CN110479380A - A kind of temperature sensitive type chiral amino acid copper complex catalyst and preparation method thereof - Google Patents
A kind of temperature sensitive type chiral amino acid copper complex catalyst and preparation method thereof Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
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- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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Abstract
The present invention relates to chiral catalyst preparation fields more particularly to a kind of temperature sensitive type chiral amino acid copper complex catalyst and preparation method thereof.The preparation method of temperature sensitive type chiral amino acid copper complex catalyst designed by the present invention, comprising steps of (1) by chiral amino acid and acyl chloride reaction containing double bonds, so that introducing unsaturated carbon-carbon double bond on chiral amino acid obtains the chiral amino acids compound containing carbon-carbon double bond；(2) the chiral amino acids compound containing carbon-carbon double bond and n-isopropyl acrylamide are then subjected to polymerization reaction and obtain temperature sensitive type chiral amino acid block polymer；(3) last temperature sensitive type chiral amino acid block polymer carries out autofolding by coordination under the action of copper salt and forms temperature sensitive type chiral amino acid copper complex.The catalyst that the present invention obtains not only increases the catalysis reaction efficiency of asymmetry Henry addition reaction in pure water phase, and has recycling simply, the excellent feature of repeat performance.
Description
Technical field
The present invention relates to chiral catalyst preparation fields more particularly to a kind of temperature sensitive type chiral amino acid copper complex to be catalyzed
Agent and preparation method thereof.
Background technique
Chiral beta-nitro alcoholic compound is a kind of bifunctional compound, and purposes is very extensive.It obtains at present chiral single
β-nitroalcohol most efficient method be to be obtained by asymmetric catalysis, i.e., by nitroparaffins and aldehyde material in chirality
Asymmetry Henry addition reaction directly occurs under the action of catalyst, obtains chiral beta-nitro alcoholic compound, is applied to Henry
Asymmetric catalyst in reaction mainly has oxazoline class catalyst, chiral diamine class catalyst, Schiff class catalyst, life
Alkaloids complex catalyst etc..
2002, Denmark chemist(C.Christensen,K.Juhl,R.G.Hazell and K.The Journal of Organic Chemistry2002,67,4875-4881.) use is reported for the first time
Double complex-catalyzed Henry reactions of oxazoline class, and achieve preferable catalytic effect.
2003, (D.A.Evans, D.Seidel, M.Rueping, et al., Journal of the such as Evans
American Chemical Society2003,125,12692-12693.) the double oxazoline ligands of several classes are prepared, using gold
Belong to compound Cu (OAc)2Obtain catalyst with chiral oxazoline ligand complexes ira situ, by such catalyst be used for nitromethane and
In the Henry asymmetric reduction reaction of benzaldehydes substance, solvent is done with methanol and shows preferable catalytic performance.But catalyst
It is difficult to recycle and reuse.
2016, (S.Samadi, K.Jadidi, B.Khanmohammadi, et al., the Journal of such as Samadi
Catalysis2016,340,344-353.) by the way that monosubstituted oxazolyl quinoline is immobilized to preparing a kind of chiral monosubstituted oxazolyl quinoline on MCM-41
Heterogeneous catalyst, and be coordinated using Ni metal atom and the nitrogen-atoms on oxazoline ring, prepare a metalloid corrdination type
Heterogeneous catalyst.The catalyst effect is good, but is reacted in organic solvent, and environmental pollution is easily led to.
In conclusion applied to the catalyst of Henry asymmetric reduction reaction, there are aqueous catalysis low efficiencys, catalysis at present
The problem of agent difficulty recycles.
Summary of the invention
In order to solve problem above, the object of the present invention is to provide a kind of temperature sensitive type chiral amino acid copper complex catalyst
And preparation method thereof, it is not right in pure water phase that the temperature sensitive type chiral amino acid copper complex catalyst that the present invention obtains not only increases
Claim the catalysis reaction efficiency of Henry addition reaction, and there is recycling simply, the excellent feature of repeat performance.
To achieve the above object, the temperature sensitive type chiral amino acid copper complex catalyst designed by the present invention, feature exist
In, be general formula (1) compound:
In formula (1):
* R configuration or S configuration are indicated；
R1、R2Independently selected from for hydrogen, alkyl, aryl, aryl substituted alkyl；
R3Selected from hydrogen atom or alkyl group；
R4Selected from C1~C16Alkyl, isopropyl, isobutyl group, tert-butyl, benzyl or substituted aryl；
X:Y is (1~100): 1.
Preferably, X:Y is (5~50): 1.
Preferably, the R3Selected from hydrogen atom or methyl；The R4Selected from methyl, ethyl, phenyl.
The preparation method of temperature sensitive type chiral amino acid copper complex catalyst designed by the present invention, comprising steps of
(1) by the chiral amino acid of R configuration or S configuration and the acyl chloride reaction containing carbon-carbon double bond, thus in chiral ammonia
Unsaturated carbon-carbon double bond is introduced on base acid obtains the chiral amino acids compound containing carbon-carbon double bond；
(2) then the chiral amino acids compound containing carbon-carbon double bond polymerize instead with n-isopropyl acrylamide
It should obtain temperature sensitive type chiral amino acid block polymer；
(3) last temperature sensitive type chiral amino acid block polymer is carried out certainly under the action of copper salt by coordination
Folding forms temperature sensitive type chiral amino acid copper complex.
Preferably, optical pure compound structure of the chiral amino acid with general formula (2) in the step (1)；Contain
There is the acyl chlorides of carbon-carbon double bond that there is the structure of general formula (3)；Chiral amino acids compound containing carbon-carbon double bond has general formula (4)
Structure；
In formula (2), R4Selected from C1~C16Alkyl, isopropyl, isobutyl group, tert-butyl, benzyl or substituted aryl etc., *
Indicate R configuration or S configuration；
In formula (3), R3Selected from hydrogen atom or alkyl group；
The reaction equation of chiral amino acid and the acyl chlorides containing carbon-carbon double bond are as follows:
Preferably, in the step (2), the above-mentioned chiral amino acids compound Y containing carbon-carbon double bond is taken
Mmol and temperature sensing material n-isopropyl acrylamide (NIPAAm) X mmol is reaction monomers, poly- using controllable-fracture chain tra nsfer
Legal (RAFT) method, with azodiisobutyronitrile (AIBN) for chain initiator, carbon thioesters is as molecular weight regulator in organic solvent
Middle carry out controllable polymerization, keep polymerization system reaction temperature be 60~70 DEG C between reaction 12~for 24 hours；After reaction, it removes
Organic solvent, precipitation agent, which is added, is precipitated polymerizate, and vacuum drying obtains puffy temperature sensitive type chiral amino acid block polymerization
Object PNxAy；Carbon thioesters is molecular weight regulator, can effectively control the molecular weight of reaction product, meanwhile, according to two kinds of lists of addition
The difference of body ratio, can effectively adjust the structure and ratio of polymer, thus obtain molecular weight, structure, morphology controllable it is temperature sensitive
Type chiral amino acid block polymer.
Wherein, n-isopropyl acrylamide has the structure of general formula (5)；Carbon thioesters has the structure of general formula (6)；Temperature sensitive type
Chiral amino acid block polymer PNxAy has the structure of general formula (7)；
R1、R2Separately be selected from is hydrogen, alkyl, aryl, aryl substituted alkyl；
X:Y is (1~100): 1.
Controllably-fracture chain transfer polymerization method (RAFT) method synthesis temperature sensitive type block polymer PNxAy reaction equation are as follows:
Preferably, in the step (3), puffy temperature sensitive type block polymer PNxAy is dissolved in organic solvent
In, mantoquita is added and is coordinated, single-stranded folding occurs under the coordination of metal for temperature sensitive type block polymer PNxAy, is formed
Temperature sensitive type chiral amino acid copper complex catalyst CuII-PNxAy。
Preferably, the mantoquita is one of copper acetate, nitric acid ketone, copper chloride, copper sulphate.
Preferably, the X:Y is (5~50): 1.
The present invention has the advantages that compared with tradition has general formula (11) structure catalyst, Cu of the inventionII- PNxAy is urged
Agent has had the advantage that:
(1) Cu of the inventionII- PNxAy catalyst can be used in pure water phase having in asymmetry Henry addition reaction system
Mass transfer is difficult in water for the traditional catalyst that solves of effect, the low problem of catalytic efficiency.
(2) Cu of the inventionII- PNxAy catalyst can form nano-reactor in water phase, and water-wet side is dissolved in water, hydrophobic
End forms activated centre aggregation, greatly improves catalysis reaction efficiency, obtains the chirality of high selectivity and enantio-selectivity
Product.
(3) pass through control reaction temperature, CuII- PNxAy catalyst can realize hydrophilic and hydrophobic conversion, utilize CuII-
Cu can be realized by improving reaction temperature in PNxAy hydrophobe-hydrophile conversion performanceIIThe recycling of-PNxAy catalyst；And this
The Cu of inventionIIRepeat performance is excellent after the recycling of-PNxAy catalyst.
In addition, Cu of the present inventionII- PNxAy catalyst during the preparation process, does not add any acid-base material, will not destroy hand
The activated centre of acidic amino acid, and synthesis material is from a wealth of sources, and synthetic method is simple, and safe operation, process conditions are mild, has
Conducive to large-scale industrial production.
Detailed description of the invention
Fig. 1 is CuII-PN50A5Transmission electron microscope (TEM) figure (20 times) in aqueous solution；
Fig. 2 is CuII-PN50A5Transmission electron microscope (TEM) figure (200 times) in aqueous solution；
Fig. 3 is catalyst CuII-PN50A5Dynamic light scattering in aqueous solution characterizes (DLS) figure.
Specific embodiment
For a better understanding of the invention, invention is described in detail below with reference to drawings and concrete examples.
It uses and writes a Chinese character in simplified form below: n-isopropyl acrylamide (NIPAAm), azodiisobutyronitrile (AIBN), temperature sensitive type chirality ammonia
Base acid block polymer (PN50A5), temperature sensitive type chiral amino acid copper complex catalyst (CuII-PN50A5)。
Embodiment 1
CuII-PN50A5Preparation method, comprising steps of
(1) synthesis of the chiral amino acids compound containing carbon-carbon double bond
Reaction equation 1
In above-mentioned reaction equation 1, R3For hydrogen atom, R4For benzyl.
Specific operation process is L-phenylalanine 10mmol to be added in the three-necked flask dry to 100mL, and add thereto
Enter anhydrous methylene chloride 20mL, triethylamine 11mmol, reaction flask is placed in magnetic agitation in ice-water bath, is cooled to 0 to reaction solution
After DEG C, in 30mL is slowly added dropwise in 30min thereto dissolved with the dichloromethane solution of acryloyl chloride (11mmol).It is added dropwise
Afterwards, when emerging in solution without steam, reaction temperature is slowly increased to room temperature, the reaction was continued 2~8h.After reaction, to anti-
It answers and adds 10mL saturation NH in liquid4Cl solution, CH2Cl2(2 × 5ml) aqueous layer extracted, organic layer are saturated NaHCO with 30mL3Washing,
Na2SO4Dry organic phase, is concentrated to get faint yellow oil product.Column chromatography (ethyl acetate/n-hexane=1:1) obtains target
Product.FT-IR(KBr):γmax/cm-1:3283,3063,3030,2959,2926,2855,1732,1659,1632,1543,
1501,1452,1406,1316,1296,1268,1191,1126,1066,1031,986,965,915,849,814,748,
700,668,605,576,516,489。
(2)PN50A5Synthesis
Reaction equation 2
Temperature sensitive type chiral amino acid block polymer is prepared with controllable-fragmentation chain transfer free radical polymerization method (RAFT).Point
NIPAAm (50mmol) and the above-mentioned chiral amino acids compound (5mmol) containing carbon-carbon double bond prepared is not taken to be dissolved in nothing
It in water methanol, transfers the solution into Schlenk pipe, propane thioic acid Bian ester (chain-transferring agent, 1/6mmol, 0.0330g) and AIBN
(chain initiator, 1/30mmol, 0.0052g) is added in reaction solution.N2Under protection, 60 DEG C of reactions are placed reaction liquid into for 24 hours, instead
After answering, it is concentrated in vacuo reaction solution, precipitating reagent processing reaction solution is done using more times of excess diethyl ethers, obtains faint yellow solid production
Object, 30 DEG C of vacuum drying, obtains puffy temperature sensitive type chiral amino acid block polymer PN50A5。
(3)CuII-PN50A5Synthesis
Take the PN of the above-mentioned preparation of 4mmol50A5, it is dissolved in 30mL dehydrated alcohol/ethyl acetate, and 2mmol is added thereto
Copper sulphate, back flow reaction is for 24 hours.After reaction, it is spin-dried for solvent, 2mLTHF dissolution is added thereto, then anti-with 3 × 50mL ether
Multiple precipitating obtains blue solid and precipitates, and at 30 DEG C, vacuum drying obtains CuII-PN50A5.To CuII-PN50A5Accordingly characterized
FT-IR(KBr):γmax/cm-1 3423,3062,2965,2930,2875,1728,1614,1556,1454,1395,1336,
1272,1174,1135,1105,1044,1016,924,836,675,617,558,511,452cm-1.α25 D=-73.4 (C=
0.005g mL-1,CH2Cl2)。
Embodiment 2
The Cu that embodiment 1 is obtainedII-PN50A5For being catalyzed Henry addition reaction；I.e. in an aqueous medium, aldehyde compound
With nitroparaffins in CuII-PN50A5Asymmetry Henry addition reaction is carried out under the catalytic action of catalyst, obtains β-nitro alcohol compound
Object.
Aldehyde compound has the structure of general formula (8)；Nitroparaffins have the structure of general formula (9)；β-nitro alcoholic compound
Structure with general formula (10).
R5- CHO formula (8)
R6-NO2Formula (9)
Reaction equation 3
Aldehyde compound is benzaldehyde in the present embodiment, and nitroparaffins are nitromethane, and specific catalytic process is In
The catalyst Cu of 0.5mmol% is added in 10mL reaction flaskII-PN50A5, 1mL H2O catalyst-solvent, is then added thereto
The substrate (benzaldehyde) and 3mmol nitromethane of 1mmol is stirred to react under conditions of 25 DEG C.Thin-layered chromatography real time monitoring is anti-
It answers, catalyst is precipitated automatically to after reaction, increase temperature of reaction system, separates water phase, catalyst is washed with n-hexane
It dries and reuses afterwards, water phase obtains product after being extracted with dichloromethane, and product is carried out liquid-phase chromatographic analysis detection and is turned
The enantio-selectivity of rate and selectivity and product, column chromatography wait until product, and calculated yield, nuclear-magnetism characterization, which determines, to be produced
Object structure.Obtain the characterize data of product are as follows: (R) -2- nitro -1- (4- nitrobenzophenone) alcohol: white solid, silica gel column chromatography point
From (ethyl alcohol: n-hexane=85:15 (volume ratio)), (98% yield, 99%ee).Product structure characterization: IR (film) 3508,
2921,2851,1552,1515,1416,1379,1347,1080,855cm-1；1H NMR(400MHz,CDCl3)8.31-8.27
(m, 2H, ArH), 7.65-7.63 (m, 2H, ArH), 5.62 (dt, 1H, J=8.0,4.0Hz, CHOH), 4.65-4.55 (m, 2H,
CH2NO2), 3.09 (d, J=4.0Hz, OH)；13C NMR(100MHz,CDCl3)148.0,145.0,126.9,124.1,80.6,
69.9.Ee value measured by chiral high performance liquid chromatography (chromatographic column: Daicel chiralpak AD, mobile phase: isopropanol/just oneself
Alkane=15:85 (volume ratio), flow velocity: 0.8mL/min, wavelength: 215nm, 25 DEG C of temperature).
The Cu that the present embodiment 1 is obtainedII-PN50A5It is compared with traditional catalyst for being catalyzed Henry addition reaction,
Its result is as shown in table 1 below:
Table 1
Traditional catalyst has the structure of general formula (11) in table 1:
R is other amino acid substitution groups such as methyl, carboxyl, phenyl, chain alkyl.
Seen from table 1, it is poor to be catalyzed Henry asymmetric reduction reaction effect in water for copper salt copper acetate, due to reaction
Substrate is all organic matter, therefore mantoquita is difficult to contact with organic substrates and causes catalytic effect poor.Traditional catalyst indissoluble solution in water,
But it is good compared with copper acetate that organic catalyst is contacted with organic substrates, thus react 48 hours, yield 35%, enantio-selectivity compared with
It is low.As use temperature sensitive type chiral amino acid copper catalyst CuII-PN50A5When reaction, due to catalyst have in water it is good molten
Xie Xing, and catalyst can be acted in water by hydrophobe and metal coordination carries out being self-assembly of nano-reactor, it will
Organic reaction substrate is wrapped up into inside hydrophobic cavity, and reaction substrate can be concentrated, and increases effective collision number, accelerates reaction speed,
Completion can be reacted within final 18 hours, yield is up to 98%, and enantio-selectivity is up to 99%.
Embodiment 3
The temperature sensitive type chiral amino acid copper complex catalyst Cu that embodiment 1 is obtainedII-PN50A5Different substrates are urged
Change effect.
By catalyst CuII-PN50A5With nontraditional amino acid copper catalyst for being catalyzed other aldehyde compounds and nitroparaffins
Reaction, result is as shown in table 2 below:
Table 2
18h, catalyst Cu are reacted it can be seen from tableII-PN50A5Catalytic effect be substantially better than the effect of traditional catalyst
Fruit has big advantage on yield and ee value.Such catalyst is shown very in water phase Henry asymmetric reduction reaction
Good catalytic effect can solve the problems, such as that aqueous phase reactions mass transfer is difficult in industry.
The characterize data of portion of product is as follows:
(R) -1- phenyl -2- nitroalcohol: colorless oil, silica gel column chromatography separate (ethyl alcohol: methylene chloride=90:10 (volume
Than)), (68% yield, 87%ee).Product structure characterization: IR (film) 3542,3033,2920,1688,1555,1494,
1454,1418,1379,1288,1201,1066,894,765,700,508cm-1；1H NMR(400MHz,CDCl3)7.42-
7.35 (m, 5H, ArH), 5.45-5.42 (m, 1H, CHOH), 4.54-4.49 (dd, 1H, J=13.2,9.8Hz, CH2NO2),
4.43-4.40 (dd, 1H, J=13.2,2.9Hz, CH2NO2), 2.96 (d, 1H, J=3.9Hz, OH)；13C NMR(125MHz,
CDCl3)138.3,129.3,129.2,126.2,81.4,71.2；Ee value measured by chiral high performance liquid chromatography (chromatographic column:
Daicel chiralpak AD, mobile phase: isopropanol/n-hexane=15:85 (volume ratio), flow velocity: 0.8mL/min, wavelength:
215nm, 25 DEG C of temperature).
(R) -1- (4- bromophenyl) -2- nitroalcohol: colorless oil, silica gel column chromatography separation (ethyl alcohol: methylene chloride=90:
10 (volume ratios)), (76% yield, 85%ee).Product structure characterization: IR (film) 3527,2921,1596,1556,1493,
1414,1379,1343,1296,1210,1192,1090,1014,896,829,740,661,526cm-1；1H NMR(500MHz,
CDCl3) 7.38-7.32 (m, 4H, ArH), 5.44-5.41 (m, 1H, CHOH), 4.56 (dd, 1H, J=13.3,9.5Hz,
CH2NO2), 4.48 (dd, 1H, J=13.3,2.9, CH2NO2),3.14(d,1H,4.0Hz,OH)；13C NMR(125MHz,
CDCl3) 136.5,134.7,129.1,127.3,80.9,70.2, ee value measured by chiral high performance liquid chromatography (chromatographic column:
Daicel chiralpak AD, mobile phase: isopropanol/n-hexane=15:85 (volume ratio), flow velocity: 0.8mL/min, wavelength:
215nm, 25 DEG C of temperature).
(R) -1- (4- cyano-phenyl) -2- nitroalcohol: colorless oil, silica gel column chromatography separation (ethyl alcohol: methylene chloride=
90:10 (volume ratio)), (87% yield, 92%ee).Product structure characterization: IR (film) 3527,2921,1597,1555,
1496,1416,1377,1342,1294,1013,895,825,743,664,526cm-1；1H NMR(500MHz,CDCl3)
7.38-7.32 (m, 4H, ArH), 5.51-5.55 (m, 1H, CHOH), 4.53-4.56 (dd, 2H, J=13.3,9.5Hz,
CH2NO2),3.25(d,1H,4.0Hz,OH)；13C NMR(125MHz,CDCl3)143.2,132.3,126.6,118.3,112.4,
78.1,70.3, ee values measure (chromatographic column: Daicel chiralpak AD, mobile phase: isopropyl by chiral high performance liquid chromatography
Alcohol/n-hexane=15:85 (volume ratio), flow velocity: 0.8mL/min, wavelength: 215nm, 25 DEG C of temperature).
(R) -1- (2- nitrobenzophenone) -2- nitroalcohol: brown crystal, silica gel column chromatography separation (ethyl alcohol: n-hexane=80:
20 (volume ratios)), (93% yield, 99%ee).Product structure characterization: IR (film) 3541,1548,1532,1410,1365,
1354,1093,1071,865cm-1；1H NMR(500MHz,CDCl3)8.11-8.08(m,1H,ArH),7.98-7.96(m,1H,
), ArH 7.78-7.74 (m, 1H, ArH), 7.59-7.55 (m, 1H, ArH), 6.07 (ddd, 1H, J=8.8,4.2,2.2Hz,
), CHOH 4.89 (dd, 1H, J=13.9,2.2Hz, CH2NO2), 4.57 (dd, 1H, J=13.9,8.8Hz, CH2NO2),3.15
(d,1H,4.2Hz,OH)；13C NMR(100MHz,CDCl3)147.1,134.4,133.9,129.7,128.7,125.0,
80.0,66.8, ee values measure (chromatographic column: Daicel chiralpak AD, mobile phase: isopropyl by chiral high performance liquid chromatography
Alcohol/n-hexane=10:90 (volume ratio), flow velocity: 0.8mL/min, wavelength: 215nm, 25 DEG C of temperature).
(R) -1- (2- chlorphenyl) -2- nitroalcohol: brown crystal, silica gel column chromatography separate (ethyl alcohol: n-hexane=80:20
(volume ratio)), (69% yield, 90%ee).Product structure characterization: IR (film) 3531,1556,1493,1414,1379,
1296,1210,1090,1014,896,829,740,661,530cm-1；1H NMR(500MHz,CDCl3) 7.64 (dd, 1H J=
8.0,2.0Hz,ArH),7.37-7.32(m,2H,ArH),7.30-7.27(m,1H,ArH),5.84-5.81(m,1H,CHOH),
4.65 (dd, 1H, J=13.7,2.4Hz, CH2NO2), 4.43 (dd, 1H, J=13.7,9.8Hz, CH2NO2),3.01(d,1H,
4.4Hz,OH)；13C NMR(125MHz,CDCl3)135.4,131.4,129.9,129.7,127.6,127.5,79.2,67.8,
Ee value measured by chiral high performance liquid chromatography (chromatographic column: Daicel chiralpak AD, mobile phase: isopropanol/n-hexane=
3:97 (volume ratio), flow velocity: 0.8mL/min, wavelength: 215nm, 25 DEG C of temperature).
(R) -1- (2- aminomethyl phenyl) -2- nitroalcohol: brown crystal, silica gel column chromatography separation (ethyl alcohol: n-hexane=80:
20 (volume ratios)), (50% yield, 87%ee).Product structure characterization: IR (film) 3522,3444,3033,2911,1688,
1550,1483,1461,1411,1378,1286,1208,1069,895,762,730,616cm-1；1H NMR(500MHz,
CDCl3)7.51-7.49(m,1H,ArH),7.27-7.25(m,2H,ArH),7.19-7.18(m,1H,ArH),5.66-5.64
(m, 1H, CHOH), 4.54-4.49 (dd, 1H, J=13.2,9.8Hz, CH2NO2), 4.43-4.40 (dd, 1H, J=13.2,
2.4Hz,CH2NO2),2.97(s,1H,OH),2.38(s,3H,CH3)；13C NMR(125MHz,CDCl3)136.5,134.7,
131.1,128.9,127.0,125.8,80.4,68.1；19.1, ee values measured by chiral high performance liquid chromatography (chromatographic column:
Daicel chiralpak AD, mobile phase: isopropanol/n-hexane=15:85 (volume ratio), flow velocity: 0.8mL/min, wavelength:
215nm, 25 DEG C of temperature).
Embodiment 4
Catalyst CuII-PN50A5The experiment of repeat performance
Solution after reaction is warming up to 35 DEG C, catalyst CuII-PN50A5It can be precipitated from reaction system, using mistake
Filter, wash, drying and etc., catalyst is used for next catalystic converter system, it is as shown in table 3 below to reuse effect:
Table 3
From the above data, it can be seen that the reusability of catalyst is preferable.The reaction system is molten for reaction with water
The environmentally protective technique of agent can provide the route an of economy, environmental protection for the industrial nitroalcohol that generates, solve industrial processes
Middle problem of environmental pollution.
And as can be seen that catalyst can form the particle of nanometer spherical in water from Fig. 1 and Fig. 2, uniform particle,
Form is single.When the aqueous temperature of catalyst is increased to 35 DEG C, catalyst will show hydrophobicity and reunite together, after
And be precipitated from water phase, reach the effect of " room temperature efficient catalytic, heat up simple and direct separation ", realizes simple recycling and the height of catalyst
Effect repeats.From figure 3, it can be seen that catalyst can form the particle of ball shaped nano in water, particle size is about 13nm, and
PDI is only 0.104, shows that Nanoparticle Size is uniform, form is single.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of temperature sensitive type chiral amino acid copper complex catalyst, which is characterized in that it is the compound of general formula (1):
In formula (1):
* R configuration or S configuration are indicated；
R1、R2Independently selected from for hydrogen, alkyl, aryl, aryl substituted alkyl；
R3Selected from hydrogen atom or alkyl group；
R4Selected from C1~C16Alkyl, isopropyl, isobutyl group, tert-butyl, benzyl or substituted aryl；
X:Y is (1~100): 1.
2. temperature sensitive type chiral amino acid copper complex catalyst according to claim 1, which is characterized in that the X:Y is
(5~50): 1.
3. temperature sensitive type chiral amino acid copper complex catalyst according to claim 1, which is characterized in that the R3It is selected from
Hydrogen atom or alkyl group；The R4Selected from methyl, ethyl, phenyl.
4. a kind of preparation method of temperature sensitive type chiral amino acid copper complex catalyst, which is characterized in that comprising steps of
(1) by the chiral amino acid of R configuration or S configuration and acyl chloride reaction containing double bonds, to draw on chiral amino acid
Enter unsaturated carbon-carbon double bond and obtains the chiral amino acids compound containing carbon-carbon double bond；
(2) the chiral amino acids compound containing carbon-carbon double bond is then carried out polymerization reaction with n-isopropyl acrylamide to obtain
To temperature sensitive type chiral amino acid block polymer；
(3) last temperature sensitive type chiral amino acid block polymer is under the action of mantoquita by matching
Position effect carries out autofolding and forms temperature sensitive type chiral amino acid copper complex catalyst.
5. the preparation method of temperature sensitive type chiral amino acid copper complex catalyst according to claim 4, which is characterized in that
Chiral amino acid has the optical pure compound structure of general formula (2) in the step (1)；Acyl chlorides containing carbon-carbon double bond has logical
The structure of formula (3)；Chiral amino acids compound containing carbon-carbon double bond has the structure of general formula (4)；
In formula (2), R4Selected from C1~C16Alkyl, isopropyl, isobutyl group, tert-butyl, benzyl or substituted aryl etc., * indicates R
Configuration or S configuration；
In formula (3), R3Selected from hydrogen atom or alkyl group.
6. the preparation method of temperature sensitive type chiral amino acid copper complex catalyst according to claim 4, which is characterized in that
In the step (2), above-mentioned chiral amino acids compound Y mmol and temperature sensing material N- isopropyl containing carbon-carbon double bond is taken
Acrylamide (NIPAAm) X mmol is reaction monomers, and X:Y is (1~100): 1；Using controllable-fracture chain transfer polymerization method
(RAFT) method, with azodiisobutyronitrile (AIBN) be chain initiator, carbon thioesters as molecular weight regulator in organic solvent into
Row controllable polymerization, keep polymerization system reaction temperature be 60~70 DEG C between reaction 12~for 24 hours；After reaction, it removes organic
Solvent, precipitation agent, which is added, is precipitated polymerizate, and vacuum drying obtains puffy temperature sensitive type chiral amino acid block polymer
PNxAy；
Wherein, n-isopropyl acrylamide has the structure of general formula (5)；Carbon thioesters has the structure of general formula (6)；Temperature sensitive type is chiral
Amino acid block polymer PNxAy has the structure of general formula (7)；
R1、R2Separately be selected from is hydrogen, alkyl, aryl, aryl substituted alkyl.
7. the preparation method of temperature sensitive type chiral amino acid copper complex catalyst according to claim 4, which is characterized in that
In the step (3), puffy temperature sensitive type block polymer PNxAy is dissolved in organic solvent, mantoquita is added and is coordinated, temperature
Single-stranded folding occurs under the coordination of metal for quick type block polymer PNxAy, forms the cooperation of temperature sensitive type chiral amino acid copper
Object catalyst CuII-PNxAy。
8. the preparation method of temperature sensitive type chiral amino acid copper complex catalyst according to claim 7, which is characterized in that
The mantoquita is one of copper acetate, nitric acid ketone, copper chloride, copper sulphate.
9. the preparation method of temperature sensitive type chiral amino acid copper complex catalyst according to claim 6, which is characterized in that
The X:Y is (5~50): 1.
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