98%.
Dane spektroskopowe (+)-(1S,4S,5R,6R)-5-jodo-4-izopropylo-1-metylo-7-oksa-bicyklo[4.3.0]nonan-8-onu są takie same jak (±)-c-5-jodo-c-4-izopropylo-r-1-metylo-7-oksa-cis-bicyklo[4.3.0]nonan-8-onu.The spectroscopic data of (+) - (1S, 4S, 5R, 6R) -5-iodo-4-isopropyl-1-methyl-7-oxa-bicyclo [4.3.0] nonan-8-one are the same as (±) -c-5-iodo-c-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,4S)-piperitolu, wynosi 54%.The yield of this three-step synthesis, based on the amount of (-) - (3S, 4S) -piperitol used, is 54%.
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 do przeprowadzenia reakcji stosuje się (+)-(3R,4R)piperytol.The procedure is as in Example 1 except that (+) - (3R, 4R) piperitol is used for the reaction.
Z 1,68 g (10,91 mmola) (+)-(3R,4R)-piperytolu otrzymuje się 1,73 g (7,72 mmola) estru etylowego kwasu (-)-(1'R,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego ([a]22 = -37,6° (c = 0,8, CHCl3); ee = 96%).From 1.68 g (10.91 mmol) of (+) - (3R, 4R) -pipererythole 1.73 g (7.72 mmol) of (-) - (1'R, 4'R) acid ethyl ester are obtained - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ([a] 22 = -37.6 ° (c = 0.8, CHCl3); ee = 96%).
Wydajność reakcji wynosi 71%.The reaction yield is 71%.
Dane spektroskopowe estru etylowego kwasu (-)-(1'R,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są takie same jak estru etylowego kwasu (±)-trans-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego.The spectroscopic data of (-) - (1'R, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid ethyl ester is the same as (± ) -trans- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic.
W reakcji hydrolizy 1,73 g (7,72 mmola) estru etylowego kwasu (-)-(1'R,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego otrzymuje się, z 99% wydajnością, 1,50 g (7,65 mmola) kwasu (-)-(1'R,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego [a]24 = -30,6° (c = 1,60, CHCl3)).1.73 g (7.72 mmol) of (-) - (1'R, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acid ethyl ester by hydrolysis ) acetic acid is obtained, in 99% yield, 1.50 g (7.65 mmol) of (-) - (1'R, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-ene -1'-yl) acetic [a] 24 = -30.6 ° (c = 1.60, CHCl 3)).
Dane spektroskopowe kwasu (-)-(1'R,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego są takie same jak kwasu (±)-trans-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego.The spectroscopic data of (-) - (1'R, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid is the same as for (±) -trans- (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic.
W wyniku laktonizacji 1,50 g (7,65 mmola) kwasu (-)-(1'R,4'R)-(4'-izopropylo-1'-metylocykloheks-2'-en-1'-ylo)octowego otrzymuje się, z 87% wydajnością, 2,14 g (6,64 mmola) (-)-(1R,4R, 5S,6S)-5-jodo-4-izopropylo-1-metylo-7-oksabicyklo[4.3.0]nonan-8-onu, o wzorze 3, i następujących stałych fizycznych: [a]31= -21,2° (c = 1,42, CHCl3); ee = 94%.By lactonization, 1.50 g (7.65 mmol) of (-) - (1'R, 4'R) - (4'-isopropyl-1'-methylcyclohex-2'-en-1'-yl) acetic acid obtained, in 87% yield, 2.14 g (6.64 mmol) of (-) - (1R, 4R, 5S, 6S) -5-iodo-4-isopropyl-1-methyl-7-oxabicyclo [4.3. O] nonan-8-one, of formula 3, and the following physical constants: [a] 31 = -21.2 ° (c = 1.42, CHCl3); ee = 94%.
Dane spektroskopowe (-)-(1R,4R,5S,6S)-5-jodo-4-izopropylo-1-metylo-7-oksabi-cyklo[4.3.0]nonan-8-onu są takie same jak (±)-c-5-jodo-c-4-izopropylo-r-1-metylo-7-oksa-cis-bicyklo[4.3.0]nonan-8-onu.The spectroscopic data of (-) - (1R, 4R, 5S, 6S) -5-iodo-4-isopropyl-1-methyl-7-oxabicyclo [4.3.0] nonan-8-one is the same as (±) -c-5-iodo-c-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,4R)-piperytolu, wynosi 61%.The yield of this three-step synthesis, based on the amount of (+) - (3R, 4R) -piperiteol used, is 61%.
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