CN102872914A - Chiral double-oxazoline amino metal catalyst, as well as preparation method and application thereof - Google Patents

Chiral double-oxazoline amino metal catalyst, as well as preparation method and application thereof Download PDF

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CN102872914A
CN102872914A CN2012103510083A CN201210351008A CN102872914A CN 102872914 A CN102872914 A CN 102872914A CN 2012103510083 A CN2012103510083 A CN 2012103510083A CN 201210351008 A CN201210351008 A CN 201210351008A CN 102872914 A CN102872914 A CN 102872914A
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catalyst
amido
bisoxazoline
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CN102872914B (en
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李晓芳
刘慧�
刘战雄
贺剑云
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Beijing Institute of Technology BIT
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Abstract

The invention discloses a chiral double-oxazoline amino metal catalyst, as well as a preparation method and application thereof and belongs to the technical field of catalysts. The structural formula of the catalyst is as follows: wherein n represents the number of R2 connected with a center metal M, R1 is CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, C(CH3)3, CH2CH(CH3)2, CH2Ph or Ph; R2 is CH2SiMe3, CH(SiMe3)2, CH2-(2,6-iPr2-C6H3), CH2CHCH2, MeCHCHCH2, CH2CPhCH2, CH2CMeCH2, CH2C6H4NMe2-O, CH2C6H4OMe-O or C1. The method is simple and is low in cost; the selectivity of the obtained polymer is trans-1,4-99.9 percent; and the activity is high and the application range is wide.

Description

A kind of Shou bisoxazoline amido metallic catalyst, preparation method and application
Technical field
The present invention relates to a kind of Shou bisoxazoline amido (NNN) metallic catalyst, preparation method and application, be particularly related to hand bisoxazoline amido (NNN) metallic catalyst, preparation method and the application aspect organic molecule and macromolecule thereof, belong to catalyst technical field.
Background technology
The Pincer part refers to contain the symmetry cheland of tridentate ligand, is widely used in the Organometallic Chemistry research field.1976, Moulton and Shaw synthesized first case Pincer part first, i.e. negative monovalence PCP part.Wherein, in the middle of carbanion was positioned at, two phosphorus atoms were positioned at both sides.Yet two phosphorus structures of its novelty were not attracting much attention at that time.Until the eighties, people redeterminate its character, find that it has good heat endurance to metallo-organic compound, so that it is used widely in homogeneous catalysis.Along with the further investigation to the PCP part, it uses the nano science field that extends to gradually chemical sensor and chemical converter.Subsequently, people are with the sulphur atom in the thioether, and tertiary amine is incorporated into the position of phosphorus atoms or the position that the nitrogen-atoms in the pyridine is incorporated into central carbon atom, form SCS, NCN, SNS, PNP, the Pincer part of the configurations such as PCN.These Pincer parts can with rare earth or transition-metal coordination, obtain the metallo-organic compound of different structure.The fact shows that the metallo-organic compound that contains the Pincer part can be used as olefin polymerization catalysis and promotes Polymer Synthesizing.For example the metallo-organic compound centered by main group, rare earth and transition metal is at multiple alkene such as ethene, alpha-olefin, and 1,3-butadiene shows fine catalytic activity and stereoselectivity in the reaction of the polymerized coordinations such as isoprene.Such metallo-organic compound also organic molecule reaction as: the henry reaction, the heck reaction, the Suzuki-Miyaura coupling, the dehydrogenation reaction of alkane, hydrogen transfer reaction, aldol reaction, asymmetric allylic alkylation shows good catalytic activity in Friedel-Crafts alkylation and the c h bond priming reaction.In these traditional organic reactions, the Pincer part that the Pincer part especially contains chiral radicals can significantly increase the stability of metal center, improves functional group's tolerance of substrate, improves the selective of reaction.
The chirality Pincer part of report only has NON at present, NSN, the NNN type, and these chiralitys Pincer part does not form metallo-organic compound with all transition metal or rare earth metal, although these are take selective certain as the metallo-organic compounds that support can both show of chirality Pincer part, but but do not reach the directed effect of selecting, can't be applied to traditional organic reaction.Especially present catalyst obtains trans-1 to isoprene polymerization, 4 polyisoprene selectively not high enough, activity is also lower.
Summary of the invention
For prior art exist selectively not high enough, range of application is wide not, especially present catalyst obtains trans-1 to isoprene polymerization, selectively not high enough, the active also lower defective of 4 polyisoprene, the object of the present invention is to provide a kind of Shou bisoxazoline amido (NNN) metallic catalyst, preparation method and application, method for preparing catalyst of the present invention is simple, and is cheap; The polymer that obtains selectively all is 99.9%, and is active high, applied range.
Purpose of the present invention is realized by following technical scheme:
A kind of Shou bisoxazoline amido (NNN) metallic catalyst, described catalyst structure formula is as follows:
Figure BDA00002162940700021
Wherein, n represents the R that links to each other with central metal M 2Quantity, R 1Be CH 3, CH 2CH 3, CH 2CH 2CH 3, CH (CH 3) 2, C (CH 3) 3, CH 2CH (CH 3) 2, CH 2Ph or Ph; R 2Be CH 2SiMe 3, CH (SiMe 3) 2, CH 2-(2,6- iPr 2-C 6H 3), CH 2CHCH 2, MeCHCHCH 2, CH 2CPhCH 2, CH 2CMeCH 2, CH 2C 6H 4NMe 2-o, CH 2C 6H 4OMe-o or Cl; Ph is phenyl, and Me is methyl, iPr is isopropyl, and o represents the ortho position;
(1) as M=Sc, Y, Lu, Yb, Tm, Er, Ho, Dy, Tb, Gd, Eu, Sm, Pm, Nd, Pr, Ce or La, and M is when being positive trivalent; N=2;
(2) work as M=Hf, when Ti or Zr, be divided into two kinds of situations:
The first, when M is positive tetravalence, n=3;
The second, when M is positive trivalent, n=2;
(3) work as M=Au, Cr, Rh, during Ir, and M is when being positive trivalent, n=2;
(4) work as M=Pd, when M is positive divalence, n=1.
The preparation method of Shou bisoxazoline amido of the present invention (NNN) metallic catalyst is as follows:
Method one
1. in the environment of anhydrous and oxygen-free with M (R 2) nJoin in the reactor with the oxolane of anhydrous and oxygen-free, make M (R 2) n is dissolved in the oxolane fully;
2. will be suc as formula the oxolane dissolving of Shou bisoxazoline amido (NNN) part shown in the I with anhydrous and oxygen-free in the environment of anhydrous and oxygen-free, then dropwise be added drop-wise in the reactor of step in 1., make Shou bisoxazoline amido (NNN) part and M (R 2) nReaction can stop reaction until reaction solution becomes claret by yellow;
3. reaction is removed oxolane after finishing, and with the solid n-hexane dissolution that obtains, and insoluble matter is removed by filter rear recrystallization, can obtain suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II;
Wherein, thf is oxolane; Shou bisoxazoline amido (NNN) part and the M (R of step described in 2. 2) nThe ratio of amount of substance be 1:1.
Figure BDA00002162940700031
Method two
1. under≤35 ° of C, will join in the reactor suc as formula Shou bisoxazoline amido (NNN) part and the ether shown in the I, and make Shou bisoxazoline amido (NNN) part be dissolved in the ether fully;
2. the n-butyllithium solution that with concentration is 2.5mol/L dropwise joins in the step reactor 1., until the color of the solution yellowing stops to drip in the reactor, desolventizing is dissolved in the grease that obtains in the toluene, obtains solution;
3. with M (Cl 2) after n is dissolved in toluene, dropwise join in the solution that 2. step obtain, be stirred to solution and be Chinese red, and have precipitation to occur, remove precipitation, and after the solvent in the solution that obtains removed, normal temperature spent the night.
4. with R 2Li joins in the solution of generation, reacts desolventizing after 2 hours, obtains the peony viscous mixture, and washing is filtered, and obtains yellow solution, drain light yellow solid namely shown in formula III hand bisoxazoline amido (NNN) metallic catalyst;
Wherein, M (R 2) ratio of amount of substance of n and Shou bisoxazoline amido (NNN) part is 1:1.
Figure BDA00002162940700032
Figure BDA00002162940700041
The application of bisoxazoline amido of the present invention (NNN) metallic catalyst is as follows:
(1) as the catalyst for preparing (S)-3-indyl-3-phenyl alcohol or pyrimido indolone;
(2) as the catalyst of isoprene, 1,3-butadiene self-polymeric reaction;
(3) as the catalyst of ethene self-polymeric reaction;
Wherein, co-catalyst is fluoro borate or alkyl aluminum, is preferably [Ph 3C] [B (C 6F 5) 4], [PhNHMe 2] [B (C 6F 5) 4], B (C 6F 5) 3, Al iBu 3Or MAO (=MAO), Ph is phenyl, Me is methyl, iBu represents isobutyl group.
Beneficial effect
Catalyst of the present invention is non-metallocene rare earth and transition metal organic catalyst, and the preparation method of described catalyst is simple, and is cheap; That uses polymer that described catalyst obtains selectively can both reach 99.9%, and active high, applied range.In addition, chirality rare earth catalyst first Application of the present invention is synthetic in olefinic polymerization and organic molecule.By the present invention, 4 polyisoprene, trans-1, the effective catalyst of 4 poly-1,3-butadienes have been found a series ofly can access 99.9%trans-1.
Description of drawings
Fig. 1 is the mono-crystalline structures of catalyst II among the embodiment 2-1;
Fig. 2 is the mono-crystalline structures of catalyst II among the embodiment 4-3.
The specific embodiment
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but is not limited to this.
The physical quantity that relates among the embodiment 1 ~ 18 is obtained by following methods:
(1) productive rate: actual production/theoretical yield.
(2) polymerization yield rate: the quality of the quality/polymerization single polymerization monomer of the polymer that obtains.
(3) trans-1, the 4-polymerization is selective: by polymer 1H and 13C nuclear magnetic spectrogram and following formula calculate:
1,4-IP%={I H1/(I H1+0.5I H2)}×100
trans-1,4-IP%={I C3/(I C1+I C2+I C3)}×100
In the formula, IP represents polyisoprene;
I H1: refer to 1The integration at 5.13ppm place in the H spectrum;
I H2: refer to 2The integration at 4.72ppm place in the H spectrum;
I C1: refer to 13The integration at 23.2ppm place in the C spectrum;
I C2: refer to 13The integration at 18.5ppm place in the C spectrum;
I C3: refer to 13The integration at 15.9ppm place in the C spectrum.
(4) M n: the molecular weight of polymer can obtain by infiltration gel chromatography (GPC) test.
(5) M w/ M n: the molecular weight distribution of polymer can obtain by the GPC test.
(6) T g: the vitrification point of polymerization can obtain by differential scanning calorimetry (DSC) test.
(7) activity: (obtaining the mole of the quality/catalyst of polymer)/polymerization time, unit: g/mol/h.
Embodiment 1
The preparation method of Shou bisoxazoline amido (NNN) part (Shao-Feng Lu, Da-Ming Du, Tetrahedron:Asymmetry 15 (2004) 3433 – 3441), its preparation process is:
1. add 7.0mmol diphenylamines-2,2 in the 100mL of drying reaction bulb ,-dicarboxylic acids dropwise adds thionyl chloride 10ml, back flow reaction 4h.Take unnecessary thionyl chloride away with oil pump, use CH 2Cl 2The product that obtains of dissolving dropwise joins above-mentioned product under the condition of ice bath and contains 14.0mmol L-valerian ammonia alcohol, 35.0mmolEt 3N and 20mL CH 2Cl 2Solution in, react 24h under the room temperature.The mixed solution that has reacted is used saturated NH successively 4Cl solution, 1mol/L HCl, saturated NaHCO 3Solution, saturated NaCl solution washing organic layer, anhydrous Na 2SO 4Dry.By silica gel column chromatography (ethyl acetate is made eluant, eluent), obtain intermediate product 2.6g behind the concentrated solution, by 1The H nuclear-magnetism detects, and described intermediate product is acid amides (C 22H 27N 3O 4) sterling, productive rate is 88.0%.
2. dropwise join at lower mesyl chloride 8.2mmol of condition of ice bath and contain acid amides 3.71mmolC 22H 27N 3O 4, 2.3mL Et 3N and 30mL CH 2Cl 2Solution in, add saturated NH behind the reaction 20h under the room temperature 4Cl solution 35ml divide to get organic layer, water layer CH 2Cl 2Extraction merges organic layer by saturated NaCl washing, anhydrous Na 2SO 4Drying, the concentrated crude product that obtains.Crude product is dissolved in the 7.5mL methyl alcohol, dropwise adds 7.5mL NaOH solution (0.3g NaOH is dissolved in the 7.5ml water), backflow 3h takes methyl alcohol away with oil pump, uses CH 2Cl 2Extract remaining solution, organic layer washs with saturated NaCl, anhydrous Na 2SO 4Dry.Obtain product 2.5g by silica gel column chromatography (benzinum: ethyl acetate=10:1 makes eluant, eluent) behind the concentrated solution, by 1The H nuclear-magnetism detects, and product is for being Shou bisoxazoline part of the present invention, and productive rate is 91%.
Embodiment 2
Under the environment of anhydrous and oxygen-free, in the 25mL reaction bulb, add 1.1523g Sc (CH 2SiMe 3) 3(thf) 2With the thf of 15mL anhydrous and oxygen-free, make Sc (CH 2SiMe 3) 3(thf) 2Fully dissolving.Dissolving suc as formula the thf of Shou bisoxazoline amido (NNN) part shown in the I with anhydrous and oxygen-free 1.0g embodiment 1 preparation in the environment of anhydrous and oxygen-free, then dropwise be added drop-wise in the reaction bulb, behind the reaction 3h, reaction solution becomes claret by yellow, drain thf, obtain yellow solid, remove by filter with n-hexane dissolution and with insoluble matter, then be placed in the refrigerator of-30 ° of C and be recrystallized, namely obtain the 1.066g product, detect by single crystal diffractometer, described product is that productive rate is 68% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-1.Fig. 1 is the mono-crystalline structures of described catalyst II-1.
Figure BDA00002162940700061
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-1:
(1) self-polymeric reaction of isoprene: in glove box, in the 50mL reaction bulb, add successively 40 μ mol triisobutyl aluminiums, 20 μ mol catalyst IIs-1,20mmol isoprene, 20 μ mol[Ph 3C] [B (C 6F 5) 4], 5mL toluene behind the reaction 6h, adds the ethanol cessation reaction, obtains the dope of white, and vacuum drying oven is dried to constant weight, obtains polyisoprene 1.361g, and polymerization yield rate is 100%, by 1H and 13The C nuclear-magnetism detects, and trans-1, the content of 4-polyisoprene are 99.9%, i.e. catalyst II-1 couple trans-1, the 4-polyisoprene selectively be 99.9%, M n=25 * 10 3, M w/ M n=1.14, Tm=50.43 ℃, activity: 11351g/mol/h.Show that catalyst system therefor not only has high selectivity, and activity is very high.
(2) self-polymeric reaction of isoprene: in glove box, in the 50mL reaction bulb, add successively 20 μ mol catalyst IIs-1,20mmol isoprene, 20 μ mol[Ph 3C] [B (C 6F 5) 4], 5mL toluene behind the reaction 6h, adds the ethanol cessation reaction, obtains the dope of white, and vacuum drying oven is dried to constant weight, obtains polyisoprene 1.361g, and polymerization yield rate is 100%, by 1H and 13The C nuclear-magnetism detects, and trans-1, the content of 4-polyisoprene are 99.9%, i.e. catalyst II-1 couple trans-1, the 4-polyisoprene selectively be 99.9%, M n=21 * 10 3, M w/ M n=1.04, Tm=52.43 ℃, activity: 11351g/mol/h.Show that catalyst system therefor not only has high selectivity, and activity is very high.
(3) self-polymeric reaction of isoprene: in glove box, in the 50mL reaction bulb, add successively 20 μ mol catalyst IIs-1,20mmol isoprene, 20 μ mol[Ph 3C] [B (C 6F 5) 4], 5mL toluene behind 90 ℃ of lower reaction 6h, adds the ethanol cessation reaction, obtains the dope of white, and vacuum drying oven is dried to constant weight, obtains polyisoprene 1.351g, and polymerization yield rate is 100%, by 1H and 13The C nuclear-magnetism detects, and trans-1, the content of 4-polyisoprene are 99.9%, i.e. catalyst II-1 couple trans-1, the 4-polyisoprene selectively be 99.9%, M n=24 * 10 3, M w/ M n=1.24, Tm=56.43 ℃, activity: 11351g/mol/h.Show that catalyst system therefor not only has high selectivity, and activity is very high.
(4) self-polymeric reaction of isoprene: in glove box, in the 50mL reaction bulb, add successively 20 μ mol catalyst IIs-1,20mmol isoprene, 20 μ mol[Ph 3C] [B (C 6F 5) 4], 5mL toluene behind 0 ℃ of lower reaction 12h, adds the ethanol cessation reaction, obtains the dope of white, and vacuum drying oven is dried to constant weight, obtains polyisoprene 1.351g, and polymerization yield rate is 100%, by 1H and 13The C nuclear-magnetism detects, and trans-1, the content of 4-polyisoprene are 99.9%, i.e. catalyst II-1 couple trans-1, the 4-polyisoprene selectively be 99.9%, M n=16 * 10 3, M w/ M n=1.44, Tm=50.23 ℃, activity: 11351g/mol/h.Show that catalyst system therefor not only has high selectivity, and activity is very high.
(5) self-polymeric reaction of 1,3-butadiene: in glove box, in the 50mL reaction bulb, add successively 40 μ mol triisobutyl aluminiums, 20 μ mol catalyst IIs-1,20mmol1,3-butadiene, 20 μ mol[Ph 3C] [B (C 6F 5) 4], 5mL toluene behind the reaction 6h, adds the ethanol cessation reaction, obtains the dope of white, and vacuum drying oven is dried to constant weight, obtains poly-1,3-butadiene 1.361g, and polymerization yield rate is 100%, by 1H and 13The C nuclear-magnetism detects, trans-1, the content of the poly-1,3-butadiene of 4-is 99.9%, i.e. catalyst II-1 couple trans-1, the poly-1,3-butadiene of 4-selectively be 99.9%, M n=85 * 10 3, M w/ M n=1.14, Tm=50.43 ℃, activity: 11351g/mol/h.Show that catalyst system therefor not only has high selectivity, and activity is very high.
(6) self-polymeric reaction of 1,3-butadiene: in glove box, in the 50mL reaction bulb, add successively 40 μ mol triisobutyl aluminiums, 20 μ mol catalyst IIs-1,20mmol1,3-butadiene, 20 μ mol[Ph 3C] [B (C 6F 5) 4], 5mL toluene behind 90 ℃ of reaction 6h, adds the ethanol cessation reaction, obtains the dope of white, and vacuum drying oven is dried to constant weight, obtains poly-1,3-butadiene 1.461g, and polymerization yield rate is 100%, by 1H and 13The C nuclear-magnetism detects, trans-1, the content of the poly-1,3-butadiene of 4-is 99.9%, i.e. catalyst II-1 couple trans-1, the poly-1,3-butadiene of 4-selectively be 99.9%, M n=85 * 10 3, M w/ M n=1.14, Tm=58.43 ℃, activity: 11351g/mol/h.Show that catalyst system therefor not only has high selectivity, and activity is very high.
(7) self-polymeric reaction of 1,3-butadiene: in glove box, in the 50mL reaction bulb, add successively 40 μ mol triisobutyl aluminiums, 20 μ mol catalyst IIs-1,20mmol1,3-butadiene, 20 μ mol[Ph 3C] [B (C 6F 5) 4], 5mL toluene behind 0 ℃ of reaction 12h, adds the ethanol cessation reaction, obtains the dope of white, and vacuum drying oven is dried to constant weight, obtains poly-1,3-butadiene 1.461g, and polymerization yield rate is 100%, by 1H and 13The C nuclear-magnetism detects, trans-1, the content of the poly-1,3-butadiene of 4-is 99.9%, i.e. catalyst II-1 couple trans-1, the poly-1,3-butadiene of 4-selectively be 99.9%, M n=65 * 10 3, M w/ M n=1.04, Tm=52.13 ℃, activity: 11351g/mol/h.Show that catalyst system therefor not only has high selectivity, and activity is very high.
(8) self-polymeric reaction of 1,3-butadiene: in glove box, in the 50mL reaction bulb, add successively 20 μ mol catalyst IIs-1,20mmol1,3-butadiene, 20 μ mol[Ph 3C] [B (C 6F 5) 4], 5mL toluene behind the reaction 6h, adds the ethanol cessation reaction, obtains the dope of white, and vacuum drying oven is dried to constant weight, obtains poly-1,3-butadiene 1.361g, and polymerization yield rate is 100%, by 1H and 13The C nuclear-magnetism detects, trans-1, the content of the poly-1,3-butadiene of 4-is 99.9%, i.e. catalyst II-1 couple trans-1, the poly-1,3-butadiene of 4-selectively be 99.9%, M n=75 * 10 3, M w/ M n=1.12, Tm=50.43 ℃, activity: 11351g/mol/h.Show that catalyst system therefor not only has high selectivity, and activity is very high.
(9) (S)-and 3-indyl-3-phenyl alcoholic compound preparation: under the nitrogen protection, with 20 μ mol catalyst II-1,20 μ mol[Ph 3C] [B (C 6F 5) 4], be dissolved in 1mL methyl alcohol, cool to-10 ℃.To wherein adding the 0.5mmol cinnamic acid, stir 30min, then add the 1.0mmol indoles, reaction 12h.Add 1.5mmolNaBH 4With 1mL methyl alcohol.Be warming up to 0 ℃, slowly add the saturated NH of 5mL to reaction system 4Cl solution continues to stir 20min again.Then use extracted with diethyl ether three times.The ether layer that merges is used first the 5mL water washing, uses the water washing of 5mL saturated common salt again, uses anhydrous sodium sulfate drying.Obtain product by silica gel column chromatography (benzinum: ethyl acetate=1:1 makes eluant, eluent) behind the concentrated solution, by 1The H nuclear-magnetism detects, and product is (S)-3-indyl-3-phenyl alcohol, and productive rate is 86%.Reaction equation is as follows:
Figure BDA00002162940700081
(10) preparation pyrimido indolone: under nitrogen protection, the 0.55mmol methylphenylamine is dissolved in the 4mL toluene, drips 152mg neighbour together with dibromo vinyl phenyl isocyanate, then at room temperature stir lh.Add 20 μ mol catalyst II-1,20 μ mol[Ph in the reaction system 3C] [B (C 6F 5) 4] and 1.0mmolK 2CO 3, and be heated to 120 ℃, reaction 12h.Then add 0.05mmol pd (dppf) Cl to reaction system 2 (), 1.5mmol KOAc reacts 12h again.After reaction finishes, with carrene (3 * 10mL) washings merge organic layer, use anhydrous sodium sulfate drying, obtain product by silica gel column chromatography (benzinum: ethyl acetate=2:1 makes eluant, eluent) behind the concentrated solution, by 1The H nuclear-magnetism detects, and product is the pyrimido indolone, and productive rate is 78%, and wherein, Ac is acetate, and dppf is two (diphenylphosphine) ferrocene of 1,1'-, and reaction equation is as follows:
Figure BDA00002162940700091
Embodiment 3
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-2, its preparation process the difference is that 1.1523g Sc (CH in the example 2 with embodiment 2 2SiMe 3) 3(thf) 2Replace with 0.896gY (CH 2SiMe 3) 3(THF) 2, obtain catalyst 1.201g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 72% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-2.
Figure BDA00002162940700092
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-2, its application process is with embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-2, and the time replaces with 3h, and the consumption of isoprene replaces with 30mmol, and obtaining polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=68 * 10 3, M w/ M n=1.04, Tm=56.05 ℃; Active: 34055g/mol/h.
The catalyst II-1 of (9) among the embodiment 2 is replaced with catalyst II-2, and the productive rate that obtains (S)-3-indyl-3-phenyl alcohol compound is 92%, and is higher than the productive rate with catalyst II-1.
The catalyst II-1 of (10) among the embodiment 2 is replaced with catalyst II-2, and the productive rate that obtains the pyrimido indolone is 85%, and is higher than the productive rate with catalyst II-1.
Embodiment 4
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-3, its preparation process the difference is that 1.1523g Sc (CH in the example 2 with embodiment 2 2SiMe 3) 3(thf) 2Replace with 1.484gLu (CH 2SiMe 3) 3(thf) 2Obtain catalyst 1.087g, by 1H and 13The C nuclear-magnetism detects, and described product is suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-3, and productive rate is that 73%, Fig. 2 is the mono-crystalline structures of described catalyst II-3.
Figure BDA00002162940700101
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-3, its application process is with embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-3, and the time replaces with 2h, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=45 * 10 3, M w/ M n=1.12, Tm=50.27 ℃, activity: 68106g/mol/h exceeds 3 times than the activity of catalyst II-1, exceeds 1.5 times than catalyst II-2
The catalyst II-1 of (2) among the embodiment 2 is replaced with catalyst II-3, and the time replaces with 2h, and it is 100%, trans-1 that the consumption of isoprene replaces with the 30mmol polymerization yield rate, and the 4-polymerization selectively is 99.9%, M n=47 * 10 3, M w/ M n=1.08, Tm=50.67 ℃, activity: 204330g/mol/h.
The catalyst II-1 of (3) among the embodiment 2 is replaced with catalyst II-3, and the time replaces with 0.5h, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=47 * 10 3, M w/ M n=1.08, Tm=48.67 ℃, activity: 272424g/mol/h.
The catalyst II-1 of (4) among the embodiment 2 is replaced with catalyst II-3, and the time replaces with 0.5h, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=47 * 10 3, M w/ M n=1.08, Tm=50.67 ℃, activity: 272424g/mol/h.
The catalyst II-1 of (9) among the embodiment 2 is replaced with catalyst II-3, and the productive rate of (the S)-3-indyl that obtains-3-phenyl alcohol compound is 82%.
The catalyst II-1 of (10) among the embodiment 2 is replaced with catalyst II-3, and the productive rate of the pyrimido indolone that obtains is 75%.
Embodiment 5
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-4, its preparation process the difference is that 1.1523gSc (CH in the example 2 with embodiment 2 2SiMe 3) 3(thf) 2Replace with 1.439gGd (CH 2SiMe 3) 3(thf) 2Obtain catalyst 1.054g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 57% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-4.
Figure BDA00002162940700111
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-4, its application process is with embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-4, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=33 * 10 3, M w/ M n=1.07, Tm=47.51 ℃, activity: 11351g/mol/h.
The middle catalyst II-1 of (9) among the embodiment 2 is replaced with catalyst II-4, and the productive rate that obtains (S)-3-indyl-3-phenyl alcohol compound is 60%.
The middle catalyst II-1 of (10) among the embodiment 2 is replaced with catalyst II-4, and the productive rate of the pyrimido indolone that obtains is 65%.
Embodiment 6
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-5, its preparation process the difference is that 1.1523g Sc (CH in the example 2 with embodiment 2 2SiMe 3) 3(thf) 2Replace with 1.4516gDy (CH 2SiMe 3) 3(thf) 2Obtain catalyst 1.004g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 54% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-5.
Figure BDA00002162940700112
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-5, its application process is with embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-5, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=42 * 10 3, M w/ M n=1.18, Tm=44.75 ℃; Active: 11351g/mol/h is the same with catalyst II-1;
The catalyst II-1 of (9) among the embodiment 2 is replaced with catalyst II-5, obtain the productive rate 80% of (S)-3-indyl-3-phenyl alcoholic compound;
The catalyst II-1 of (10) among the embodiment 2 is replaced with catalyst II-5, the productive rate 79% of the pyrimido indolone that obtains.
Embodiment 7
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-6, its preparation process the difference is that 1.1523g Sc (CH in the example 2 with embodiment 2 2SiMe 3) 3(thf) 2Replace with 1.4590gHo (CH 2SiMe 3) 3(thf) 2Obtain catalyst 1.3436g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 70% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-6.
Figure BDA00002162940700121
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-6, its application process is with embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-6, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=110 * 10 3, M w/ M n=1.22, Tm=37.35 ℃; Active: 11351g/mol/h is the same with catalyst II-1.
The catalyst II-1 of (9) among the embodiment 2 is replaced with catalyst II-6, obtain the productive rate 50% of (S)-3-indyl-3-phenyl alcoholic compound;
The catalyst II-1 of (10) among the embodiment 2 is replaced with catalyst II-6, the productive rate 55% of the pyrimido indolone that obtains.
Embodiment 8
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-7, its preparation process the difference is that 1.1523g Sc (CH in the example 2 with embodiment 2 2SiMe 3) 3(thf) 2Replace with 0.8692gEr (CH 2SiMe 3) 3(thf) 2Obtain catalyst 1.3445g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 72% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-7.
Figure BDA00002162940700131
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-7, its application process is with embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-7, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=59 * 10 3, M w/ M n=1.26, Tm=39.85 ℃.Active: 11351g/mol/h is the same with catalyst II-1.
The catalyst II-1 of (9) among the embodiment 2 is replaced with catalyst II-7, obtain the productive rate 84% of (S)-3-indyl-3-phenyl alcoholic compound;
The catalyst II-1 of (10) among the embodiment 2 is replaced with catalyst II-7, the productive rate 77% of the pyrimido indolone that obtains.
Embodiment 9
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-8, its preparation process the difference is that 1.1523g Sc (CH in the example 2 with embodiment 2 2SiMe 3) 3(thf) 2Replace with 0.8768gTm (CH 2SiMe 3) 3(thf) 2Obtain catalyst 0.4445g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 51% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-8.
Figure BDA00002162940700132
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-8, its application process is with embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-8, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=110 * 10 3, M w/ M n=1.22, Tm=37.35 ℃.Active: 11351g/mol/h is the same with catalyst II-1.
The catalyst II-1 of (9) among the embodiment 2 is replaced with catalyst II-8, obtain the productive rate 66% of (S)-3-indyl-3-phenyl alcoholic compound.
The catalyst II-1 of (10) among the embodiment 2 is replaced with catalyst II-8, the productive rate 71% of the pyrimido indolone that obtains.
Embodiment 10
1. in 100ml Si Langke bottle, add 40ml oxolane and 5mmolScCl 3Be back to solution 80 ℃ of heating and be transparence, the stirring at room cooling white solid can occur and be ScCl 3(thf) 2
2. under the environment of anhydrous and oxygen-free in the 50ml reaction bulb, with 5mmol embodiment 1 preparation suc as formula in the dissolving of Shou bisoxazoline amido (NNN) part shown in the I 10ml ether.
3. under the environment of anhydrous and oxygen-free, in the 25mL reaction bulb, add 5mmol nBuLi.
4. with dropper the n-BuLi of step in 3. slowly splashed in the step solution 2., stirring at normal temperature reaction 12 hours generates yellow solution.The lithium salts that obtains dropwise joined to be 5mmolScCl 3(thf) 2Reaction bulb in, stirring at normal temperature 24 hours obtains the peony viscous mixture, repeatedly washes with n-hexane, glass sand hourglass filters, and obtains yellow solution, drains to get light yellow solid 1.527g.By 1H and 13The C nuclear-magnetism detects and is suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-9, productive rate 47.0%.
Figure BDA00002162940700141
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-9: its application process is with the application of (1) among the embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-9, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=97 * 10 3, M w/ M n=1.24, Tm=47.65 ℃.Active: 10443g/mol/h is all lower than above-mentioned catalyst II-1 ~ II-8 activity.
Embodiment 11
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-10, its preparation process the difference is that ScCl in the example 10 with embodiment 10 3(thf) 2Replace with HfCl 4, obtain catalyst 1.453g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 69% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-10.
Figure BDA00002162940700151
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-10: its application process is with the application of (1) among the embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-10, and polymerization yield rate is 92%, trans-1, and the 4-polymerization selectively is 99.9%, M n=67 * 10 3, M w/ M n=1.64, Tm=47.65 ℃.Active: 10443g/mol/h is all lower than above-mentioned catalyst II-1 ~ II-8 activity.
Embodiment 12
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-11, its preparation process the difference is that ScCl in the example 10 with embodiment 10 3(thf) 2Replace with ZrCl 4, obtain catalyst 1.335g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 59% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-11.
Figure BDA00002162940700152
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-11: its application process is with the application of (1) among the embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-11, and polymerization yield rate is 89%, trans-1, and the 4-polymerization selectively is 99.9%, M n=79 * 10 3, M w/ M n=1.44, Tm=47.35 ℃.Active: 10103g/mol/h is all lower than above-mentioned catalyst II-1 ~ II-8 activity.
Embodiment 13
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-12, its preparation process the difference is that ScCl in the example 10 with embodiment 10 3(thf) 2Replace with TiCl 4, obtain catalyst 1.445g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 47% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-12.
Figure BDA00002162940700161
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-12: its application process is with the application of (1) among the embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-12, and polymerization yield rate is 86%, trans-1, and the 4-polymerization selectively is 99.9%, M n=97 * 10 3, M w/ M n=1.54, Tm=47.95 ℃.Active: 9762g/mol/h is all lower than above-mentioned catalyst II-1 ~ II-8 activity.
Embodiment 14
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-13, its preparation process the difference is that ScCl in the example 10 with embodiment 10 3(thf) 2Replace with AuCl 3, obtain catalyst 1.378g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 63% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-13.
Figure BDA00002162940700162
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-13: its application process is with the application of (1) among the embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-13, and polymerization yield rate is 96%, trans-1, and the 4-polymerization selectively is 99.9%, M n=87 * 10 3, M w/ M n=1.14, Tm=57.35 ℃.Active: 10897g/mol/h is all lower than above-mentioned catalyst II-1 ~ II-8 activity.
Embodiment 15
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-14, its preparation process the difference is that ScCl in the example 10 with embodiment 10 3(thf) 2Replace with CrCl 3Obtain catalyst 1.398g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 49% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-14.
Figure BDA00002162940700171
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-14: its application process is with the application of (1) among the embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-14, and polymerization yield rate is 89%, trans-1, and the 4-polymerization selectively is 99.9%, M n=107 * 10 3, M w/ M n=1.45, Tm=49.85 ℃.Active: 8967g/mol/h is all lower than above-mentioned catalyst II-1 ~ II-8 activity.
Embodiment 16
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-15, its preparation process the difference is that ScCl in the example 10 with embodiment 10 3(thf) 2Replace with IrCl 3Obtain catalyst 1.468g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 35% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-15.
Figure BDA00002162940700172
Figure BDA00002162940700181
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-15: its application process is with the application of (1) among the embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-15, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=112 * 10 3, M w/ M n=1.51, Tm=59.85 ℃.Active: 11351g/mol/h is active the same with catalyst II-1.
Embodiment 17
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-16, its preparation process the difference is that ScCl in the example 10 with embodiment 10 3(thf) 2Replace with RhCl 3Obtain catalyst 1.365g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 41% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-16.
Figure BDA00002162940700182
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-16: its application process is with the application of (1) among the embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-16, and polymerization yield rate is 81%, trans-1, and the 4-polymerization selectively is 99.9%, M n=98 * 10 3, M w/ M n=1.41, Tm=55.85 ℃.Active: 9340g/mol/h is all lower than above-mentioned catalyst II-1 ~ II-8 activity.
The polymerization of catalyst II-16 pair ethene: under nitrogen protection, in the 50mL reaction bulb, add 15ml toluene, 0.020mmol catalyst II-16,0.020mmol[Ph 3C] [B (C 6F 5) 4].Pass into ethylene gas under the room temperature to saturated, behind the 30min, stop ventilation.Add the ethanol cessation reaction in reaction bulb, obtain the dope of white, vacuum drying oven is dried to constant weight.Obtain polyethylene 0.6g.M n=5 * 10 3, M w/ M n=1.12, Tm=40.27 ℃, activity: 68106g/mol/h.
Embodiment 18
The preparation method of Shou bisoxazoline amido (NNN) metallic catalyst II-17, its preparation process the difference is that ScCl in the example 10 with embodiment 10 3(thf) 2Replace with PdCl 2Obtain catalyst 1.415g, by 1H and 13The C nuclear-magnetism detects, and described product is that productive rate is 40% suc as formula Shou bisoxazoline amido (NNN) metallic catalyst shown in the II-17.
Figure BDA00002162940700191
The application of Shou bisoxazoline amido (NNN) metallic catalyst shown in the formula II-17, its application process is with the application of (1) among the embodiment 2, and wherein difference is as follows:
The catalyst II-1 of (1) among the embodiment 2 is replaced with catalyst II-17, and polymerization yield rate is 100%, trans-1, and the 4-polymerization selectively is 99.9%, M n=107 * 10 3, M w/ M n=1.25, Tm=59.75 ℃.Active: 11351g/mol/h is active the same with catalyst II-1.
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the principle of spirit of the present invention, replace or local improvement, all will be considered as within protection scope of the present invention.

Claims (4)

1. hand bisoxazoline amido metallic catalyst, it is characterized in that: described catalyst structure formula is as follows:
Figure FDA00002162940600011
Wherein, n represents the R that links to each other with central metal M 2Quantity, R 1Be CH 3, CH 2CH 3, CH 2CH 2CH 3, CH (CH 3) 2, C (CH 3) 3, CH 2CH (CH 3) 2, CH 2Ph or Ph; R 2Be CH 2SiMe 3, CH (SiMe 3) 2, CH 2-(2,6- iPr 2-C 6H 3), CH 2CHCH 2, MeCHCHCH 2, CH 2CPhCH 2, CH 2CMeCH 2, CH 2C 6H 4NMe 2-o, CH 2C 6H 4OMe-o or Cl; Ph is phenyl, and Me is methyl, iPr is isopropyl, and o represents the ortho position;
(1) as M=Sc, Y, Lu, Yb, Tm, Er, Ho, Dy, Tb, Gd, Eu, Sm, Pm, Nd, Pr, Ce or La, and M is when being positive trivalent; N=2;
(2) when M=Hf, Ti or Zr, be divided into two kinds of situations:
The first, when M is positive tetravalence, n=3;
The second, when M is positive trivalent, n=2;
(3) work as M=Au, Cr, Rh, during Ir, and M is when being positive trivalent, n=2;
(4) work as M=Pd, when M is positive divalence, n=1.
2. the preparation method of a hand bisoxazoline amido metallic catalyst as claimed in claim 1, it is characterized in that: the chemical equation of described method is as follows:
Figure FDA00002162940600012
Described method step is as follows:
1. in the environment of anhydrous and oxygen-free with M (R 2) nJoin in the reactor with the oxolane of anhydrous and oxygen-free, make M (R 2) n is dissolved in the oxolane fully;
2. will be suc as formula the Shou bisoxazoline amido part shown in the I with the dissolving of the oxolane of anhydrous and oxygen-free in the environment of anhydrous and oxygen-free, then dropwise be added drop-wise in the reactor of step in 1., make Shou bisoxazoline amido part and M (R 2) nReaction can stop reaction until reaction solution becomes claret by yellow;
3. reaction is removed oxolane after finishing, and with the solid n-hexane dissolution that obtains, and insoluble matter is removed by filter rear recrystallization, can obtain suc as formula the Shou bisoxazoline amido metallic catalyst shown in the II;
Wherein, thf is oxolane; Shou bisoxazoline amido part and the M (R of step described in 2. 2) nThe ratio of amount of substance be 1:1.
3. the preparation method of a hand bisoxazoline amido metallic catalyst as claimed in claim 1, it is characterized in that: the chemical equation of described method is as follows:
Described method step is as follows:
1. under≤35 ° of C, will join in the reactor suc as formula Shou bisoxazoline amido part and the ether shown in the I, and make Shou bisoxazoline amido part be dissolved in the ether fully;
2. the n-butyllithium solution that with concentration is 2.5mol/L dropwise joins in the step reactor 1., until the color of the solution yellowing stops to drip in the reactor, desolventizing is dissolved in the grease that obtains in the toluene, obtains solution;
3. after M (Cl) n being dissolved in toluene, dropwise join in the solution that 2. step obtain, be stirred to solution and be Chinese red, and have precipitation to occur, remove precipitation, and after the solvent in the solution that obtains removed, normal temperature spent the night;
4. with R 2Li joins in the solution of generation, reacts desolventizing after 2 hours, obtains the peony viscous mixture, and washing is filtered, and obtains yellow solution, drain light yellow solid namely shown in formula III hand bisoxazoline amido metallic catalyst;
Wherein, M (R 2) n is 1:1 with the ratio of the amount of substance of Shou bisoxazoline amido part.
4. the purposes of Shou bisoxazoline amido metallic catalyst as claimed in claim 1 is characterized in that:
(1) as the catalyst for preparing (S)-3-indyl-3-phenyl alcohol or pyrimido indolone;
(2) as the catalyst of isoprene, 1,3-butadiene self-polymeric reaction;
(3) as the catalyst of ethene self-polymeric reaction;
Wherein, co-catalyst is fluoro borate or alkyl aluminum, is preferably [Ph 3C] [B (C 6F 5) 4], [PhNHMe 2] [B (C 6F 5) 4], B (C 6F 5) 3, Al iBu 3, AlEt 3, AlMe 3Or MAO, iBu represents isobutyl group.
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