CN105879914A - Temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst and preparation method thereof - Google Patents
Temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst and a preparation method thereof. The catalyst comprises a chiral Salen Ti complex catalyst unit and a temperature-sensitive material unit simultaneously and is obtained from temperature-sensitive monomers and an ionic liquid functionalized chiral Salen Ti complex containing alkenyl through a controllable free radical polymerization method. The catalyst is used for aqueous-phase catalysis of a thioether asymmetric oxidation reaction, and compared with a traditional Salen Ti catalyst, the catalyst is good in water solubility, capable of adopting water as a reaction medium and easy to recycle and repeatedly use and has the advantages of being high in catalytic efficiency and good in selectivity.
Description
Technical field
Salen Ti composition catalyst that the present invention relates to a kind of improvement and preparation method thereof, temperature sensitive particularly to one
Type ionic liquid Salen Ti composition catalyst and preparation method thereof, belongs to new catalytic material preparing technical field.
Background technology
Optically pure sulfoxide is a kind of important chiral auxiliaries, and it is widely used in asymmetric catalysis synthesis, such as
C-C key-like becomes reaction, and C-O key-like becomes reaction, asymmetric Michael addition reaction, the reduction reaction of carbonyl, Diels-Alder
Reaction and Radical Addition etc. (Chemical Communications, 2009,6129-6144).Optically pure chirality
Sulfoxide is also the active group of many medicines, and they application in terms of synthesis has bioactive compound are the most quite varied,
Such as some commercially fast-selling drug modafinil, Shu Lindake and Esomeprazole.Many bioactive molecules all contain one
Individual chirality sulfinyl unit, and the different enantiomer of stereochemical structure has different physiologically actives and metabolism.
Chiral sulfoxide is also used as chiral ligand and is applied in enantioselectivity catalytic reaction simultaneously.Therefore, it is thus achieved that high mapping selects
The sulfoxide of property has important theory significance and realistic price.In the past few decades, researchers are developing various preparations
The method aspect of optical voidness sulfoxide works it out the biggest effort, mainly has biological method and chemical method.Biological sulfoxide method
Prepare chiral sulfoxide including enzyme, microorganism etc., there is Substratspezifitaet, the advantage such as efficient, green, but enzyme or microorganism because of
The deficiency of the aspects such as poor stability, price be high and substrate spectrum is narrow, its application is restricted.Chemical method is divided into hands
Property adjuvant induction, split and the method such as asymmetry catalysis oxidation, up to now, wherein the asymmetric oxidation of thioether is to prepare chirality
The method that sulfoxide most has practicality.1984, Kagan used the Sharpless epoxidation catalyst of improvement to achieve first
Asymmetric oxidation (Synthesis, the 1984,325-326 of thioether；Tetrahedron Letters,1984,25,1049-
1052), afterwards, researchers have carried out research extensively and profoundly to this field, develop a series of based on Titanium, vanadium,
Catalyst system and catalyzing (Tanaka, the T. such as aluminum, ferrum, copper；Saito,B.；Katsuki,T.Tetrahedron Lett.2002,43,
3259；Katsuki,T.J.Am.Chem.Soc.2007,129,8940；O Mahony,G.E.；Ford,A.；Maguire,
A.R.J.Org.Chem.2012,77,3288；Matsumoto,K.；Yamaguchi,T.；Katsuki,
T.Chem.Commum.2008,1704.), and the conversion of some simple substrates such as aromatic alkyl thioether is achieved, but right
The progress of these substrates with challenge of Yu Huan, big steric hindrance or long-chain class thioether is the slowest, until 2013, by metalloporphyrin
Inspiration, the complex that Gao uses a kind of chirality four tooth nitrogen organic ligand and manganese metal compound to be formed is catalyst, hydrogen peroxide
For oxidant, it is successfully realized conversion (Dai, W. that big steric hindrance, long-chain or side chain class have the substrate of challenge；Li,J.；
Chen,B.；Li,G.；Lv,Y.；Wang,L.；Gao,S.Org.Lett.2013,15,5658).Document report transition metal at present
Catalysis asymmetric oxidation system specifically includes that have C2 symmetry chiral diol (phenol)-titanium catalyst system by chiral ligand classification,
There is C3 symmetry chirality three hydramine-titanium and pick catalyst system and catalyzing, chirality porphyrin metal coordination catalysis system, Chiral Schiff Base gold
Genus complex catalysis system (Arkivoc, 2011, (i), 1-110；Journal of Sulfur Chemistry,2013,34
(3),301-341).But, this catalyst series system is to carry out in the methylene chloride of not environment friendly, and product is sub-
Sulfone selectivity is low, brings the biggest difficulty to product separation and purification.It is sub-that the existence of these problems considerably increases chirality
The synthesis cost of sulfone, limits the commercial production of thioether asymmetric oxidation reaction.
International monopoly W091/12221 and W094/27988 describe and are directly split by the sulfoxide compound of racemic modification
The method becoming single enantiomer, it should be particularly mentioned and omeprazole is split into single enantiomer.Chinese patent CN1087739, international
Patent application W02006/094904, W02007/013743 etc. describe use (S)-binaphthol or tartaric acid resolution of omeprazole
Obtaining the interior inclusion complex of levo-omeprazole, then recycle silicon glue post or alkaline hydrolysis obtain the side of levo-omeprazole from this inclusion complex
Method.The omeprazole of half can be wasted by this type of Split Method resolution of omeprazole, cause environmental pollution and economic loss, Er Qieyou
The most costly, the most this Split Method large-scale use industrially is restricted optically active resolving agent price.
International monopoly W096/02535, Chinese patent CN1070489 discloses at chirality bidentate ligand diethyl tartrate.
In the presence of titanium complex and alkali, obtain the side of esomprazole with hydrogen peroxide analog derivative oxidation omeprazole thioether
Method.International monopoly W003/089408 describe chiral monodentate (S)-(+) under the complex catalysis of-mandelate and titanium or vanadium,
The method that oxidation omeprazole thioether obtains levo-omeprazole the most in the presence of base.
Chinese patent CN200380104409.8, international monopoly W02004/052881 describes use chirality pick complex
Or the method that chiral hafnium complex prepares S-pantoprazole.The method be (+)-or (-)-tartaric acid derivatives and alkoxyl pick
Or in the presence of alkoxyl hafnium, selectively oxidizing sulfur ether synthesis S-pantoprazole.CN200610023955 and CN181080803B retouches
State a kind of use Titanium reagent and chiral diol has been coordinated generated in-situ titanium-containing catalyst, made in tert-butyl hydroperoxide
Under with, selectively oxidizing sulfur ether.
International monopoly W096/17076 and W096/17077 describe use microorganism and are selectively oxidized thioether or choosing
Selecting property reduction sulfone compound, the method obtaining the sulfoxide compound of single enantiomer.
Summary of the invention
The defect existed for prior art, it is an object of the invention to be to provide one to contain temperature sensitive polymer unit,
Can control to realize the temperature sensitive type ionic liquid chirality Salen Ti composition catalyst that hydrophilic-hydrophobic converts by temperature,
This catalyst the most existing chirality Salen Ti coordination compound has and is preferably catalyzed activity and selectivity, and achieves water-soluble
In agent, asymmetry catalysis sulfide compound selective oxidation becomes sulfoxide, can be by the water solublity of temperature adjusting catalyst, it is achieved urge
The recovery of agent.
Second object of the present invention be to provide a kind of simple to operate, low cost, mild condition prepare described temperature
The method of quick type ionic liquid chirality Salen Ti composition catalyst.
In order to realize above-mentioned technical purpose, the invention provides a kind of temperature sensitive type ionic liquid chirality Salen Ti coordination compound
Catalyst, has formula 1 structure:
Wherein,
For temperature sensitive polymer unit；
X/Y is (1～100): 1；
R1、R2、R3Independently selected from hydrogen, alkyl, aryl, aryl substituted alkyl or alkoxyl；
R4ForN is 0～3；
R5For C1～C3Alkyl or hydrogen atom.
Preferably in temperature sensitive type ionic liquid chirality Salen Ti composition catalyst, R1、R2And R3It is respectively hydrogen, C1～C5
Alkyl, phenyl, C containing phenyl substituent1～C5Alkyl or C1～C5Alkoxyl；R4ForN is 0～2；R5For hydrogen
Atom.
Preferably in temperature sensitive type ionic liquid chirality Salen Ti composition catalyst, X/Y is (5～50): 1.
Preferably in temperature sensitive type ionic liquid chirality Salen Ti composition catalyst, temperature sensitive polymer unit is N-isopropyl
Base acrylamide polymer unit and/or N, N '-dimethyl acrylamide polymer unit.
Preferably in temperature sensitive type ionic liquid chirality Salen Ti composition catalyst, X in the range of 10～100, Y's
Scope is 1～10.
Present invention also offers and a kind of prepare described temperature sensitive type ionic liquid chirality Salen Ti composition catalyst
Method, the method comprises the following steps:
1) formula 2 structure Chiral Schiff Base compound and formula 3 structure imidazolium compounds carry out substitution reaction, obtain formula 4 and tie
The Chiral Schiff Base compound of structure ion liquid functionalization；
2) the Chiral Schiff Base compound of described ion liquid functionalization and tetra isopropyl titanate carry out complexation reaction,
Obtain formula 5 structure ion liquid chirality Salen Ti coordination compound；
3) use temperature sensitive polymer unit and formula 5 structure ion liquid functional chirality Salen Ti coordination compound by controlled
Radical polymerization, obtains temperature sensitive type ionic liquid Salen Ti composition catalyst；
Wherein,
R1、R2、R3Independently selected from hydrogen, alkyl, aryl, aryl substituted alkyl or alkoxyl；
R4ForN is 0～3；
R5For C1～C3Alkyl or hydrogen atom.
Preferably scheme, R1、R2And R3It is respectively hydrogen, C1～C5Alkyl, phenyl, C containing phenyl substituent1～C5Alkane
Base or C1～C5Alkoxyl；R4ForN is 0～2；R5For hydrogen atom.
Preferably scheme, temperature sensitive monomer and described ionic liquid chirality Salen Ti coordination compound mol ratio are (1～100):
1；It is more preferably (5～50): 1.
More preferably scheme, temperature sensitive polymer monomer is NIPA and/or N, N '-dimethyl acryloyl
Amine.
The present invention is based on described temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether not
The method of symmetrical oxidation reaction: in aqueous medium, formula 6 structure sulfide compound and hydrogen peroxide are at described temperature sensitive type ionic liquid
Carry out asymmetric oxidation reaction under the catalytic action of Salen Ti composition catalyst, obtain formula 7 structure chiral sulfoxides:
Wherein,
R6And R7Independently selected from aryl, containing heterocyclic group, alkyl or replacement alkyl.
Preferably scheme, R in sulfide compound and chiral sulfoxides6And R7Independently selected from: without the C of substituent group6
～C12Aryl, or containing halogen, C1～4Alkyl, C1～4Alkoxyl, C2～5The C of alkoxy carbonyl, nitro or cyano substituent6～C12
Aryl, or without substituted C1～C6Alkyl, or containing the C of aryl substituent1～C6Alkyl (wherein, aryl substituent is excellent
Elect the C without substituent group as6～C12Aryl, or containing halogen, C1～4Alkyl, C1～4Alkoxyl, C2～5Alkoxy carbonyl, nitro or
The C of cyano substituent6～C12Aryl), or containing halogen, nitro, hydroxyl or the C of cyano substituent1～C6Alkyl, or containing pyrrole
The group of pyridine, or the group containing imidazoles.
It is more preferably: R6And R7Independently selected from a kind of in following substituent group: With
Most preferably sulfide compound is: aminomethyl phenyl thioether (molecular formula C7H8S)；4-Bromophenylmethyl thioether (molecular formula
C7H7BrS)；4-methoxyphenyl thioether (molecular formula C8H10OS)；4-nitrobenzophenone thioether (molecular formula C7H7NO2S)；2-methoxyl group
Aralkyl sulfid (molecular formula C8H10OS)；Omeprazole thioether (5-methoxyl group-2-(4-methoxyl group-3,5-dimethyl-2-pyridine radicals)
Methyl thio-1H-benzimidazole, molecular formula C17H19N3O2S)。
Most preferably chiral sulfoxides is: methyl phenyl sulfoxide (molecular formula C7H8OS)；4-Bromophenylmethyl sulfoxide
(molecular formula C7H7BrOS)；4-methoxyphenyl methyl sulfoxide (molecular formula C8H10O2S)；4-nitrobenzophenone methyl sulfoxide (molecular formula
C7H7NO3S)；2-methoxyphenyl methyl sulfoxide (molecular formula C8H10O2S)；Omeprazole (5-methoxyl group-2-[[(4-methoxyl group-
3,5-dimethyl-2-pyridine radicals) methyl] sulfinyl]-1H-benzimidazole, molecular formula C17H19N3O3S)。
Preferably scheme, is slowly dropped to hydrogenperoxide steam generator containing described sulfide compound and described temperature sensitive type ionic liquid
In the aqueous solution of body Salen Ti composition catalyst, carry out asymmetric oxidation reaction.
More preferably scheme, described temperature sensitive type ionic liquid Salen Ti composition catalyst and described sulfide compound
Mol ratio is 1:50～1:1000；It is preferably 1:100～1:300.
More preferably scheme, in described hydrogenperoxide steam generator, hydrogen peroxide is (1 with the mol ratio of described sulfide compound
～2): 1；It is preferably (1～1.2): 1.
More preferably scheme, hydrogenperoxide steam generator concentration is 15wt%～70wt%；It is preferably 25wt%～35wt%.
More preferably scheme, asymmetric oxidation reaction, under the conditions of temperature is-50 DEG C～50 DEG C, reacts 0.1～5h.Enter one
Walk preferred reaction temperature and be-5 DEG C～20 DEG C.The further preferred response time is 1～1.5h.
More preferably scheme, after asymmetric oxidation reaction completes, rises reaction system high-temperature and realizes temperature sensitive type ionic liquid
Body Salen Ti composition catalyst hydrophilic-hydrophobic changes, and separates out temperature sensitive type ionic liquid Salen Ti composition catalyst, mistake
Filter is reclaimed.
Hinge structure, the Advantageous Effects that technical scheme is brought:
1) the temperature sensitive type ionic liquid chirality Salen Ti composition catalyst of technical scheme design mainly wraps
Containing catalyst elements and temperature sensing material unit, catalyst elements is with Ti for catalytic active center atom, with chirality Salen for joining
Body, this catalyst elements shows higher selectivity and high catalytic activity to the asymmetric oxidation reaction of thioether, and chirality is sub-
The productivity of sulfone is up to 85%～98%.And temperature sensing material unit imparts temperature sensitive type ionic liquid chirality Salen Ti coordination compound and urges
The preferable water solublity of agent, it is achieved carry out the asymmetric oxidation reaction of thioether, simultaneously temperature sensing material unit tool using water as solvent
There is the function that hydrophilic-hydrophobic converts, the water solublity of catalyst, the beneficially recycling of catalyst can be controlled by temperature.
2) temperature sensing material water-wet side shape in water in the temperature sensitive type ionic liquid Salen Ti composition catalyst of the present invention
Becoming hydrophilic outer shell, hydrophobic active center is assembled rapidly, forms micelle, is preferable nano-reactor, hydrophobic thioether class
After reaction substrate adds in aqueous solution, hydrophobic inner core can be rapidly entered, during with the aqueous solution of hydrogen peroxide for oxygen source, hydrogen peroxide
Hydrophobic inner core oxidizing sulfur ether can be slowly entered and generate chiral sulfoxide, substantially increase selectivity and the reaction effect of chiral oxidization
Rate.
3) in the preparation process of the temperature sensitive type ionic liquid chirality Salen Ti composition catalyst of the present invention, temperature sensitive type from
Catalyst elements and temperature sensing material unit in sub-liquid chirality Salen Ti composition catalyst can arbitrarily regulate and control, and can obtain
Obtain the block polymer PN of a series of different hydrophobe ratiosX(IS)y, meet different catalytic applications requirements.
4) present invention is catalyzed thioether asymmetric oxidation based on temperature sensitive type ionic liquid chirality body Salen Ti composition catalyst
Reaction can be carried out in aqueous medium, overcomes the defect that prior art need to carry out reacting in organic solvent.
5) present invention makes full use of its temperature sensing material based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst
The hydrophobe-hydrophile conversion performance that unit has, has hydrophilic under relatively lower temp, has hydrophobic at relatively high temperatures
Property, only need to can realize the recovery of temperature sensitive type ionic liquid chirality Salen Ti composition catalyst by controlling temperature.Overcome
In prior art, Salen Ti composition catalyst is difficult to the defect reclaimed, and is substantially reduced the use cost of catalyst.
6) present invention's is simple based on temperature sensitive type ionic liquid Salen Ti composition catalyst preparation method, process conditions
Gentleness, beneficially large-scale industrial production.
Accompanying drawing explanation
[Fig. 1] is catalyst transmission electron microscope (TEM) figure in aqueous；B, c, e, respectively PN in figure60(IS)2、PN68
(IS)4、PN66(IS)6Three kinds of representative aqueous catalyst solutions transmission electron microscope picture at room temperature；From figure 1 it appears that catalysis
Agent can form the particle of nanometer spherical in water, and the upper right corner is the aqueous solution figure of three kinds of catalyst, three kinds of catalyst
To be well dissolved in water, form micellar nanoparticles.B ' is figure b PN60(IS)2When aqueous temperature is increased to 35 DEG C, catalyst
The photo assembled, from upper right photo it can be seen that rise high-temperature, catalyst separates out from aqueous phase, and this has just reached, and " room temperature is efficiently urged
Changing, heat up simple and direct separation " effect, thus realize the simple of catalyst and reclaim and efficiently repeat.
[Fig. 2] is Infrared Characterization (FT-IR) figure of several feature catalyst, and a is the infrared of traditional catalyst Salen Ti
Figure, b is catalyst PN68(IS)4Infrared figure, b ' is catalyst PN68(IS)4Infrared figure after reusing.From figure permissible
Finding out, after catalyst has a characteristic peak of traditional Salen Ti, and catalyst is reused, what infrared figure did not have changes
Becoming, catalyst still has good catalytic effect.
Detailed description of the invention
Below in conjunction with example, the present invention is further detailed explanation, is exemplary describing rather than to the present invention's
Limit.
Embodiment 1
Preparation (the R of temperature sensitive type chirality nanometer catalysts1、R2、R3It is the tert-butyl group), R4For vinyl, selection from
Sub-liquid is vinyl imidazole.
Under room temperature, by (R, R)-cyclohexanediamine tartrate (11.2mmol) split and potassium carbonate (22.5mmol)
Being dissolved in 20mL dehydrated alcohol and deionized water (5/l, V/V) mixed solvent, be to slowly warm up to 80 DEG C, reflux 2h, puts into refrigerator.
Free (R, R)-cyclohexanediamine chloroform extraction (4 × 5mL) out merges organic facies afterwards.0 DEG C, it is slowly added to ethereal HCI molten
Liquid (11.2mmol, 2mol/L), the most overnight.Then by protected for above-mentioned single amino (R, R)-cyclohexanediamine
(8mmol) the mixed of 60mL absolute methanol and dehydrated alcohol (1/1, V/V) it is dissolved in 3,5-di-tert-butyl salicylaldehyde (8mmol)
In bonding solvent, add activity 4A molecular sieve (1g), react 4h under room temperature, obtain faint yellow solid.By the 20mL 3-tert-butyl group-5-
Chloromethyl salicylaldehyde (8mmol) is slowly added dropwise into above-mentioned solution with the anhydrous methylene chloride mixed solution of triethylamine (16mmol)
In, react 4h under room temperature, filter afterwards, in dehydrated alcohol, recrystallization obtains thick product.Through column chromatography purification (SiO2, ethyl acetate/
Normal hexane=1/5, V/V), obtain pale yellow powder shape solid CL (3.57g, 83%).Calc.for C33H47ClN2O2:C,
73.51；H,8.79；N,5.20.Found:C,73.46；H,8.91；N, 5.12%.1H-NMR(CDCl3,400MHz):δppm
14.29(s,1H),13.67(s,1H),8.44(s,1H),8.31(s,1H),7.30(d,1H),7.26(d,1H),6.99(d,
1H),6.89(d,1H),4.43(s,2H),3.55-3.32(m,2H),1.97-1.46(m,8H),1.40(s,9H),1.23(s,
18H).FT-IR(KBr):3446,2954,2862,1629,1591,1479,1469,1439,1391,1361,1271,1252,
1241,1201,1174,1144,1086,1040,981,934,879,828,803,772,731,711,644cm-1。
The above-mentioned solid CL (3.2mmol, 1.725g) of the material amount such as addition and vinyl miaow in the toluene that 50mL is dried
Azoles (3mmol, 0.28g), N2Under protection, 110 DEG C of backflow 48h.Decompression solvent distillation, vacuum drying, at room temperature, by above-mentioned product
Thing is dissolved in CH2Cl2In, it is added thereto to the tetra isopropyl titanate (Ti (O of equimolar amountsiPr)4, 3.2mmol, 0.91g), room
Temperature reaction 3h, obtains yellow product IL/Ti (salen).FT-IR(KBr):γmax/cm-1 3437,3310,3073,2973,
2933,2882,1653,1540,1458,1384,1365,1263,1172,1130,1051,986,922,881,838,626,
518cm-1.1H NMR(500MHz,CD3Cl3): δ 8.11～7.65 (s, 2H, CH=N), 7.18～7.59 (m, 4H, ArH), 6.05
(m, 1H, N-CH=CH2) 4.15 (s, 1H, C=NCH), 3.87 (m, 1H, C=NCH), 3.56 (m, 4H, N-CH=CH2and-N-
CH2-N-), 2.36～2.65 (m, 2H, CH3-CH-CH3in iPrO-), 1.46 (m, 8H, cyclohexyl-H), 1.23～1.37
(m,27H,H-in t-butyl),1.31(m,12H,CH3-CH-CH3in iPrO-)。
In Schlenk, add temperature sensing material and the IL/Ti (salen) of different proportion amount, be dissolved in absolute methanol
In, and it is added thereto to initiator azo-bis-isobutyl cyanide (AIBN, 0.5mmol, 0.082g) and chain-transferring agent propanethiol (n-
Propanethiol, 1mmol, 0.076g), N2Under conditions of protection, after 60 DEG C of reaction 24h, being cooled to room temperature, decompression distillation removes
Removing solvent, then dissolve with oxolane, ether sedimentation, vacuum drying obtains yellow solid product PNx(IS)y, (x represents temperature sensitive
The polymer of unit, y represents the degree of polymerization of ion liquid functionalization Salen Ti unit).X and y is characterized by nuclear-magnetism and draws.
Other catalyst are prepared according to the method described above.Enumerate four examples, be respectively as follows: PN60(IS)2:FT-IR(KBr):γmax/
cm-1 3436,3313,3075,2971,2942,2891,1653,1542,1457,1386,1368,1263, 1170,1131,
1054,985,927,880,836,806,709,624,519 cm-1.1H NMR(500 MHz,CDCl3): δ 6.24～6.89 (m,
60H, HC-NH-C=O), 6.08 (m, 2H, N-CH-CH2-of N-vinyl), 4.18 (m, 2H, C=NCH), 3.99 (m, 60H ,-
CH-CH2In NIPAAm), 3.88 (m, 2H, C=NCH), 3.67 (m, 8H ,-CH-CH2-of N-vinyl in IL and-N-
CH2-N-),3.45(m,60H,CH3-CH-CH3 in NIPAAm),3.06(m,12H,-N-CH2-CH2-N-and-N-CH2-
Ph-),2.84(m,2H,SH-CH2-CH2-CH3), 2.64～2.73 (m, 4H, CH3-CH-CH3 of iPrO-in Ti
(salen)),2.38(m,2H,SH-CH2-CH2-CH3), 1.86～2.12 (m, 120H ,-CH2-CH-in NIPAAm),1.71
(s,3H,SH-CH2-CH2-CH3), 1.43 (16H, cyclohexyl-H), 1.13～1.33 (54H, H-in t-butyl), 1.09
～1.16 (m, 384H, CH3-CH-CH3 in iPrO-and NIPAAm)；
PN68(IS)4:FT-IR(KBr):γmax/cm-1 3436,3302,3064,2967,2923,2867,1645,1541,
1454,1382,1365,1265,1175,1128,1053,965,920,882,834,809,709,635,624,509 cm-1.1H
NMR(500 MHz,CD3Cl3): δ 8.15～7.68 (m, 8H, CH=N), 7.14～7.64 (m, 16H, ArH), 6.24～6.89
(m, 68H, HC-NH-C=O), 6.05 (m, 4H, N-CH-CH2-of N-vinyl), 4.14 (m, 4H, C=NCH), 3.99 (m,
68H,-CH-CH2-in NIPAAm), 3.85 (m, 4H, C=NCH), 3.58 (m, 16H ,-CH-CH2-of N-vinyl in IL
and-N-CH2-N-),3.26(m,68H,CH3-CH-CH3 in NIPAAm),2.90(m,24H,-N-CH2-CH2-N-and-N-
CH2-Ph-),2.78(m,2H,SH-CH2-CH2-CH3), 2.34～2.68 (m, 8H, CH3-CH-CH3 of iPrO-in Ti
(salen)),2.10(m,2H,SH-CH2-CH2-CH3), 1.78～1.98 (m, 136H ,-CH-CH2 in NIPAAm),1.73
(s,3H,SH-CH2-CH2-CH3), 1.47 (m, 32H, cyclohexyl-H), 1.21～1.38 (m, 108H, H-in t-
Butyl), 1.06～1.15 (m, 456H, CH3-CH-CH3 in iPrO-and NIPAAm)；
PN66(IS)6:FT-IR(KBr):γmax/cm-1 3441,3309,3061,2974,2927,2864,1651,1530,
1453,1382,1363,1266,1176,1123,1051,963,920,883,836,805,708,625,504 cm-1.1H NMR
(500 MHz,CD3Cl3): δ 8.13～7.72 (m, 12H, CH=N), 7.18～7.69 (m, 24H, ArH), 6.21～6.92 (m,
66H, HC-NH-C=O), 6.16 (m, 6H, N-CH-CH2-of N-vinyl), 4.04 (m, 6H, C=NCH), 3.97 (m, 66H ,-
CH-CH2-in NIPAAm), 3.81 (m, 6H, C=NCH), 3.56 (m, 24H ,-CH-CH2-of N-vinyl in IL and-N-
CH2-N-),3.23(m,66H,CH3-CH-CH3 in NIPAAm),3.09(m,36H,-N-CH2-CH2-N-and-N-CH2-
Ph-),2.75(m,2H,SH-CH2-CH2-CH3), 2.41～2.61 (m, 12H, CH3-CH-CH3 of iPrO-in Ti
(salen)),2.23(m,2H,SH-CH2-CH2-CH3), 1.76～1.82 (m, 132H ,-CH-CH2 in NIPAAm),1.75
(s,3H,SH-CH2-CH2-CH3), 1.41 (m, 48H, cyclohexyl-H), 1.22～1.31 (m, 162H, H-in t-
Butyl), 1.01～1.12 (m, 469H, CH3-CH-CH3in iPrO-and NIPAAm)；
PN64(IS)8:FT-IR(KBr):γmax/cm-1 3435,3302,3066,2974,2924,2860,1655,1535,
1455,1380,1365,1264,1174,1125,1054,967,924,882,839,806,709,634,625,507cm-1.1H
NMR(500MHz,CD3Cl3): δ 8.11～7.62 (m, 16H, CH=N), 7.13～7.67 (m, 32H, ArH), 6.24～6.87
(m, 64H, HC-NH-C=O), 6.22 (m, 8H, N-CH-CH2-of N-vinyl), 4.46 (m, 8H, C=NCH), 4.05 (m,
64H,-CH-CH2-in NIPAAm), 3.78 (m, 8H, C=NCH), 3.58 (m, 32H ,-CH-CH2-of N-vinyl in IL
and-N-CH2-N-),3.18(m,64H,CH3-CH-CH3in NIPAAm),2.86(m,48H,-N-CH2-CH2-N-and-N-
CH2-Ph-),2.75(m,2H,SH-CH2-CH2-CH3), 2.45～2.63 (m, 16H, CH3-CH-CH3of iPrO-in Ti
(salen)),2.12(m,2H,SH-CH2-CH2-CH3), 1.75～1.87 (m, 128H ,-CH-CH2-in NIPAAm),1.73
(s,3H,SH-CH2-CH2-CH3), 1.41 (m, 64H, cyclohexyl-H), 1.22～1.31 (m, 216H, H-in t-
Butyl), 1.01～1.12 (m, 480H, CH3-CH-CH3in iPrO-and NIPAAm)。
According to the method described above, a series of catalyst is prepared with different temperature sensing materials.
Embodiment 2
Being optimized reaction condition with aminomethyl phenyl thioether for model substrates, result is as follows.
Reaction scheme:
The substrate (aminomethyl phenyl thioether) of 1mmol, the catalyst PN of 0.5mmol% is added in 10mL reaction bulb68(IS)
4,1mL H2O makees solvent, under conditions of 25 DEG C, is slowly added dropwise the H of 1.2mmol30% in 15min2O2, continue reaction 45min.
After reaction terminates, catalyst separates out automatically, separates aqueous phase, is dried and reuses after the washing of catalyst normal hexane, and aqueous phase is used
Obtaining product after dichloromethane extraction, and product carries out gas chromatographic analysis detection conversion ratio and selectivity, liquid chromatograph is divided
Analysis obtains ee value, and column chromatography waits until product, calculated yield, and nuclear-magnetism characterizes and determines product structure.
Four kinds of comparative catalysts are used for being catalyzed aminomethyl phenyl sulfide oxidation with tradition Salen Ti catalyst and become sulfoxide
Reaction, its result is as shown in the table:
[a]Yield of the isolated product.[b]Determined by HPLC.
From table, the ratio regular meeting of hydrophobe substituent group affects catalytic effect, presents the change of regularity.PN68(IS)4It is
The most moderate hydrophobe ratio, (the PN when hydrophilic group is long60(IS)2), active center will be substantially reduced, and catalytic efficiency is less than
PN68(IS)4(yield only has 75%).When hydrophobe ratio, < when 17, catalysis activity also can reduce, (PN66(IS)6It is 89%, PN64
(IS)8It is 86%), and ee value also presents regular change.
Methyl phenyl sulfoxide, white solid, silica gel column chromatography separates (methanol: dichloromethane=20:80 (volume ratio))
(93% yield, 98%ee).1H NMR(CDCl3,500MHz):δ(ppm):2.56(s,3H,Me),7.37-7.52(m,5H,
ArH).13C NMR(CDCl3,125MHz):δ(ppm):43.8(SCH3),123.4,129.3,131.0,145.5；Conversion ratio and
Selectivity is recorded (Agilent Co, HP19091G-B213, column temperature 180 DEG C, flow velocity: 1.6mL/min), ee value by gas chromatogram
(chromatographic column: Daicel chiralpak AD, flowing phase: isopropanol/normal hexane=10:90 is recorded by chiral high performance liquid chromatography
(volume ratio), flow velocity: 1.0mL/min, wavelength: 254nm, temperature 25 DEG C).
Embodiment 3
Choose PN68(IS)4Carry out the examination of different substrate.
Reaction scheme:
Reactions steps and processing mode example performed as described above 2
By catalyst PN68(IS)4Sulfoxide is become for being catalyzed other five kinds of sulfide oxidations with tradition Salen Ti catalyst
Reaction, its result is as shown in the table:
By table it can be seen that catalyst PN68(IS)4Catalytic effect be substantially better than the effect of traditional catalyst, at productivity
Big advantage is had with in ee value.
The sign data of portion of product are as follows:
4-Bromophenylmethyl sulfoxide, yellow solid, silica gel column chromatography separates (methanol: dichloromethane=20:80 (volume
Than)) (productivity 82%, ee value > 99%).1H NMR(CDCl3,500MHz):δ(ppm):3.07(s,3H,SCH3),7.84(d,
2H,ArH),7.74(d,2H,ArH).13C NMR(CDCl3,125MHz):δ(ppm):44.5(SCH3),129.0,132.7,
139.5；Ee value is recorded by chiral high performance liquid chromatography that (chromatographic column: Daicel chiralpak AD, flow phase: isopropanol/just
Hexane=50:50 (volume ratio), flow velocity: 1.0mL/min, wavelength: 254nm, temperature 25 DEG C)
4-methoxyphenyl methyl sulfoxide, colourless liquid, silica gel column chromatography separates (methanol: dichloromethane=20:80 (body
Long-pending ratio)) (productivity 90%, ee value 94%).1H NMR(CDCl3,500MHz):δ(ppm):3.01(s,3H,SCH3),3.91(s,
3H,OCH3),7.04(d,2H,ArH),7.89(d,2H,ArH).13C NMR(CDCl3,125MHz):δ(ppm):44.9(SCH3),
55.7(OCH3),114.5,129.6,132.3,163.7；Ee value is recorded (chromatographic column: Daicel by chiral high performance liquid chromatography
Chiralpak AD, flow phase: isopropanol/normal hexane=20:80 (volume ratio), flow velocity: 1.0mL/min, wavelength: 254nm, temperature
Spend 25 DEG C)
4-nitrobenzophenone methyl sulfoxide, yellow solid, silica gel column chromatography separates (methanol: dichloromethane=20:80 (volume
Than)) (productivity 97%, ee value 88%).1H NMR(CDCl3,500MHz):δ(ppm):2.57(s,3H,SCH3),7.30(d,2H,
ArH),8.16(d,2H,ArH).13C NMR(CDCl3,125MHz):δ(ppm):43.9(SCH3),113.9,125.0,144.7,
148.9；Ee value is recorded by chiral high performance liquid chromatography that (chromatographic column: Daicel chiralpak AD, flow phase: isopropanol/just
Hexane=30:70 (volume ratio), flow velocity: 1.0mL/min, wavelength: 254nm, temperature 25 DEG C)
2-methoxyphenyl methyl sulfoxide, colourless liquid, silica gel column chromatography separates (methanol: dichloromethane=20:80 (body
Long-pending ratio)) (productivity 88%, ee value 99%).1H NMR(CDCl3,500MHz):δ(ppm):2.67(s,3H,SCH3),3.78(s,
3H,OCH3),6.84-7.37(m,4H,ArH).13C NMR(CDCl3,125MHz):δ(ppm):13C NMR(CDCl3,
125MHz):δ(ppm):41.1(SCH3),55.7(OCH3),118.6,121.5,124.3,132.0,154.7；Ee value is by chirality
High performance liquid chromatography records (chromatographic column: Daicel chiralpak AD, flowing phase: isopropanol/normal hexane=20:80 (volume
Than), flow velocity: 1.0mL/min, wavelength: 254nm, temperature 25 DEG C)
Omeprazole, white powder, silica gel column chromatography separates (methanol: dichloromethane=20:80 (volume ratio)) (productivity
80%, ee value 87%).1H NMR(DMSO,500MHz):δ(ppm):2.15(s,6H),3.65(s,3H),3.78(s,3H),
4.66and 4.75(AB-system,2H),6.90(dd,1H),7.08(s,1H),7.53(d,1H),8.15(s,1H)；Ee value
(chromatographic column: Daicel chiralpak AD, flowing phase: isopropanol/normal hexane=20:80 is recorded by chiral high performance liquid chromatography
(volume ratio), flow velocity: 1.0mL/min, wavelength: 254nm, temperature 25 DEG C)
The Thermo-sensitive of this catalyst is embodied in, and after reaction terminates, catalyst separates out from reaction system, when rising high-temperature, urges
Agent separates out completely and separates, and under conditions of room temperature, catalyst is dissolved in water, and when temperature raises, catalyst just separates out from aqueous phase
Assemble.Concrete figure, can be found out by transmission electron microscope.
Embodiment 4
The examination of catalyst repeat performance
By above-mentioned reacted solution by heating up, catalyst just can separate out from reaction system, then through filtering, washing
Wash, the step such as drying, catalyst is used for next catalystic converter system, it is as shown in the table that it reuses effect:
[a]Yield of the isolated product.[b]Determined by HPLC.
From the above data, it can be seen that the reusability of catalyst is preferable.This reaction system is all with water for reaction
Solvent, environmental protection.The most important thing is, the Stability Analysis of Structures of catalyst, Reaction Separation is simple, can repeatedly use.
Claims (9)
1. a temperature sensitive type ionic liquid chirality Salen Ti composition catalyst, it is characterised in that: there is formula 1 structure:
Wherein,
For temperature sensitive polymer unit；
X/Y is (1～100): 1；
R1、R2、R3Independently selected from for hydrogen, alkyl, aryl, aryl substituted alkyl or alkoxyl；
R4ForN is 0～3；
R5For C1～C3Alkyl or hydrogen atom.
Temperature sensitive type ionic liquid chirality Salen Ti composition catalyst the most according to claim 1, it is characterised in that: R1、
R2And R3Independently selected from hydrogen, C1～C5Alkyl, phenyl, C containing phenyl substituent1～C5Alkyl or C1～C5Alkoxyl；
R4ForN is 0～2；R5For hydrogen atom.
Temperature sensitive type ionic liquid chirality Salen Ti composition catalyst the most according to claim 1, it is characterised in that: X/
Y is (5～50): 1.
Temperature sensitive type ionic liquid chirality Salen Ti composition catalyst the most according to claim 1, it is characterised in that: institute
The temperature sensitive polymer unit stated is NIPA polymer unit and/or N, N '-dimethyl acrylamide polymer
Unit.
5. the side of preparation temperature sensitive type ionic liquid chirality Salen Ti composition catalyst described in any one of Claims 1 to 4
Method, it is characterised in that: comprise the following steps:
1) formula 2 structure Chiral Schiff Base compound and formula 3 structure imidazolium compounds carry out substitution reaction, obtain formula 4 structure from
The Chiral Schiff Base compound of sub-liquid functional；
2) the Chiral Schiff Base compound of described ion liquid functionalization and tetra isopropyl titanate carry out complexation reaction, to obtain final product
Formula 5 structure ion liquid Salen Ti coordination compound；
3) use temperature sensitive monomer and formula 5 structure ion liquid Salen Ti coordination compound by controllable free-radical polymerisation method, obtain temperature
Quick type ionic liquid chirality Salen Ti composition catalyst；
Wherein,
R1、R2、R3Independently selected from hydrogen, alkyl, aryl, aryl substituted alkyl or alkoxyl；
R4ForN is 0～3；
R5For C1～C3Alkyl or hydrogen atom.
The method preparing temperature sensitive type ionic liquid chirality Salen Ti composition catalyst the most according to claim 5, its
It is characterised by: R1、R2And R3Independently selected from hydrogen, C1～C5Alkyl, phenyl, C containing phenyl substituent1～C5Alkyl or C1
～C5Alkoxyl；R4ForN is 0～2；R5For hydrogen atom.
The method preparing temperature sensitive type catalyst the most according to claim 5, it is characterised in that: described temperature sensitive polymer monomer
It is (1～100) with described ionic liquid chirality Salen Ti coordination compound mol ratio: 1.
The method preparing temperature sensitive type catalyst the most according to claim 7, it is characterised in that: described temperature sensitive polymer monomer
It is (5～50) with described ionic liquid chirality Salen Ti coordination compound mol ratio: 1.
9. according to the side preparing temperature sensitive type ionic liquid chirality Salen Ti composition catalyst described in claim 1,7 or 8
Method, it is characterised in that: described temperature sensitive polymer monomer is NIPA and/or N, N '-dimethyl acrylamide.
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