PL217468B1 - Method of obtaining esters and lactones in the environment of ionic liquids - Google Patents
Method of obtaining esters and lactones in the environment of ionic liquidsInfo
- Publication number
- PL217468B1 PL217468B1 PL385859A PL38585908A PL217468B1 PL 217468 B1 PL217468 B1 PL 217468B1 PL 385859 A PL385859 A PL 385859A PL 38585908 A PL38585908 A PL 38585908A PL 217468 B1 PL217468 B1 PL 217468B1
- Authority
- PL
- Poland
- Prior art keywords
- lactones
- ionic liquids
- environment
- otf
- esters
- Prior art date
Links
- 239000002608 ionic liquid Substances 0.000 title claims description 13
- 150000002596 lactones Chemical class 0.000 title claims description 11
- 150000002148 esters Chemical class 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- XPEMYYBBHOILIJ-UHFFFAOYSA-N trimethyl(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](C)(C)C XPEMYYBBHOILIJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- -1 adamantonu Chemical compound 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000003997 cyclic ketones Chemical class 0.000 claims description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 2
- 241000723346 Cinnamomum camphora Species 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229960000846 camphor Drugs 0.000 claims description 2
- 229930008380 camphor Natural products 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- KPMKEVXVVHNIEY-RITPCOANSA-N norcamphor Chemical compound C1C[C@@H]2C(=O)C[C@H]1C2 KPMKEVXVVHNIEY-RITPCOANSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000003998 acyclic ketones Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- FRZPYEHDSAQGAS-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+]=1C=CN(C)C=1 FRZPYEHDSAQGAS-UHFFFAOYSA-M 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku jest sposób otrzymywania estrów z acyklicznych ketonów o budowie 1 2 1 2 ogólnej R1COR2 gdzie R1 oznacza metyl lub fenyl; R2 oznacza fenyl oraz laktonów z cyklicznych ketonów np.: cyklobutanonu, cyklopentanonu, cykloheksanonu, adamantonu, norkamfory lub kamfory w obecności cieczy jonowych w reakcji utleniania Baeyera- Villigera.The subject of the invention is a process for the preparation of esters from acyclic ketones of general structure R 1 COR 2 where R 1 is methyl or phenyl; R 2 is phenyl and lactones with cyclic ketones e.g. .: cyclobutanone, cyclopentanone, cyclohexanone, adamantonu, or camphor, norcamphor in the presence of ionic liquids in the reaction Baeyera- Villiger oxidation.
Reakcja utleniania Baeyera-Villigera odpowiednich ketonów do estrów i laktonów jest szeroko stosowana w syntezie organicznej. Laktony są ważnymi związkami przejściowymi chętnie wykorzystywanymi w przemyśle, znajdują zastosowanie w produkcji polimerów, farmaceutyków, herbicydów oraz stosowane są jako rozpuszczalniki.The Baeyer-Villiger oxidation reaction of the respective ketones to esters and lactones is widely used in organic synthesis. Lactones are important intermediates readily used in industry, they are used in the production of polymers, pharmaceuticals, herbicides and are used as solvents.
Znana jest dotychczas metoda syntezy estrów i laktonów w wyniku reakcji utleniania Baeyera-Villigera acyklicznych i cyklicznych ketonów prowadzona wobec substancji nadtlenowych takich jak: nadtlenokwasy organiczne, nadtlenek wodoru, nadtlenek bis(trimetylosililowy), wodoronadtlenki alkilowe, w obecności kwaśnych lub zasadowych katalizatorów w środowisku klasycznych rozpuszczalników np. chloroformu, chlorku metylenu, acetonitrylu. Zastosowanie nadtlenku bis(trimetylosililowego) jako utleniacza w powyższych reakcjach wymaga zastosowania jako katalizatora kwasu Lewisa np. BF3*OEt2, SnCl4 lub estru trifluorometanosulfonianu trimetylosililowego.The method of synthesizing esters and lactones as a result of the Baeyer-Villiger oxidation of acyclic and cyclic ketones in the presence of peroxy substances such as: organic peroxyacids, hydrogen peroxide, bis (trimethylsilyl) peroxide, alkyl hydroperoxides in the presence of acidic or basic catalysts solvents, e.g. chloroform, methylene chloride, acetonitrile. The use of bis (trimethylsilyl) peroxide as the oxidant in the above reactions requires the use of a Lewis acid catalyst, e.g., BF3 * OEt2, SnCl4, or trimethylsilyl triflate ester.
Sposób według wynalazku polega na tym, że związki otrzymuje się w obecności cieczy jonowych o wzorze [Y]+ [OTf] , gdzie [Y]+ oznacza kation dialkiloimidazoliowy, w którym alkil to butyl, pentyl lub heksyl, a [OTf] oznacza anion trifluorometanosulfonowy oraz nadtlenku bis(trimetylosililowego) w temperaturze 20 - 40°C w czasie 2 - 24 godzin.The method according to the invention consists in that the compounds are obtained in the presence of ionic liquids of formula [Y] + [OTf], where [Y] + is a dialkylimidazolium cation, where alkyl is butyl, pentyl or hexyl and [OTf] is an anion trifluoromethanesulfonic acid and bis (trimethylsilyl) peroxide at 20 - 40 ° C for 2 - 24 hours.
Ciecze jonowe to sole zawierające w swej strukturze kation organiczny i anion, najczęściej nieorganiczny występujące w postaci ciekłej w temperaturach poniżej 100°C. Są one wykorzystywane jako nowe, ekologiczne rozpuszczalniki w syntezie organicznej. Stosowane przez nas ciecze jonowe obok funkcji rozpuszczalnika spełniają również rolę aktywatora reakcji.Ionic liquids are salts containing in their structure an organic cation and an anion, most often inorganic, occurring in liquid form at temperatures below 100 ° C. They are used as new, ecological solvents in organic synthesis. The ionic liquids we use, apart from the solvent function, also act as a reaction activator.
Sposób według wynalazku polega na tym, że do cieczy jonowej o budowie [Y]+ [OTf] wprowadza się nadtlenek bis(trimetylosililowy) oraz keton. Układ reakcyjny utrzymuje się w temperaturze 20 - 40°C przez 2 - 24 godzin. W tych warunkach następuje reakcja utleniania ketonu do odpowiedniego estru lub laktonu. Produkty reakcji są wydzielane ze środowiska cieczy jonowych poprzez ekstrakcję mieszaniny reakcyjnej eterem dietylowym. Po zatężeniu warstwy eterowej otrzymuje się odpowiednie estry i laktony z dobrymi wydajnościami 41 - 95%. Po oddzieleniu produktów ubocznych i nieprzereagowanych substratów oraz osuszeniu zastosowane ciecze jonowe można użyć ponownie.The method according to the invention consists in introducing bis (trimethylsilyl) peroxide and a ketone into the ionic liquid of the structure [Y] + [OTf]. The reaction system is held at 20-40 ° C for 2-24 hours. Under these conditions, the ketone oxidizes to the corresponding ester or lactone. The reaction products are separated from the ionic liquid environment by extracting the reaction mixture with diethyl ether. After concentration of the ether layer, the corresponding esters and lactones are obtained in good yields of 41-95%. After separation of by-products and unreacted substrates and drying, the used ionic liquids can be reused.
Wynalazek umożliwia otrzymywanie estrów i laktonów w obecności cieczy jonowych posiadających w swej strukturze anion trifluorometanosulfonowy [OTf] .The invention makes it possible to obtain esters and lactones in the presence of ionic liquids containing in their structure the trifluoromethanesulfonic anion [OTf].
Sposób według wynalazku stwarza możliwości syntezy ketonów i laktonów bez konieczności stosowania dodatkowych katalizatorów oraz przy zastosowaniu czystych dla środowiska rozpuszczalników. Zastosowane do syntezy ciecze jonowe pełnią jednocześnie rolę rozpuszczalnika i aktywatora reakcji.The process according to the invention enables the synthesis of ketones and lactones without the need to use additional catalysts and with the use of environmentally friendly solvents. The ionic liquids used for the synthesis act both as a solvent and as a reaction activator.
P r z y k ł a d I.P r z x l a d I.
Metoda syntezy ε-kaprolaktonu: Do kolby okrągłodennej o pojemności 5 ml wprowadza się 2 ml cieczy jonowej trifluorometanosulfonianu 1-butylo-3-metyloimidazoliowego [BMIM]'[OTf] , cykloheksanon (0.50 mmol) oraz nadtlenek bis(trimetylosililowy) (1.00 mmol). Zawartość kolby miesza się w temperaturze 20°C przez 2 h, a następnie produkt ekstrahuje się z mieszaniny poreakcyjnej przy pomocy eteru dietylowego. Warstwę eterową przemywa się 2 ml 1 molowego NaHCO3, oraz 1 ml wody a następnie zatęża pod próżnią. Otrzymuje się ε-kaprolakton z wydajnością 90%. Po usunięciu wody ciecz jonową poddaje się recyklowi.Method for the synthesis of ε-caprolactone: 2 ml of 1-butyl-3-methylimidazolium triflate [BMIM] '[OTf], cyclohexanone (0.50 mmol) and bis (trimethylsilyl) peroxide (1.00 mmol) are introduced into a 5 ml round-bottom flask. . The contents of the flask are stirred at 20 ° C for 2 h, then the product is extracted from the reaction mixture with diethyl ether. The ether layer is washed with 2 mL of 1M NaHCO3, and 1 mL of water and then concentrated in vacuo. Ε-caprolactone is obtained with a yield of 90%. After removing the water, the ionic liquid is recycled.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL385859A PL217468B1 (en) | 2008-08-11 | 2008-08-11 | Method of obtaining esters and lactones in the environment of ionic liquids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL385859A PL217468B1 (en) | 2008-08-11 | 2008-08-11 | Method of obtaining esters and lactones in the environment of ionic liquids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL385859A1 PL385859A1 (en) | 2010-02-15 |
| PL217468B1 true PL217468B1 (en) | 2014-07-31 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL385859A PL217468B1 (en) | 2008-08-11 | 2008-08-11 | Method of obtaining esters and lactones in the environment of ionic liquids |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL217468B1 (en) |
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2008
- 2008-08-11 PL PL385859A patent/PL217468B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| PL385859A1 (en) | 2010-02-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Decisions on the lapse of the protection rights |
Effective date: 20110811 |