CN112851597A - Method for synthesizing oxazolidinone by using imidazolium salt as catalyst - Google Patents
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- oxazolidinone
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- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 150000004693 imidazolium salts Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000012948 isocyanate Substances 0.000 claims abstract description 26
- 150000002118 epoxides Chemical class 0.000 claims abstract description 25
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000004440 column chromatography Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 13
- -1 monochloromethyl Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229910052740 iodine Chemical group 0.000 claims description 2
- 239000011630 iodine Chemical group 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 6
- 239000002184 metal Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- 238000001035 drying Methods 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 26
- 239000011261 inert gas Substances 0.000 description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- FMDGXCSMDZMDHZ-UHFFFAOYSA-N 1-isocyanato-4-methoxybenzene Chemical compound COC1=CC=C(N=C=O)C=C1 FMDGXCSMDZMDHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000007363 ring formation reaction Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OTOSIXGMLYKKOW-UHFFFAOYSA-M 1,3-bis(2,4,6-trimethylphenyl)imidazol-1-ium;chloride Chemical compound [Cl-].CC1=CC(C)=CC(C)=C1N1C=[N+](C=2C(=CC(C)=CC=2C)C)C=C1 OTOSIXGMLYKKOW-UHFFFAOYSA-M 0.000 description 2
- CPPGZWWUPFWALU-UHFFFAOYSA-N 1-isocyanato-3-methylbenzene Chemical compound CC1=CC=CC(N=C=O)=C1 CPPGZWWUPFWALU-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical class N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- MYPYJXKWCTUITO-LYRMYLQWSA-N vancomycin Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C2C=C3C=C1OC1=CC=C(C=C1Cl)[C@@H](O)[C@H](C(N[C@@H](CC(N)=O)C(=O)N[C@H]3C(=O)N[C@H]1C(=O)N[C@H](C(N[C@@H](C3=CC(O)=CC(O)=C3C=3C(O)=CC=C1C=3)C(O)=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)O2)=O)NC(=O)[C@@H](CC(C)C)NC)[C@H]1C[C@](C)(N)[C@H](O)[C@H](C)O1 MYPYJXKWCTUITO-LYRMYLQWSA-N 0.000 description 2
- 150000000179 1,2-aminoalcohols Chemical class 0.000 description 1
- IKQCDTXBZKMPBB-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;iodide Chemical compound [I-].CCN1C=C[N+](C)=C1 IKQCDTXBZKMPBB-UHFFFAOYSA-M 0.000 description 1
- NRSSOFNMWSJECS-UHFFFAOYSA-N 1-isocyanato-3,5-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC(N=C=O)=CC(C(F)(F)F)=C1 NRSSOFNMWSJECS-UHFFFAOYSA-N 0.000 description 1
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000194033 Enterococcus Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Chemical class 0.000 description 1
- 241001652963 Speranza Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 108010059993 Vancomycin Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 229940005513 antidepressants Drugs 0.000 description 1
- 239000000164 antipsychotic agent Substances 0.000 description 1
- 229940005529 antipsychotics Drugs 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000013501 data transformation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 229960003085 meticillin Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002866 paraformaldehyde Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229960003165 vancomycin Drugs 0.000 description 1
- MYPYJXKWCTUITO-UHFFFAOYSA-N vancomycin Natural products O1C(C(=C2)Cl)=CC=C2C(O)C(C(NC(C2=CC(O)=CC(O)=C2C=2C(O)=CC=C3C=2)C(O)=O)=O)NC(=O)C3NC(=O)C2NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(CC(C)C)NC)C(O)C(C=C3Cl)=CC=C3OC3=CC2=CC1=C3OC1OC(CO)C(O)C(O)C1OC1CC(C)(N)C(O)C(C)O1 MYPYJXKWCTUITO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/24—Oxygen atoms attached in position 2 with hydrocarbon radicals, substituted by oxygen atoms, attached to other ring carbon atoms
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Abstract
The invention discloses a method for synthesizing oxazolidinone by using imidazolium salt as a catalyst, belonging to the technical field of organic synthesis. The invention adopts epoxide and isocyanate as raw materials, and adopts the catalyst of formula (I) provided by the invention to react to obtain oxazolidinone. The method has the advantages of cheap and easily-obtained reagents, capability of synthesizing the product by a one-step method, mild conditions, high efficiency and no metal residue in the whole reaction system.
Description
Technical Field
The invention belongs to the technical field of organic catalysis, and particularly relates to a method for producing oxazolidinone by using a [3+2] cyclization reaction between epoxide and isocyanate.
Background
Oxazolidinones are five-membered heterocycles containing N and O atoms and can be used as chiral auxiliary in asymmetric syntheses, intermediates and precursors for amino alcohol syntheses and building blocks for polymers, and oxazolidinones themselves have important applications as an emerging pharmacophore in pharmaceutical chemistry. (Eur.J.org.chem.2020, 1881-1895). Among them, N-aryl substituted oxazolidinones are useful as precursors of antibacterial agents against enterococcus Vancomycin (VRE) and methicillin-resistant Staphylococcus aureus (MRSA). (Med. chem. Lett.2008,18, 4868-4871) in addition, oxazolidinones are useful for the synthesis of antipsychotics and antidepressants, and therefore, the development of a simple and efficient method for oxazolidinones has been a major concern. (J.Med.chem.2002,45, 1180-
Up to now, a large number of synthetic oxazolidinones have been reported, such as the cyclization of alpha-amino acids or 1, 2-amino alcohols with carbonyl derivatives, carbamation, Au and Ag catalyzed cyclization of N boropropylalkynylamines and propargyl alcohols, and the [3+2] cyclization of epoxides with isocyanates, the most direct, atom-efficient and economically efficient method being the [3+2] cyclization of epoxides with isocyanates, which can lead to a variety of substituted oxazolidinones by varying the substituents on the epoxides and isocyanates. Oxygen on the epoxide is activated by lewis acid, then lewis base nucleophilically attacks methylene carbon in the epoxide to open the ring, and finally isocyanate is inserted to close the ring to form oxazolidinone. Speranza and Pepple et al, 1958, reported the use of tetrabutylammonium salts to catalyze the synthesis of oxazolidinones from epoxides and isocyanates. (J.org.chem.1958,23,1922). After that, many metal salt catalysts are reported to catalyze the [3+2] cyclization reaction of epoxides with isocyanates, but the reaction conditions are very harsh, high temperature, high loading, excess epoxide, and the isocyanate needs to be added slowly. Recently, the use of metal complex catalysts has been effective in improving the above problems, but when isocyanates are substituted with an electron withdrawing group isocyanate or an alkyl group, the effect is not desirable. (ACS Catal.2013,3,790) and the toxic metal ions remained in the metal ions hinder the application of oxazolidinones in biomedicine.
Recently, organic catalysis has made very important advances in the field of catalysis, which has enabled many reactions to avoid the use of expensive and toxic metal catalysts. Imidazolium salts have been reported as an important organic catalyst in 2018 by Byun et al to use alkyl substituted imidazolium salts to catalyze the fixation of carbon dioxide to form cyclic carbonates. (Chemcathem 2018,10(20),4610-4616) unlike the fixed carbon dioxide mechanism, the difference in the nucleophilic attack sites of the anion leads to the formation of different oxazolidinones (see below) due to the asymmetric hetero-accumulative diene as isocyanate. To date, the use of aryl-substituted imidazolium salts has not been reported.
The invention firstly provides the synthesis of oxazolidinone by catalyzing the cyclization of epoxide and isocyanate by using imidazolium salt. The aryl substituted imidazolium salt catalyst is commercially available, and other preparation methods are reported in a large number (Nature Communications,2018,9, 4251-4261), and the aryl substituted imidazolium salt catalyst is prepared by directly preparing N, N '-substituted diimine from 2, 6-substituted aniline and glyoxal aqueous solution, and then directly preparing the N, N' -substituted diimine, paraformaldehyde and trimethyl halogenated silane, and has the advantages of simple steps and high yield. The product is directly obtained by filtration and washing without column chromatography.
In order to expand the application of oxazolidinones in the field of biomedicine, the invention discovers and solves the problems from the actual requirements, and various substituted oxazolidinones are synthesized by utilizing various imidazolium salts. The catalytic system is firstly proposed and applied to synthesis of oxazolidinone from epoxide and isocyanate.
Disclosure of Invention
The invention aims to provide a method for catalyzing epoxide and isocyanate to generate oxazolidinone based on imidazolium salt. Compared with the existing metal ion or metal complex catalyst, the method can prepare the oxazolidinone by a one-pot method, and has the advantages of no metal residue, high efficiency, mild conditions and the like.
In order to solve the technical problem of the invention, the technical scheme is as follows: a method for synthesizing oxazolidinone by using imidazolium salt as a catalyst comprises the steps of using epoxide and isocyanate as raw materials, and reacting the epoxide and isocyanate by using the catalyst shown in the formula (I) to obtain oxazolidinone and derivatives thereof;
wherein R is1、R2Is aryl; x is selected from bromine or iodine;
the preparation route of the oxazolidinone synthesized by the epoxide and the isocyanate is as follows:
wherein R is3Is monochloromethyl, phenoxymethyl or phenyl; r4P-methoxyphenyl, 3, 5-bistrifluoromethylphenyl, m-tolyl or p-tolyl.
Preferably, X in said formula (I)-Is composed of
Or
Preferably, the catalyst represented by the formula (I) is selected from the following structures:
preferably, the epoxy substrate is epichlorohydrin, styrene oxide or phenyl glycidyl ether.
Preferably, the molar ratio of epoxy substrate to catalyst is 100: 2-5.
Preferably, the synthesis method of the oxazolidinone comprises the following specific steps: epoxide, isocyanate and organic catalyst shown in formula (I) react for 8 hours in solvent at 70-100 ℃, and the product oxazolidinone is obtained by column chromatography of reaction liquid.
Preferably, the reaction is carried out at 100 ℃.
Has the advantages that:
(1) the invention can efficiently synthesize oxazolidinones with diversity through the catalytic system, and compared with oxazolidinones synthesized by using a metal catalyst or a metal composite catalyst in the prior art, the invention has the characteristics of high yield, no metal residue, wide application and the like. Has great commercial application potential in biomedicine and fields.
(2) The catalytic system activates epoxide through the action of hydrogen bond at C-2 position in imidazolium salt, and catalyzes the epoxide to cyclize with isocyanate to synthesize oxazolidinone. At present, no report is available on the synthesis of oxazolidinone by catalyzing the cyclization of epoxide and isocyanate by using imidazolium salt. Compared with other methods for synthesizing oxazolidinone by cyclizing epoxide and isocyanate under the conditions of high temperature and high catalyst loading, the method has the advantages of relatively mild reaction conditions and convenience.
(3) The catalysts used in the present invention can be purchased directly or prepared in two simple steps, giving the corresponding oxazolidinones in yields of more than 80% for most epoxides and isocyanates, with reaction times of only 8 hours.
(4) The test is carried out at 70-100 ℃, the yield is increased along with the increase of the reaction temperature, and the high yield of the oxazolidinone can be achieved at 100 ℃. Compared with the high temperature of the metal catalyst, the reaction condition is milder.
Compared with other existing catalytic systems, the catalyst has the obvious advantages of being mild, efficient, easy to prepare, wide in substrate universality, free of metal and the like.
Drawings
Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein
FIG. 1: examples 1-7 Hydrogen spectra of oxazolidinones as products
FIG. 2: EXAMPLE 8 Hydrogen spectrum of oxazolidinone product
FIG. 3: EXAMPLE 9 Hydrogen spectrum of oxazolidinone product
FIG. 4: EXAMPLE 10 Hydrogen Spectroscopy of oxazolidinone product
FIG. 5: EXAMPLE 11 Hydrogen spectrum of oxazolidinone product
FIG. 6: example 1 Hydrogen Spectrum of catalyst
FIG. 7: example 2 Hydrogen Spectrum of catalyst
FIG. 8: example 3 Hydrogen Spectrum of catalyst
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative and not limiting. It will be understood by those of ordinary skill in the art that these examples are not intended to limit the present invention in any way and that suitable modifications and data transformations may be made without departing from the spirit of the invention and from the scope of the invention.
The structure of the catalytic system used in the examples is as follows:
example 1:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was introduced for protection, catalyst (1) (19.22mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and finally p-methoxyphenyl isocyanate (0.155mL, 1.2mmol, 1.2equiv) was added. The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 100 ℃ for 8 hours. After the reaction was completed, cooling, column chromatography (petroleum ether: ethyl acetate: 5:1) and spin-drying on a rotary evaporator to obtain white powder, which was dried to constant weight with a yield of 57%.1H NMR(400MHz,Chloroform-d)δ7.51–7.43(m,2H),7.33–7.28(m,2H),7.02–6.98(m,1H),6.94–6.88(m,4H),4.97(dtd,J＝9.0,5.6,4.5Hz,1H),4.24–4.14(m,3H),4.03(dd,J＝8.9,6.0Hz,1H),3.81(s,3H).
Example 2:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was introduced for protection, catalyst (2) (21.5mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and p-methoxyphenyl isocyanate (0.155mL, 1.2 mm) was addedol, 1.2 equiv). The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 100 ℃ for 8 hours. After the reaction was completed, cooling and column chromatography (petroleum ether: dichloromethane ═ 1:1) were performed, followed by spin-drying on a rotary evaporator to obtain a white powder, which was dried to constant weight, with a yield of 86%.1H NMR(400MHz,Chloroform-d)δ7.51–7.43(m,2H),7.33–7.28(m,2H),7.02–6.98(m,1H),6.94–6.88(m,4H),4.97(dtd,J＝9.0,5.6,4.5Hz,1H),4.24–4.14(m,3H),4.03(dd,J＝8.9,6.0Hz,1H),3.81(s,3H).
Example 3:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was introduced for protection, catalyst (3) (27.5mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and p-methoxyphenyl isocyanate (0.155mL, 1.2mmol, 1.2equiv) was added. The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 100 ℃ for 8 hours. After the reaction was completed, cooling, column chromatography (petroleum ether: ethyl acetate: 5:1) and spin-drying on a rotary evaporator to obtain white powder, which was dried to constant weight with a yield of 53%.1H NMR(400MHz,Chloroform-d)δ7.51–7.43(m,2H),7.33–7.28(m,2H),7.02–6.98(m,1H),6.94–6.88(m,4H),4.97(dtd,J＝9.0,5.6,4.5Hz,1H),4.24–4.14(m,3H),4.03(dd,J＝8.9,6.0Hz,1H),3.81(s,3H).
Example 4:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was introduced for protection, catalyst (2) (21.5mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and finally p-methoxyphenyl isocyanate (0.155mL, 1.2mmol, 1.2equiv) was added. The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 90 ℃ for 8 hours. After the reaction is finished, cooling, performing column chromatography (petroleum ether: ethyl acetate: 5:1), and performing spin drying on a rotary evaporator to obtain white powder, and drying to constant weight to obtain the yield of 80%.1H NMR(400MHz,Chloroform-d)δ7.51–7.43(m,2H),7.33–7.28(m,2H),7.02–6.98(m,1H),6.94–6.88(m,4H),4.97(dtd,J＝9.0,5.6,4.5Hz,1H),4.24–4.14(m,3H),4.03(dd,J＝8.9,6.0Hz,1H),3.81(s,3H).
Example 5:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was introduced for protection, catalyst (2) (21.5mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and finally p-methoxyphenyl isocyanate (0.155mL, 1.2mmol, 1.2equiv) was added. The reaction kettle is inserted with a balloon filled with inert gas and put into an oil bath kettle at the temperature of 80 ℃ for reaction for 8 hours. After the reaction was completed, cooling, column chromatography (petroleum ether: ethyl acetate: 5:1) and spin-drying on a rotary evaporator to obtain white powder, which was dried to constant weight, yielding 69%.1H NMR(400MHz,Chloroform-d)δ7.51–7.43(m,2H),7.33–7.28(m,2H),7.02–6.98(m,1H),6.94–6.88(m,4H),4.97(dtd,J＝9.0,5.6,4.5Hz,1H),4.24–4.14(m,3H),4.03(dd,J＝8.9,6.0Hz,1H),3.81(s,3H).
Example 6:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was introduced for protection, catalyst (2) (21.5mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and finally p-methoxyphenyl isocyanate (0.155mL, 1.2mmol, 1.2equiv) was added. The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 70 ℃ for 8 hours. After the reaction was completed, cooling, column chromatography (petroleum ether: ethyl acetate: 5:1) and spin-drying on a rotary evaporator to obtain white powder, which was dried to constant weight with a yield of 43%.1H NMR(400MHz,Chloroform-d)δ7.51–7.43(m,2H),7.33–7.28(m,2H),7.02–6.98(m,1H),6.94–6.88(m,4H),4.97(dtd,J＝9.0,5.6,4.5Hz,1H),4.24–4.14(m,3H),4.03(dd,J＝8.9,6.0Hz,1H),3.81(s,3H).
Example 7:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was introduced for protection, catalyst (2) (8.6mg, 0.02mmol, 0.02equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and finally p-methoxyphenyl isocyanate (0.155mL, 1.2mmol, 1.2equiv) was added. Inserting a balloon filled with inert gas, placing at 100 deg.CWas reacted in an oil bath for 8 hours. After the reaction is finished, cooling, performing column chromatography (petroleum ether: ethyl acetate: 5:1), and performing spin drying on a rotary evaporator to obtain white powder which is dried to constant weight, wherein the yield is 40%.1H NMR(400MHz,Chloroform-d)δ7.51–7.43(m,2H),7.33–7.28(m,2H),7.02–6.98(m,1H),6.94–6.88(m,4H),4.97(dtd,J＝9.0,5.6,4.5Hz,1H),4.24–4.14(m,3H),4.03(dd,J＝8.9,6.0Hz,1H),3.81(s,3H).
Example 8:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was purged, and catalyst (2) (21.5mg, 0.05mmol, 0.05equiv) and epichlorohydrin (0.08mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and finally m-tolyl isocyanate (0.151mL, 1.2mmol, 1.2equiv) was added. The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 100 ℃ for 8 hours. After the reaction is finished, cooling, performing column chromatography (petroleum ether: ethyl acetate: 5:1), and performing spin drying on a rotary evaporator to obtain white powder, drying to constant weight, wherein the yield is 92%1H NMR(400MHz,Chloroform-d)δ7.39(d,J＝2.0Hz,1H),7.35–7.26(m,2H),6.98(d,J＝7.3Hz,1H),4.86(dddd,J＝8.7,6.8,5.6,4.1Hz,1H),4.16(t,J＝9.0Hz,1H),3.96(dd,J＝9.2,5.7Hz,1H),3.77(qd,J＝11.6,5.4Hz,2H),2.38(s,3H).
Example 9:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was introduced for protection, catalyst (2) (21.5mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and 3, 5-bistrifluoromethylphenyl isocyanate (0.21mL, 1.2mmol, 1.2equiv) was added last. The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 100 ℃ for 8 hours. After the reaction is finished, cooling, performing column chromatography (petroleum ether: ethyl acetate: 4:1), and performing spin drying on a rotary evaporator to obtain white powder, drying to constant weight, wherein the yield is 80%1H NMR(400MHz,Chloroform-d)δ8.08(d,J＝1.6Hz,2H),7.70–7.62(m,1H),7.37–7.27(m,2H),7.08–6.96(m,1H),6.95–6.86(m,2H),5.13–4.99(m,1H),4.36–4.21(m,3H),4.17(dd,J＝8.7,5.9Hz,1H).
Example 10:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was purged, and catalyst (2) (21.5mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and finally m-tolyl isocyanate (0.151mL, 1.2mmol, 1.2equiv) was added. The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 100 ℃ for 8 hours. After the reaction is finished, cooling, performing column chromatography (petroleum ether: ethyl acetate: 5:1), and performing spin drying on a rotary evaporator to obtain white powder, drying to constant weight, wherein the yield is 80%1H NMR(400MHz,Chloroform-d)δ7.42(m,J＝1.5Hz,1H),7.32(d,4H),7.00–6.92(m,4H),4.98(m,1H),4.30–4.22(dd,3H),4.17(dd,J＝8.8,5.9Hz,1H).
Example 11:
the reaction flask was subjected to three repetitions of drying and oxygen removal, under inert gas blanketing, catalyst (2) (21.5mg, 0.05mmol, 0.05equiv) and styrene oxide (0.114mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and p-tolyl isocyanate (0.151mL, 1.2mmol, 1.2equiv) was added. The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 100 ℃ for 8 hours. After the reaction was completed, cooling, column chromatography (petroleum ether: ethyl acetate: 5:1) and spin-drying on a rotary evaporator to obtain white powder, which was dried to constant weight with a yield of 81%.1H NMR(400MHz,Chloroform-d)δ7.57–7.34(m,7H),7.21–7.15(m,2H),5.63(dd,J＝8.7,7.5Hz,1H),4.36(t,J＝8.8Hz,1H),3.94(dd,J＝9.0,7.5Hz,1H),2.33(s,3H).
Example 12
To the commercially available 1, 3- (2, 4, 6-trimethylphenyl) imidazolium chloride (0.340g,1mmol,1.00equiv.) was added 5mL of ethyl acetate to form a suspension, a saturated acetone solution of NaI (0.6g,4mmol,4.00equiv.) was added to the aqueous solution, stirred at room temperature for 12 hours, filtered, and the residue was washed with a small amount of acetone and ethyl acetate to obtain a pure product of the catalyst (2).1H NMR(400MHz,Chloroform-d)δ10.32(s,1H),7.68(s,76H),7.39(s,1H),7.24(s,2H),2.23(s,12H).
Comparative example 1:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was introduced for protection, 1, 3- (2, 4, 6-trimethylphenyl) imidazolium chloride (17.00mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and p-methoxyphenyl isocyanate (0.155mL, 1.2mmol, 1.2equiv) was added. The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 100 ℃ for 8 hours. After the reaction is finished, cooling, performing column chromatography (petroleum ether: ethyl acetate: 5:1), and performing spin drying on a rotary evaporator to obtain white powder which is dried to constant weight, wherein the yield is 6%. It is proved that in the catalytic system, the effect of the chloride ion is far less than that of the iodide ion and the bromide ion.
Comparative example 2:
the reaction flask was subjected to three repetitions of drying and oxygen removal, and inert gas was introduced for protection, and 1-methyl-3-ethylimidazolium iodide (17.00mg, 0.05mmol, 0.05equiv) and phenyl glycidyl ether (0.135mL, 1mmol,1.0 equiv) were added, chlorobenzene solvent (1.0mL) was added, and finally p-methoxyphenyl isocyanate (0.155mL, 1.2mmol, 1.2equiv) was added. The reaction vessel was inserted with a balloon filled with inert gas and placed in an oil bath pan at 100 ℃ for 8 hours. After the reaction was completed, cooling, column chromatography (petroleum ether: ethyl acetate: 5:1) and spin-drying on a rotary evaporator to obtain white powder, which was dried to constant weight with a yield of 34%. The aryl substituted imidazolium effect is proved to be far higher than that of alkyl substituted imidazolium.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the invention as claimed.
Claims (7)
1. A method for synthesizing oxazolidinone by using imidazolium salt catalysis, which is characterized in that: epoxide and isocyanate are taken as raw materials, and the catalyst shown in the formula (I) is adopted for reaction to obtain oxazolidinone and derivatives thereof;
wherein R is1、R2Is aryl; x is selected from bromine or iodine;
the preparation route of the oxazolidinone synthesized by the epoxide and the isocyanate is as follows:
wherein R is3Is monochloromethyl, phenoxymethyl or phenyl; r4P-methoxyphenyl, 3, 5-bistrifluoromethylphenyl, m-tolyl or p-tolyl.
2. A method for the catalytic synthesis of oxazolidinones using imidazolium salts according to claim 1, characterized in that: x in the formula (I)-Is composed of
3. A method for the catalytic synthesis of oxazolidinones using imidazolium salts according to claim 1 or 2, characterized in that: the catalyst shown in the formula (I) is selected from the following structures:
4. a method for the catalytic synthesis of oxazolidinones using imidazolium salts according to claim 1, characterized in that: the epoxy substrate is epichlorohydrin, styrene oxide or phenyl glycidyl ether.
5. A method for the catalytic synthesis of oxazolidinones using imidazolium salts according to any of the claims 1 to 4, characterized in that: the molar ratio of the epoxy substrate to the catalyst is 100: 2-5.
6. A method for the catalytic synthesis of oxazolidinones using imidazolium salts according to any of the claims 1 to 4, characterized in that: the synthesis method of the oxazolidinone comprises the following specific steps: epoxide, isocyanate and organic catalyst shown in formula (I) react for 8 hours in solvent at 70-100 ℃, and the product oxazolidinone is obtained by column chromatography of reaction liquid.
7. A method for the catalytic synthesis of oxazolidinones using imidazolium salts according to claim 6, characterized in that: the reaction is carried out at 100 ℃.
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| CN106045935A (en) * | 2015-04-02 | 2016-10-26 | 重庆大学 | Preparation method for oxazolone heterocyclic compounds |
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| CN111303112A (en) * | 2020-02-28 | 2020-06-19 | 南京工业大学 | Method for fixing carbon dioxide |
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| CN106045935A (en) * | 2015-04-02 | 2016-10-26 | 重庆大学 | Preparation method for oxazolone heterocyclic compounds |
| CN107746392A (en) * | 2017-12-05 | 2018-03-02 | 河南师范大学 | A kind of preparation method of the oxazole alkyl compound containing caged scaffold |
| CN111303112A (en) * | 2020-02-28 | 2020-06-19 | 南京工业大学 | Method for fixing carbon dioxide |
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