CN106045804B - A method of based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether asymmetric oxidation reaction - Google Patents
A method of based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether asymmetric oxidation reaction Download PDFInfo
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Abstract
The invention discloses a kind of methods based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether asymmetric oxidation reaction；This method is that in an aqueous medium, chiral sulfide compound and hydrogen peroxide carry out asymmetric oxidation reaction under the catalytic action of temperature sensitive type ionic liquid chirality Salen Ti composition catalyst to get chiral sulfoxides；Temperature sensitive type ionic liquid chirality Salen Ti composition catalyst contains chiral Salen Ti composition catalyst unit and temperature sensing material unit simultaneously: compared with traditional chiral Salen Ti catalyst, the catalyst good water solubility, catalysis reaction can be carried out in an aqueous medium, and is easily recycled reuse；Applied to the aqueous catalysis oxidation reaction of chiral thioether, have the characteristics that high catalytic efficiency, chiral sulfoxide are selectively good.
Description
Technical field
The present invention relates to a kind of improved chirality Salen Ti composition catalyst, in particular to a kind of temperature sensitive type ionic liquids
Body chirality Salen Ti composition catalyst, and it is complex-catalyzed based on the temperature sensitive type ionic liquid chirality Salen Ti
The method of agent aqueous catalysis thioether asymmetric oxidation reaction belongs to new catalytic material preparation and medicine intermediate synthetic technology neck
Domain.
Background technique
Optically pure sulfoxide is a kind of important chiral auxiliaries, it is widely used in asymmetric catalysis synthesis, such as
C-C key forms reaction, and C-O key forms 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 the active group of many drugs, they synthesize have bioactive compound in terms of application it is also very extensive, such as
Some drug modafinils fast-selling on the market, Shu Lindake and Esomeprazole.All contain one in many bioactive molecules
Chiral sulfinyl unit, and the different enantiomer of stereochemical structure has different physiological activity and metabolism.Together
When chiral sulfoxide be also used as chiral ligand applied to enantioselectivity catalysis reaction in.Therefore, high enantioselectivity is obtained
Sulfoxide have important theory significance and realistic price.In the past few decades, researchers various prepare light developing
Very big effort is worked it out in terms of the method for learning pure sulfoxide, mainly there is biological method and chemical method.The sulfoxide method packet of biology
It includes enzyme, microorganism etc. and prepares chiral sulfoxide, have many advantages, such as Substratspezifitaet, efficient, green, but biological enzyme or microorganism are because steady
The deficiency of qualitative poor, price height and substrate spectrum are narrow etc., application are restricted.Chemical method is divided into chirality
The methods of adjuvant induction, fractionation and asymmetry catalysis oxidation, so far, wherein the asymmetric oxidation of thioether is to prepare chiral Asia
The method of sulfone most practicability.1984, Kagan realized sulphur using the Sharpless epoxidation catalyst of improvement for the first time
Asymmetric oxidation (Synthesis, the 1984,325-326 of ether；Tetrahedron Letters, 1984,25,1049-1052),
Later, researchers have carried out research extensively and profoundly to this field, develop it is a series of based on Titanium, vanadium, aluminium, iron,
The catalyst systems such as copper (Tanaka, T.；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 realized, but it is right
These have the progress of the substrate of challenge but very slow for Yu Huan, big steric hindrance or long-chain class thioether, until 2013, by metalloporphyrin
Inspiration, Gao is catalyst, hydrogen peroxide using the complex compound that a kind of chiral four teeth nitrogen organic ligand and metal manganese compound are formed
For oxidant, being successfully realized big steric hindrance, long-chain or branch class has conversion (Dai, the W. of 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 is classified by chiral ligand to be specifically included that with C2 symmetry chiral diol (phenol)-titanium catalyst system,
With the chiral three hydramine-titanium of C3 symmetry and pick catalyst system, chirality porphyrin metal coordination catalysis system, Chiral Schiff Base gold
Category complex catalysis system (Arkivoc, 2011, (i), 1-110；Journal of Sulfur Chemistry,2013,34
(3),301-341).However, the catalyst series system is to carry out in the methylene chloride of not environment friendly, and product is sub-
Sulfone is selectively low, and the separation and purifying to product bring very big difficulty.The presence of these problems considerably increases chiral Asia
The synthesis cost of sulfone limits the industrial production of thioether asymmetric oxidation reaction.
International monopoly W091/12221 and W094/27988, which are described, directly splits the sulfoxide compound of racemic modification
At the method for single enantiomer, it should be particularly mentioned that Omeprazole is split into single enantiomer.Chinese patent CN1087739, it is international
Patent application W02006/094904, W02007/013743 etc. describe use (S)-binaphthol or tartaric acid resolution of omeprazole
The interior inclusion complex of levo-omeprazole is obtained, then obtains the side of levo-omeprazole from this inclusion complex with silicagel column or alkaline hydrolysis again
Method.The Omeprazole that half can be wasted with such Split Method resolution of omeprazole, causes environmental pollution and economic loss, Er Qieyou
Also costly, therefore the large-scale use of this Split Method industrially is restricted optically active resolving agent price.
International monopoly W096/02535, Chinese patent CN1070489 are disclosed in chiral bidentate ligand ethyl tartrate
In the presence of titanium complex compound and alkali, the side of esomprazole is obtained with hydrogen peroxide analog derivative oxidation Omeprazole thioether
Method.International monopoly W003/089408 is described under the complex catalysis of chiral monodentate (S)-(+)-mandelate and titanium or vanadium,
The method that oxidation Omeprazole thioether obtains levo-omeprazole in the presence of base simultaneously.
Chinese patent CN200380104409.8, international monopoly W02004/052881 are described using chiral pick complex compound
Or the method that chiral hafnium complex prepares S-pantoprazole.This method is in (+)-or (-)-tartaric acid derivatives and alkoxy
In the presence of pick or alkoxy hafnium, selectively oxidizing sulfur ether synthesizes S-pantoprazole.CN200610023955 and CN181080803B
Describe it is a kind of be coordinated generated in-situ titanium-containing catalyst using metal tiron and chiral diol, make in tert-butyl hydroperoxide
Under, selectively oxidizing sulfur ether.
International monopoly W096/17076 and W096/17077, which are described, is selectively oxidized thioether or choosing using microorganism
Selecting property restore sulfone compound, come obtain single enantiomer sulfoxide compound method.
Summary of the invention
In view of the defects existing in the prior art, the purpose of the invention is to provide one kind to contain temperature sensing material unit, can
To realize the temperature sensitive type ionic liquid chirality Salen Ti composition catalyst water phase of hydrophilic-hydrophobic conversion by temperature condition
The method for being catalyzed thioether asymmetric oxidation reaction, which has excellent catalytic activity and selectivity, and realizes in water
It is catalyzed sulfide compound selective oxidation in solvent into sulfoxide, and regulates and controls the water solubility of catalyst by temperature, realizes catalyst
Recycling, this method is simple and efficient, is environmentally friendly, reaction condition is mild, meets technique production requirement.
In order to achieve the above technical purposes, the present invention provides one kind is matched based on temperature sensitive type ionic liquid chirality SalenTi
The method of mixture catalyst aqueous catalysis thioether asymmetric oxidation reaction, this method are 2 structure thioether chemical combination of formula in an aqueous medium
Object and hydrogen peroxide carry out not under the catalytic action of 1 structure temperature sensitive type ionic liquid chirality Salen Ti composition catalyst of formula
Symmetrical oxidation reaction is to get 3 structure chiral sulfoxides of formula:
Wherein,
For temperature sensitive unit；
X/Y is (1~100): 1.
R1、R2、R3Independently selected from hydrogen, alkyl, aryl, aryl substituted alkyl or alkoxy；
R4ForN is 0~3；
R5For C1~C3Alkyl or hydrogen atom；
R6And R7Independently selected from aryl, containing heterocyclic group, alkyl or substitution alkyl.
Preferred scheme, R in temperature sensitive type ionic liquid chirality Salen Ti composition catalyst1、R2And R3Independently selected from
Hydrogen, C1~C5Alkyl, phenyl, the C containing phenyl substituent1~C5Alkyl or C1~C5Alkoxy；R4ForN be 0~
2；R5For hydrogen atom.
Preferred scheme, the range of X are as follows: the range of 10~100, Y are 1~10.
Preferred scheme, X/Y is (5~50) in temperature sensitive type ionic liquid chirality Salen Ti composition catalyst: 1.
Preferred scheme, temperature sensitive unit is N- isopropyl in temperature sensitive type ionic liquid chirality Salen Ti composition catalyst
Acrylamide unit and/or N, N '-dimethyl acrylamide unit.
R in preferred scheme, sulfide compound and chiral sulfoxides6And R7Independently selected from:
C without substituent group6~C12Aryl, or contain halogen, C1~4Alkyl, C1~4Alkoxy, C2~5Alkoxy carbonyl, nitre
The C of base or cyano substituent6~C12Aryl；
Or without substituted C1~C6Alkyl, or the C containing aryl substituent1~C6Alkyl (wherein, aryl substituent
Preferably be free of the C of substituent group6~C12Aryl, or contain halogen, C1~4Alkyl, C1~4Alkoxy, C2~5Alkoxy carbonyl, nitro
Or the C of cyano substituent6~C12Aryl), or the C containing halogen, nitro, hydroxyl or cyano substituent1~C6Alkyl；
Or containing pyridine or containing the group of imidazoles.
R in more preferably scheme, sulfide compound and chiral sulfoxides6And R7Independently selected from following substituent group
It is a kind of:
Most preferred sulfide compound are as follows: 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- pyridyl group)
Methyl thio -1H- benzimidazole (molecular formula C17H19N3O2S)。
Most preferred chiral sulfoxides are as follows: 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- pyridyl groups) methyl] sulfinyl] -1H- benzimidazole, molecular formula C17H19N3O3S)。
Hydrogenperoxide steam generator is slowly dropped to containing the sulfide compound and the temperature sensitive type ionic liquid by preferred scheme
In the aqueous solution of body chirality Salen Ti composition catalyst, asymmetric oxidation reaction is carried out.
More preferably scheme, the temperature sensitive type ionic liquid chirality Salen Ti composition catalyst and the thioether chemical combination
The molar ratio of object is 1:50~1:1000；Further preferably 1:100~1:300.
More preferably scheme, the molar ratio of hydrogen peroxide and the sulfide compound is 1:1~2 in hydrogenperoxide steam generator:
1；Further preferably (1~1.2): 1.
More preferably scheme, hydrogenperoxide steam generator concentration are 15wt%~70wt%；Further preferably 25wt%~
35wt%.
More preferably scheme, asymmetric oxidation reaction react 0.1~5h under the conditions of temperature is -50 DEG C~50 DEG C.Into one
Walking preferred reaction temperature is -5 DEG C~20 DEG C.The further preferred reaction time is 1~1.5h.
Reaction system after the completion of asymmetric oxidation reaction, is increased temperature and realizes temperature sensitive type ionic liquid by more preferably scheme
The transformation of body chirality Salen Ti composition catalyst hydrophilic-hydrophobic, is precipitated temperature sensitive type ionic liquid chirality Salen Ti complex
Catalyst is recovered by filtration.
The preparation method of temperature sensitive type ionic liquid chirality Salen Ti composition catalyst of the invention the following steps are included:
1) 4 structure Schiff compound of formula and 5 structure imidazolium compounds of formula carry out substitution reaction to get 6 structure of formula from
The Chiral Schiff Base compound of sub- liquid functional；
2) the Chiral Schiff Base compound of the ion liquid functionalization and tetra isopropyl titanate carry out complexation reaction,
Up to 7 structure ion liquid chirality Salen Ti complex of formula；
3) controllable free-radical polymerisation is passed through using temperature sensitive monomer and 7 structure ion liquid chirality Salen Ti complex of formula
Method obtains temperature sensitive type ionic liquid chirality Salen Ti composition catalyst；
Wherein,
R1、R2、R3Independently selected from hydrogen, alkyl, aryl, aryl substituted alkyl or alkoxy；
R4ForN is 0~3；
R5For C1~C3Alkyl or hydrogen atom.
Preferred scheme, R1、R2And R3Independently selected from hydrogen, C1~C5Alkyl, phenyl, the C containing phenyl substituent1~C5
Alkyl or C1~C5Alkoxy；R4ForN is 0~2；R5For hydrogen atom.
Preferred scheme, temperature sensitive monomer and the ionic liquid chirality Salen Ti complex molar ratio are (1~100):
1；More preferably it is (5~50): 1.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) the temperature sensitive type ionic liquid chirality Salen Ti composition catalyst that technical solution of the present invention uses mainly wraps
Containing catalyst elements and temperature sensing material unit, catalyst elements using Ti as catalytic active center atom, with chiral Salen be with
Body, which shows higher selectivity and high catalytic activity to the asymmetric oxidation reaction of thioether, chiral sub-
The yield of sulfone is up to 85%~98%.And temperature sensing material unit imparts temperature sensitive type ionic liquid chirality Salen Ti complex and urges
Agent is preferably water-soluble, realizes the asymmetric oxidation reaction that thioether is carried out using water as solvent, while temperature sensing material unit has
The function of having hydrophilic-hydrophobic to convert can be controlled the water solubility of catalyst by temperature, be conducive to the recycling of catalyst.
2) temperature sensitive type ionic liquid chirality Salen Ti composition catalyst of the invention is asymmetric in aqueous catalysis thioether
Temperature sensitive material hydrophilic end forms hydrophilic outer shell in water in oxidation reaction, and hydrophobic active center is assembled rapidly, forms micella, is
Ideal nano-reactor can rapidly enter hydrophobic inner core, after hydrophobic thioether class reaction substrate is added in aqueous solution with mistake
When the aqueous solution of hydrogen oxide is oxygen source, hydrogen peroxide, which will be slow, enters hydrophobic inner core oxidizing sulfur ether generation chiral sulfoxide, significantly
Improve the selectivity and reaction efficiency of chiral oxidization.
3) preparation method of temperature sensitive type ionic liquid chirality Salen Ti composition catalyst of the invention is simple, technique item
Part is mild, in temperature sensitive type ionic liquid chirality Salen Ti composition catalyst catalyst elements and temperature sensing material unit can
Arbitrarily to regulate and control, a series of block polymer PN of different hydrophobe ratios can be obtainedX(IS)y, meet different catalytic applications
It is required that.
4) the present invention is based on temperature sensitive type ionic liquid chirality Salen Ti composition catalysts to be catalyzed thioether asymmetric oxidation
Reaction can carry out in an aqueous medium, overcome the defect that the prior art need to be reacted in organic solvent.
5) the present invention is based on temperature sensitive type ionic liquid chirality Salen Ti composition catalysts to make full use of its temperature sensing material
The hydrophobe-hydrophile conversion performance that unit has has hydrophily under relatively lower temp, has at relatively high temperatures hydrophobic
Property, only the recycling of temperature sensitive type ionic liquid chirality Salen Ti composition catalyst need to can be realized by controlling temperature.Overcome
Chirality Salen Ti composition catalyst is difficult to the defect recycled in the prior art, substantially reduces the use cost of catalyst.
Detailed description of the invention
[Fig. 1] is transmission electron microscope (TEM) figure of catalyst in aqueous solution；B, c, e, respectively PN in figure60(IS)2、PN68
(IS)4、PN66(IS)6The transmission electron microscope picture of three kinds of representative catalyst aqueous solutions 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 dissolved in water well, micellar nanoparticles are formed.B ' is figure bPN60(IS)2When aqueous temperature is increased to 35 DEG C, catalyst
The photo of aggregation can be seen that raising temperature from upper right photo, and catalyst is precipitated from water phase, this has just reached, and " room temperature is efficiently urged
Change, heat up simple and direct separation " effect, thus realize catalyst it is simple recycling and efficiently repetition.
[Fig. 2] is IR Characterization (FT-IR) figure of several feature catalyst, and a is the infrared of traditional catalyst Salen Ti
Figure, b are catalyst PN68(IS)4Infrared figure, b ' be catalyst PN68(IS)4Infrared figure after reuse.It can be with from figure
Find out, after catalyst has the characteristic peak of tradition Salen Ti, and catalyst is reused, there is no no to change for infrared figure
Become, catalyst still has good catalytic effect.
Specific embodiment
Below with reference to example, the present invention is described in further detail, is exemplary description rather than to of the invention
Limitation.
Embodiment 1
Preparation (the R of temperature sensitive type chirality nanometer catalysts1、R2、R3It is tert-butyl), R4For vinyl, selection from
Sub- liquid is vinyl imidazole.
At room temperature, by (R, the R)-cyclohexanediamine tartrate (11.2mmol) split and potassium carbonate (22.5mmol)
It is dissolved in 20mL dehydrated alcohol and deionized water (5/l, V/V) in the mixed solvent, is to slowly warm up to 80 DEG C, flow back 2h, is put into refrigerator.
(R, R)-cyclohexanediamine chloroform extraction (4 × 5mL) of separate out merges organic phase afterwards.0 DEG C, it is molten to be slowly added to ethereal HCI
Liquid (11.2mmol, 2mol/L), at room temperature overnight.Then by above-mentioned single protected (R, the R)-cyclohexanediamine of amino
(8mmol) and 3,5- di-tert-butyl salicylaldehyde (8mmol) is dissolved in the mixing of 60mL anhydrous methanol and dehydrated alcohol (1/1, V/V)
In solvent, it is added activity 4A molecular sieve (1g), reacts 4h at room temperature, obtain faint yellow solid.By 20mL 3- tert-butyl -5- chlorine
The anhydrous methylene chloride mixed solution of cresotinic acid aldehyde (8mmol) and triethylamine (16mmol) are slowly added dropwise in above-mentioned solution,
4h is reacted at room temperature, it is rear to filter, crude product is recrystallized to obtain in dehydrated alcohol.Through column chromatographic purifying (SiO2, ethyl acetate/just
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 amount of substance such as addition and vinyl miaow in 50mL dry toluene
Azoles (3mmol, 0.28g), N2Under protection, 110 DEG C of reflux 48h.It is evaporated under reduced pressure solvent, vacuum drying, at room temperature, by above-mentioned production
Object is dissolved in CH2Cl2In, the tetra isopropyl titanate (Ti (O of equimolar amounts is added theretoiPr)4, 3.2mmol, 0.91g), room
Temperature reaction 3h, obtains yellow product IL/Ti (salen).FT-IR(KBr):γmax/cm-13437,3310,3073,2973,
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 i), PrO- 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, the temperature sensing material and IL/Ti (salen) of different proportion amount is added, is dissolved in anhydrous methanol
In, and initiator azo-bis-isobutyl cyanide (AIBN, 0.5mmol, 0.082g) and chain-transferring agent propanethiol (n- are added thereto
Propanethiol, 1mmol, 0.076g), N2Under conditions of protection, after 60 DEG C of reactions for 24 hours, it is cooled to room temperature, vacuum distillation removes
Solvent is removed, is then dissolved with tetrahydrofuran, ether precipitating, vacuum drying obtains yellow solid product PNx(IS)y, (x represents temperature sensitive
The polymer of unit, y represent the degree of polymerization of ion liquid functionalization Salen Ti unit).X and y is obtained by nuclear-magnetism characterization.
Other catalyst are prepared according to the method described above.Four are enumerated, is respectively as follows:
PN60(IS)2:FT-IR(KBr):γmax/cm-13436,3313,3075,2971,2942,2891,1653,1542,
1457,1386,1368,1263,1170,1131,1054,985,927,880,836,806,709,624,519cm-1.1H NMR
(500MHz,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-CH2), inNIPAAm 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-CH3in 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-CH3ofiPrO-in Ti(salen)),2.38(m,2H,SH-CH2-CH2-CH3), 1.86~2.12 (m, 120 H ,-CH2-
CH-in NIPAAm),1.71(s,3 H,SH-CH2-CH2-CH3), 1.43 (16 H, cyclohexyl-H), 1.13~1.33 (54
H, H-in t-butyl), 1.09~1.16 (m, 384 H, CH3-CH-CH3in 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, 8 H, CH=N), 7.14~7.64 (m, 16 H, ArH), 6.24~6.89
(m, 68 H, HC-NH-C=O), 6.05 (m, 4H, N-CH-CH2- of N-vinyl), 4.14 (m, 4 H, C=NCH), 3.99 (m,
68 H,-CH-CH2- in NIPAAm), 3.85 (m, 4 H, C=NCH), 3.58 (m, 16 H ,-CH-CH2-of N-vinyl in
IL and-N-CH2-N-),3.26(m,68 H,CH3-CH-CH3 in NIPAAm),2.90(m,24 H,-N-CH2-CH2-N-
and-N-CH2-Ph-),2.78(m,2 H,SH-CH2-CH2-CH3), 2.34~2.68 (m, 8 H, CH3-CH-CH3ofiPrO-in
Ti(salen)),2.10(m,2 H,SH-CH2-CH2-CH3), 1.78~1.98 (m, 136 H ,-CH-CH2in NIPAAm),
1.73(s,3H,SH-CH2-CH2-CH3), 1.47 (m, 32 H, cyclohexyl-H), 1.21~1.38 (m, 108 H, H-int-
), butyl 1.06~1.15 (m, 456 H, CH3-CH-CH3iniPrO-and NIPAAm)；
PN66(IS)6:FT-IR(KBr):γmax/cm-13441,3309,3061,2974,2927,2864,1651,1530,
1453,1382,1363,1266,1176,1123,1051,963,920,883,836,805,708,625,504cm-1.1H NMR
(500 MHz,CD3Cl3): δ 8.13~7.72 (m, 12 H, CH=N), 7.18~7.69 (m, 24 H, ArH), 6.21~6.92
(m, 66 H, HC-NH-C=O), 6.16 (m, 6 H, N-CH-CH2- of N-vinyl), 4.04 (m, 6H, C=NCH), 3.97 (m,
66 H,-CH-CH2- in NIPAAm), 3.81 (m, 6 H, C=NCH), 3.56 (m, 24 H ,-CH-CH2-of N-vinyl in
IL and-N-CH2-N-),3.23(m,66 H,CH3-CH-CH3in NIPAAm),3.09(m,36 H,-N-CH2-CH2-N-and-
N-CH2-Ph-),2.75(m,2 H,SH-CH2-CH2-CH3), 2.41~2.61 (m, 12 H, CH3-CH-CH3ofiPrO-in Ti
(salen)),2.23(m,2 H,SH-CH2-CH2-CH3), 1.76~1.82 (m, 132 H ,-CH-CH2in NIPAAm),1.75
(s,3 H,SH-CH2-CH2-CH3), 1.41 (m, 48 H, cyclohexyl-H), 1.22~1.31 (m, 162 H, H-in t-
), butyl 1.01~1.12 (m, 469 H, CH3-CH-CH3iniPrO-and NIPAAm)；
PN64(IS)8:FT-IR(KBr):γmax/cm-13435,3302,3066,2974,2924,2860,1655,1535,
1455,1380,1365,1264,1174,1125,1054,967,924,882,839,806,709,634,625,507cm-1.1H
NMR(500 MHz,CD3Cl3): δ 8.11~7.62 (m, 16 H, CH=N), 7.13~7.67 (m, 32 H, ArH), 6.24~
6.87 (m, 64 H, HC-NH-C=O), 6.22 (m, 8 H, 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-CH3ofiPrO-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-CH3iniPrO-and NIPAAm)。
According to the method described above, a series of catalyst is prepared with different temperature sensing materials.
Embodiment 2
Reaction condition is optimized using aminomethyl phenyl thioether as model substrates, it is as a result as follows.
Reaction route:
The substrate (aminomethyl phenyl thioether) of 1mmol, the catalyst PN of 0.5mmol% are added in 10mL reaction flask68(IS)
4,1mL H2O makees solvent, under conditions of 25 DEG C, in the H that 1.2mmol 30% is slowly added dropwise in 15min2O2, the reaction was continued
45min.After reaction, catalyst is precipitated automatically, separates water phase, and catalyst is dried and reused after being washed with n-hexane,
Water phase obtains product after being extracted with dichloromethane, and product is carried out gas chromatographic analysis detection conversion ratio and selectivity, liquid phase
Chromatography obtains ee value, and column chromatography waits until product, calculated yield, and nuclear-magnetism, which characterizes, determines product structure.
Four kinds of comparative catalysts and tradition Salen Ti catalyst are used to be catalyzed aminomethyl phenyl sulfide oxidation into sulfoxide
Reaction, result are as shown in the table:
[a]Yield of the isolated product.[b]Determined by HPLC.
By table as it can be seen that the ratio of hydrophobe substituent group will affect catalytic effect, the variation of regularity is presented.PN68(IS)4It is
Most moderate hydrophobe the ratio, (PN when hydrophilic group is too long60(IS)2), activated centre just will be greatly reduced, and catalytic efficiency is lower than
PN68(IS)4(yield only has 75%).When hydrophobe ratio < 17, catalytic activity can also be reduced, (PN66(IS)6For 89%, PN64
(IS)8For 86%), and regularity variation is also presented in ee value.
Methyl phenyl sulfoxide, white solid, silica gel column chromatography separate (methanol: methylene chloride=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 measured (Agilent Co, HP19091G-B213,180 DEG C of column temperature, flow velocity: 1.6mL/min) by gas-chromatography,
Ee value measured by chiral high performance liquid chromatography (chromatographic column: Daicel chiralpak AD, mobile phase: isopropanol/
N-hexane=10:90 (volume ratio), flow velocity: 1.0mL/min, wavelength: 254nm, 25 DEG C of temperature).
Embodiment 3
Choose PN68(IS)4Carry out the examination of different substrates.
Reaction route:
Reaction step and processing mode embodiment 2 as above
By catalyst PN68(IS)4With traditional Salen Ti catalyst for being catalyzed other four kinds of sulfide oxidations into sulfoxide
Reaction, result are as shown in the table:
The catalyst PN it can be seen from table68(IS)4Catalytic effect be substantially better than the effect of traditional catalyst, in yield
There is big advantage in ee value.
The characterize data of portion of product is as follows:
4- Bromophenylmethyl sulfoxide, yellow solid, silica gel column chromatography separate (methanol: methylene chloride=20:80 (volume
Than)) (yield 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 measured by chiral high performance liquid chromatography (chromatographic column: Daicelchiralpak AD, mobile phase: isopropanol/just oneself
Alkane=50:50 (volume ratio), flow velocity: 1.0mL/min, wavelength: 254nm, 25 DEG C of temperature)
4- methoxyphenyl methyl sulfoxide, colourless liquid, silica gel column chromatography separate (methanol: methylene chloride=20:80 (body
Product ratio)) (yield 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 measures (chromatographic column: Daicel by chiral high performance liquid chromatography
Chiralpak AD, mobile phase: isopropanol/n-hexane=20:80 (volume ratio), flow velocity: 1.0mL/min, wavelength: 254nm, temperature
25 DEG C of degree)
4- nitrobenzophenone methyl sulfoxide, yellow solid, silica gel column chromatography separate (methanol: methylene chloride=20:80 (volume
Than)) (yield 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 measures (chromatographic column: Daicel chiralpak AD, mobile phase: isopropyl by chiral high performance liquid chromatography
Alcohol/n-hexane=30:70 (volume ratio), flow velocity: 1.0mL/min, wavelength: 254nm, 25 DEG C of temperature)
2- methoxyphenyl methyl sulfoxide, colourless liquid, silica gel column chromatography separate (methanol: methylene chloride=20:80 (body
Product ratio)) (yield 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 measures (chromatographic column: Daicel chiralpak AD, mobile phase: isopropanol/n-hexane=20:80 (volume
Than), flow velocity: 1.0mL/min, wavelength: 254nm, 25 DEG C of temperature)
Omeprazole, white powder, silica gel column chromatography separate (methanol: methylene chloride=20:80 (volume ratio)) (yield
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, mobile phase: isopropanol/n-hexane=20:80 is measured by chiral high performance liquid chromatography
(volume ratio), flow velocity: 1.0mL/min, wavelength: 254nm, 25 DEG C of temperature)
The Thermo-sensitive of the catalyst is embodied in, and after reaction, catalyst is precipitated from reaction system, when increasing temperature, is urged
Agent is precipitated completely and separates, and at room temperature, catalyst is dissolved in water, and when temperature increases, catalyst is just precipitated from water phase
Aggregation.Specific figure can be found out by transmission electron microscope.
Embodiment 4
The examination of catalyst repeat performance
By the solution after above-mentioned reaction by heating, catalyst can be precipitated from reaction system, using filtering, wash
It washs, dry, catalyst is used for next catalystic converter system, it is as shown in the table to reuse 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.The reaction system is all with water for reaction
Solvent, it is environmentally protective, method is provided for enterprise's mass production chiral sulphoxide sulfoxide.
Claims (8)
1. one kind is anti-based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether asymmetric oxidation
The method answered, it is characterised in that: in an aqueous medium, 2 structure sulfide compound of formula and hydrogen peroxide are in 1 structure temperature sensitive type ion of formula
It is chiral sub- to get 3 structure of formula that asymmetric oxidation reaction is carried out under the catalytic action of liquid chirality Salen Ti composition catalyst
Sulphones:
Wherein,
For n-isopropyl acrylamide polymer unit and/or N, N '-dimethyl acrylamide polymer list
Member；
X/Y is (1~100): 1；
R1、R2And R3Independently selected from hydrogen, C1~C5Alkyl, phenyl, the C containing phenyl substituent1~C5Alkyl or C1~C5's
Alkoxy；
R4ForN is 0~3；
R5For C1~C3Alkyl or hydrogen atom；
R6And R7Independently selected from: the C without substituent group6~C12Aryl, or contain halogen, C1~4Alkyl, C1~4Alkoxy, C2~5
The C of alkoxy carbonyl, nitro or cyano substituent6~C12Aryl；
Or without substituted C1~C6Alkyl, or the C containing aryl substituent1~C6Alkyl, or containing halogen, nitro, hydroxyl or
The C of cyano substituent1~C6Alkyl；OrIt is described to contain aryl substituent
C1~C6Alkyl in aryl substituent be the C without substituent group6~C12Aryl, or contain halogen, C1~4Alkyl, C1~4Alcoxyl
Base, C2~5The C of alkoxy carbonyl, nitro or cyano substituent6~C12Aryl.
2. according to claim 1 be based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis sulphur
The method of ether asymmetric oxidation reaction, it is characterised in that: R4ForN is 0~2；R5For hydrogen atom.
3. according to claim 1 be based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis sulphur
The method of ether asymmetric oxidation reaction, it is characterised in that: X/Y is (5~50): 1.
4. according to claim 1 be based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis sulphur
The method of ether asymmetric oxidation reaction, it is characterised in that: R6And R7Independently selected from a kind of in following substituent group:
5. according to any one of claims 1 to 4 be based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst
The method of aqueous catalysis thioether asymmetric oxidation reaction, it is characterised in that: hydrogenperoxide steam generator is slowly dropped to containing the sulphur
In the aqueous solution of ether compound and the temperature sensitive type ionic liquid chirality Salen Ti composition catalyst, asymmetric oxidation is carried out
Reaction.
6. according to claim 5 be based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis sulphur
The method of ether asymmetric oxidation reaction, it is characterised in that: the temperature sensitive type ionic liquid chirality Salen Ti composition catalyst
Molar ratio with the sulfide compound is 1:50~1:1000；
The molar ratio of hydrogen peroxide and the sulfide compound is 1:1~2:1 in the hydrogenperoxide steam generator；
The hydrogenperoxide steam generator concentration is 15wt%~70wt%.
7. according to any one of claims 1 to 4 be based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst
The method of aqueous catalysis thioether asymmetric oxidation reaction, it is characterised in that: the asymmetric oxidation reaction is -50 DEG C in temperature
Under the conditions of~50 DEG C, 0.1~5h is reacted.
8. according to claim 7 be based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis sulphur
The method of ether asymmetric oxidation reaction, it is characterised in that: after the completion of asymmetric oxidation reaction, reaction system is increased into temperature and is realized
The transformation of temperature sensitive type ionic liquid chirality Salen Ti composition catalyst hydrophilic-hydrophobic, it is chiral to be precipitated temperature sensitive type ionic liquid
Salen Ti composition catalyst is recovered by filtration rear reusable.
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