CN105330662B - Preparation of imidazole type ionic liquid derived by cinchona alkaloid - Google Patents
Preparation of imidazole type ionic liquid derived by cinchona alkaloid Download PDFInfo
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- CN105330662B CN105330662B CN201510854748.2A CN201510854748A CN105330662B CN 105330662 B CN105330662 B CN 105330662B CN 201510854748 A CN201510854748 A CN 201510854748A CN 105330662 B CN105330662 B CN 105330662B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D453/00—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids
- C07D453/02—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems
- C07D453/04—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems having a quinolyl-4, a substituted quinolyl-4 or a alkylenedioxy-quinolyl-4 radical linked through only one carbon atom, attached in position 2, e.g. quinine
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- 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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- 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
- B01J31/0285—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 also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses the preparation of imidazole type ionic liquid derived by cinchona alkaloid. The preparation is characterized by adopting quinine or cinchonine to modify 9-hydroxyl of the cinchona alkaloid; carrying out a replacement reaction on chloride salt of obtained imidazole type ionic liquid and inorganic metal salt; preparing imidazole type ionic liquid catalysts of different anions. Compared with the prior art, the preparation disclosed by the invention has the advantages that the catalytic activity is high, the catalysts are easily separated and recycled and can be reused again, the preparation is simple, post-processing is easy, the stability of the catalysts is greatly increased, the application range of the catalysts in a micromolecular organic asymmetric reaction is expanded, reaction conditions are optimized, reaction requirements are reduced, the catalytic activity and the enantioselectivity of a chiral imidazole type ionic liquid catalyst in an asymmetric reaction are further increased, and great significance is obtained for researching medicinal chemistry and medical intermediate compounds.
Description
Technical field
Spread out the present invention relates to organic catalyst technical field, especially a kind of quinine being used in asymmetric reaction
The preparation of raw imidazole type ion liquid.
Background technology
It is presently used for catalyst such as noble metal complexes, native enzyme etc. of asymmetric reaction, although better catalytic activity,
But catalyst amount is big, can not recycle, and easily causes the irrational utilization of resource, and wastage of material is serious again.In recent years,
Application of the small molecule organic catalyst in asymmetric reaction gets more and more people's extensive concerning, especially quinine and its derivative
Good catalysis activity and right is shown in asymmetric Michael Reaction, asymmetric Friedel-Crafts such as react at the reaction
Selectivity is reflected also increasingly to be valued by people.Although such micromolecule catalyst preparation process is simple, raw material are cheap, the later stage
Modification is easy, and reaction environment is gentle, and catalysis activity is good, and the advantages of pollute small, but structure without imidazole type ion liquid is steady
Fixed, solvability is strong, and steam is forced down, and viscosity is suitable, electric conductivity good characteristic high, and carries the functionalized ion liquid of chirality
As reaction medium or catalyst in organic reaction, thus it is possible to vary reaction mechanism, make activity, the stability of catalyst more preferably,
Selectivity, conversion ratio are higher.So how to be combined the natural chiral center of quinine with imidazole ion liquid, one is formed
The new quinine imidazole type ion liquid catalyst of class, has considerable Research Significance in small molecule organic catalysis
And application prospect.
The content of the invention
Imidazole type ion derived from a kind of quinine that the purpose of the present invention is directed to the deficiencies in the prior art and provides
The preparation of liquid, it is quaternized with N- methylimidazoles after benzyl alkyl chloride using to the quinine 9- modification of hydroxyl, constructing
Imidazole type ion liquid derived from reaction structure quinine, makes the natural chiral center of quinine and imidazole ion liquid knot
Close and form the new quinine imidazole type ion liquid catalyst of a class, it is organic asymmetric anti-in small molecule to expand catalyst
Range of application in answering, optimizes reaction condition, reduces reaction and requires, the further chiral imidazole type ionic-liquid catalyst that improves exists
The utilization rate of catalysis activity, enantioselectivity and raw material in asymmetric reaction.
Realizing the concrete technical scheme of the object of the invention is：The system of imidazole type ion liquid derived from a kind of quinine
It is standby, it is characterized in using quinine, quinindium, cinchonine or cinchonine fourth to the quinine 9- modification of hydroxyl, then incite somebody to action
To villaumite and the inorganic metal salt of imidazole ion liquid carry out metathesis reaction, prepare the imidazole type ionic liquid of different anions
Body catalyst, specific preparation is carried out by following reaction structure formulas and operating procedure：
Wherein：Cl–May be exchanged for NO3 –、PF6 –、BF4 –、NTf2 –、OAc–Or OTf–。
The first step：By quinine (Quinine), quinindium (Quinidine), cinchonine (Cinchonine) or cinchonine fourth
(Cinchonidine) 1 is pressed with triethylamine and tetrahydrofuran, acetonitrile or dimethylformamide (DMF)：1.1~1.8：10~200
It is placed in after mixed in molar ratio in 0 DEG C of ice-water bath, is added dropwise and 1 is pressed to chloromethyl benzoic acid chlorides and dichloromethane or tetrahydrofuran：10~
The solution of 50 mixed in molar ratio, in normal temperature, synthesis under normal pressure 5~24 hours after dropwise addition, reaction be spin-dried for after terminating solvent and with etc. body
Long-pending dichloromethane and water carry out a point liquid, and water is extracted at twice with isometric dichloromethane, and saturation is used after merging organic phase
Saline solution is extracted, and extract is through the compound that drying, filtering, concentration and silica gel column chromatography obtain quinine 9- hydroxyl modified
Benzyl alkyl chloride (QN-Cl, QD-Cl, CN-Cl or CD-Cl)；It is described that 1 is pressed to chloromethyl benzoic acid chlorides and dichloromethane：10~50
Mixed in molar ratio.
Second step：Above-mentioned benzyl alkyl chloride (QN-Cl, QD-Cl, CN-Cl or CD-Cl) is pressed with N- methylimidazoles and acetonitrile
1：1.0~2.0：50~100 mixed in molar ratio, carry out 5~48 hours quaterisations, instead under 25~45 DEG C of temperature, normal pressures
Be spin-dried for solvent after should terminating, through silica gel column chromatography obtain target product for imidazole type ion liquid derived from quinine (QN-IL,
QD-IL, CN-IL or CD-IL).
3rd step：By above-mentioned imidazole type ion liquid (QN-IL, QD-IL, CN-IL or CD-IL) and silver nitrate, silver acetate
Or silver trifluoromethanesulfonate presses 1：1.0~1.2 mixed in molar ratio, carry out the metathesis reaction of 12~48 hours under normal temperature, normal pressure,
So as to obtain the imidazole type ion liquid catalyst of different anions.
The present invention has catalysis activity high compared with prior art, and catalyst is easily separated to be reclaimed and recycle again, is made
Standby simple, operation is easy, and synthetic route is short, and post processing is easy, and raw material availability is high, substantially increases the stability of catalyst,
To expand range of application of the catalyst in the organic asymmetric reaction of small molecule, optimize reaction condition, reduce reaction and require, enter one
Step improves the utilization of catalysis activity, enantioselectivity and raw material of the chiral imidazole type ionic-liquid catalyst in asymmetric reaction
Rate, the especially research to pharmaceutical chemistry and pharmaceutical intermediate compound have important practical significance.
Specific embodiment
By specific examples below, the present invention is described in further detail.
Embodiment 1
The first step：Weigh 8.68g quinines (Quinine) and 2.98g triethylamines are dissolved in 40ml tetrahydrofurans, by 5.02g
Chloromethyl benzoic acid chlorides are dissolved in 5ml tetrahydrofurans, at a temperature of 0 DEG C, the tetrahydrofuran solution of acyl chlorides are slowly dropwise dripped
Enter in the tetrahydrofuran solution of quinine triethylamine, after completion of dropping, reacted 12 hours under normal temperature, normal pressure, TLC monitoring reaction knots
Solvent is spin-dried for after beam, with 20ml dichloromethane and the isometric hybrid extraction of water, water is mutually extracted at twice with 40ml dichloromethane again,
Once add appropriate anhydrous Na afterwards with the extraction of 30ml saturations NaCl solution after merging organic phase2SO4Dry, then filter, concentrate filtrate
It is benzyl alkyl chloride (QN-Cl) (3- to obtain the quinine 9- compound of hydroxyl modified with silica gel column chromatography (EA: PE=1: 5)
(4-(((R)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)
Methoxy) carbonyl) benzyl) -1-methyl-1H-imidazol-3-ium chloride), its yield is 90%.
Second step：Weigh above-mentioned benzyl alkyl chloride (QN-Cl) compound 4.76g to be dissolved in 5ml acetonitriles, and add
0.98gN- methylimidazoles, at a temperature of 40 DEG C, synthesis under normal pressure 12 hours, reaction is spin-dried for solvent after terminating, through silica gel column chromatography
(EA∶CH3OH=1: it is imidazole type ion liquid (QN-IL) derived from quinine 1) to obtain target product, and its yield is 65%.
3rd step：Weigh 2.0g imidazole type ion liquids (QN-IL) and the inorganic salts containing different anions in normal temperature, often
Pressure carries out the metathesis reaction of 24 hours, if inorganic salts are silver nitrate, addition is 0.61g, and its yield is 70%；If nothing
Machine salt is silver acetate, then addition is 0.60g, and its yield is 76%；If inorganic salts are silver trifluoromethanesulfonate, addition is
0.92g, its yield is 83%, so as to obtain the quinine imidazole type ion liquid catalyst of different anions.
Embodiment 2
The first step：Weigh 4.15g quinindiums (Quinidine) and 1.53g triethylamines are dissolved in the acetonitrile of 20ml, will
2.46g is dissolved in 3ml tetrahydrofurans to chloromethyl benzoic acid chlorides, and at a temperature of 0 DEG C, the tetrahydrofuran solution of just acyl chlorides is slow
In dropwise instilling the acetonitrile solution of quinindium triethylamine, after completion of dropping, in normal temperature, synthesis under normal pressure 16 hours, TLC monitoring reactions
Solvent is spin-dried for after end, with 20ml dichloromethane and the isometric hybrid extraction of water, water is mutually extracted at twice with 40ml dichloromethane again
Take, appropriate anhydrous Na is once added afterwards with the extraction of 30ml saturations NaCl solution after merging organic phase2SO4Dry, then filter, concentrate
It is benzyl alkyl chloride (QD-Cl) (3- (4- (((S)-(6- that filtrate and silica gel column chromatography (EA: PE=1: 3) obtain compound
methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methoxy)carbonyl)
Benzyl) -1-methyl-1H-imidazol-3-ium chloride), its yield is 82%.
Second step：Weigh above-mentioned benzyl alkyl chloride (QD-Cl) compound 5.40g to be dissolved in 5ml acetonitriles, and add
1.86gN- methylimidazoles, at a temperature of 40 DEG C, synthesis under normal pressure 14 hours, reaction is spin-dried for solvent after terminating, through silica gel column chromatography
(EA∶CH3OH=1: it is imidazole type ion liquid (QD-IL) derived from quinindium 2) to obtain target product, and its yield is 61%.
3rd step：Weigh 1.0g imidazole type ion liquids (QD-IL) and the inorganic salts containing different anions in normal temperature, often
Pressure carries out the metathesis reaction of 24 hours, if inorganic salts are silver nitrate, addition is 0.32g, and its yield is 75%；If nothing
Machine salt is silver acetate, then addition is 0.32g, and its yield is 82%；If inorganic salts are silver trifluoromethanesulfonates, addition is
0.49g, its yield is 83%.So as to obtain the quinindium imidazole type ion liquid catalyst of different anions.
Embodiment 3
The first step：Weigh 8.59g cinchonines (Cinchonine) and 3.24g triethylamines are dissolved in the dimethylformamide of 50ml
(DMF) in, 5.46g is dissolved in 3ml tetrahydrofurans to chloromethyl benzoic acid chlorides, at a temperature of 0 DEG C, by the tetrahydrofuran of acyl chlorides
Solution is slowly dropwise instilled in the DMF solution of quinindium triethylamine, after completion of dropping, in normal temperature, synthesis under normal pressure 16 hours, TLC
Monitoring reaction is spin-dried for solvent, plus 20ml ethyl acetate after terminating, and 200ml distilled water dilutings are collected by filtration the white solid of precipitation,
Filtrate divides liquid, water mutually to be extracted at twice with 40ml ethyl acetate again again, is extracted with 20ml saturations NaCl solution after merging organic phase
Once add appropriate anhydrous Na afterwards2SO4Dry, then filter, concentration filtrate and silica gel column chromatography (EA: PE=1: 5) compound be
Benzyl alkyl chloride (CN-Cl) (1-methyl-3- (4- (((S)-quinolin-4-yl ((1S, 2S, 4S, 5R) -5-
Vinylquinuclidin-2-yl) methoxy) c-arbonyl) benzyl) -1H-imidazol-3-ium chloride),
Its yield is 90%.
Second step：Weigh above-mentioned benzyl alkyl chloride (CN-Cl) compound 3.38g to be dissolved in 5ml acetonitriles, and add
0.62gN- methylimidazoles, at a temperature of 40 DEG C, synthesis under normal pressure 14 hours, reaction is spin-dried for solvent after terminating, through silica gel column chromatography
(EA∶CH3OH=1: it is imidazole type ion liquid (CN-IL) derived from cinchonine 2) to obtain target product, and its yield is 70%.
3rd step：Weigh 0.80g imidazole type ion liquids (CN-Cl) and the inorganic salts containing different anions normal temperature,
The metathesis reaction of 36 hours is carried out under normal pressure, if inorganic salts are silver nitrate, addition is 0.26g, and its yield is 76%；If
Inorganic salts are silver acetate, then addition is 0.25g, and its yield is 86%；If inorganic salts are silver trifluoromethanesulfonate, addition is
0.39g, its yield is 73%, so as to obtain the cinchonine imidazole type ion liquid catalyst of different anions.
Embodiment 4
The first step：Weigh 4.36g cinchonines fourth (Cinchonidine) and 1.67g triethylamines be dissolved in the acetonitrile of 20ml,
2.90g 4- chloromethyl benzoic acid chlorides are dissolved in 2ml tetrahydrofurans, at a temperature of 0 DEG C, the tetrahydrofuran solution of acyl chlorides are delayed
In the slow acetonitrile solution for dropwise instilling cinchonine fourth triethylamine, then after completion of dropping, in normal temperature, synthesis under normal pressure 8 hours, TLC
Monitoring reaction is spin-dried for solvent after terminating, and with 20ml dichloromethane and the isometric hybrid extraction of water, water mutually uses 40ml dichloromethane again
Extract at twice, appropriate anhydrous Na is once added afterwards with the extraction of 30ml saturations NaCl solution after merging organic phase2SO4Dry, then mistake
It is benzyl alkyl chloride (CD-Cl) (1-methyl-3- (4- that filter, concentration filtrate and silica gel column chromatography (EA: PE=1: 2) obtain compound
(((R)-quinolin-4-yl((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methoxy)-carbonyl)
Benzyl) -1H-imidazol-3-ium chloride), its yield is 82%.
Second step：Weigh above-mentioned benzyl alkyl chloride (CD-Cl) compound 1.52g to be dissolved in 5ml acetonitriles, and add
0.28gN- methylimidazoles, at a temperature of 40 DEG C, synthesis under normal pressure 14 hours, reaction is spin-dried for solvent after terminating, through silica gel column chromatography
(EA∶CH3OH=1: it is imidazole type ion liquid (CD-IL) derived from cinchonidine 3) to obtain target product, and its yield is 57%.
3rd step：Weigh 0.80g imidazole type ion liquids (CD-IL) and the inorganic salts containing different anions normal temperature,
The metathesis reaction of 36 hours is carried out under normal pressure, if inorganic salts are silver nitrate, addition is 0.18g, and its yield is 74%；If
Inorganic salts are silver acetate, then addition is 0.18g, and its yield is 80%；If inorganic salts are silver trifluoromethanesulfonate, addition is
0.27g, its yield is 78%, so as to obtain the cinchonine Butamisole type ionic-liquid catalyst of different anions.
Various embodiments above is that the present invention will be further described, and is not used to limit patent of the present invention, all for this hair
Bright equivalence enforcement, is intended to be limited solely by within the right of patent of the present invention.
Claims (1)
1. the preparation of imidazole type ion liquid derived from a kind of quinine, it is characterised in that using quinine, quinindium, cinchonine
Or cinchonine fourth is to the quinine 9- modification of hydroxyl, the villaumite and inorganic metal salt of the imidazole ion liquid that then will be obtained
Metathesis reaction is carried out, the imidazole type ion liquid catalyst of different anions is prepared, specific preparation presses following reaction structure formulas
Carried out with operating procedure：
Wherein：Cl–May be exchanged for NO3 –、PF6 –、BF4 –、NTf2 –、OAc–Or OTf–；
The first step：By quinine (Quinine), quinindium (Quinidine), cinchonine (Cinchonine) or cinchonine fourth
(Cinchonidine) 1 is pressed with triethylamine and tetrahydrofuran, acetonitrile or dimethylformamide (DMF)：1.1~1.8：10~200
It is placed in after mixed in molar ratio in 0 DEG C of ice-water bath, is added dropwise and 1 is pressed to chloromethyl benzoic acid chlorides and dichloromethane or tetrahydrofuran：10~
The solution of 50 mixed in molar ratio, in normal temperature, synthesis under normal pressure 5~24 hours after dropwise addition, reaction be spin-dried for after terminating solvent and with etc. body
Long-pending dichloromethane and water carry out a point liquid, and water is extracted at twice with isometric dichloromethane, and saturation is used after merging organic phase
Saline solution is extracted, and extract is through the compound that drying, filtering, concentration and silica gel column chromatography obtain quinine 9- hydroxyl modified
Benzyl alkyl chloride (QN-Cl, QD-Cl, CN-Cl or CD-Cl)；It is described that 1 is pressed to chloromethyl benzoic acid chlorides and dichloromethane：10~50
Mixed in molar ratio；
Second step：Above-mentioned benzyl alkyl chloride (QN-Cl, QD-Cl, CN-Cl or CD-Cl) and N- methylimidazoles and acetonitrile are pressed 1：
1.0~2.0：50~100 mixed in molar ratio, carry out the quaterisation of 5~48 hours, instead under 25~45 DEG C of temperature, normal pressures
Be spin-dried for solvent after should terminating, through silica gel column chromatography obtain target product for imidazole type ion liquid derived from quinine (QN-IL,
QD-IL, CN-IL or CD-IL)；
3rd step：By above-mentioned imidazole type ion liquid (QN-IL, QD-IL, CN-IL or CD-IL) and silver nitrate, silver acetate or three
Fluorine methanesulfonic acid silver presses 1：1.0~1.2 mixed in molar ratio, carry out the metathesis reaction of 12~48 hours under normal temperature, normal pressure, so that
Obtain the imidazole type ion liquid catalyst of different anions.
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