CN101805373A - Preparation method of amino aryloxy rare earth metal amide - Google Patents

Preparation method of amino aryloxy rare earth metal amide Download PDF

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CN101805373A
CN101805373A CN200910231760A CN200910231760A CN101805373A CN 101805373 A CN101805373 A CN 101805373A CN 200910231760 A CN200910231760 A CN 200910231760A CN 200910231760 A CN200910231760 A CN 200910231760A CN 101805373 A CN101805373 A CN 101805373A
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rare earth
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CN101805373B (en
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姚英明
卢敏
沈琪
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Suzhou University
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Abstract

The invention relates to a rare earth metal compound containing N,O double anion ligands, in particular to a preparation method of an amino aryloxy rare earth metal amide, which comprises the steps of: 1, reacting an aminophenol ligand with butyl lithium under the condition without oxygen and water in an inert atmosphere; 2, reacting the product obtained in the step 1 with Ln[N(SiMe3)2]3(mu-Cl)Li(THF)3 in a mixed solution of tetrahydrofuran and hexane with a proportion of 10:1-15:1 to prepare [NO]2Ln[N(SiMe3)2] Li(THF)2, wherein Ln is rare earth metal and is selected from praseodymium, neodymium, samarium, ytterbium and yttrium; [NO] stands for an amino aryloxy ligand and is p-X-C6H4NCH2(3-R2-5-R3-C6H2-2-O), and X is selected from one of hydrogen, C1-C4 saturated alkyl or halogen; and R2 and R3 are respectively selected from one of methyl or tertiary butyl. The method for synthesizing the amino aryloxy rare earth metal amide is suitable for various aminophenol ligands under the mild condition, and has higher yield and simpler separation and purification compared with the method in the Chinese patent application with an application number of 200910181279.

Description

The preparation method of amino aryloxy rare earth metal amide
Technical field
The present invention relates to contain N, the rare earth metal complex of O pairs of anion part is specifically related to a kind of preparation method of amino aryloxy rare earth metal amide.
Background technology
Application number is to disclose amido aryloxy rare earth metal amide and catalytic applications thereof in 200910181279.7 the Chinese invention patent ublic specification of application, and the general formula of described amido aryloxy rare earth metal amide is [NO] 2LnN (SiMe 3) 2Li 2(THF) 2, wherein Ln is a rare earth metal, [NO]=p-R 1-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), R 1Be selected from: a kind of in the saturated alkyl of hydrogen or C1～C4, R 2And R 3Be selected from respectively: a kind of in the methyl or the tertiary butyl; And the application of this compound as the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide disclosed.The amido aryloxy rare earth metal amide is by amido phenol part and Ln[N (SiMe in this application 3) 2] 3(the Li (THF) of μ-Cl) 3The reaction synthetic, this method productive rate is low, has only about 40% product separation and purification trouble.
Summary of the invention
The object of the invention provides a kind of preparation method of amino aryloxy rare earth metal amide.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of amino aryloxy rare earth metal amide may further comprise the steps:
(1) under the anhydrous and oxygen-free condition, in the inert atmosphere, amido phenol part and n-Butyl Lithium generation permutoid reaction generate the lithium salts of amido aryloxy;
(2) with the lithium salts and the Ln[N (SiMe of step (1) products therefrom amido aryloxy 3) 2] 3(the Li (THF) of μ-Cl) 3Prepared in reaction in the mixing solutions of tetrahydrofuran (THF) and hexane [NO] 2Ln[N (SiMe 3) 2] Li 2(THF) 2
Wherein, the volume ratio of tetrahydrofuran (THF) and hexane is 10: 1～15: 1 in the mixing solutions of tetrahydrofuran (THF) and hexane.
Wherein, the synthetic method of described amino phenol part is referring to Alesso, G.; Sanz, M.; Mosquera, M.E.G.; Cuenca, T.Eur.J.Inorg.Chem.2008,4638; Described amino phenol part is [NO] H 2, its chemical structural formula is as follows:
Figure G2009102317602D00021
The chemical structural formula of the lithium salts of described amido aryloxy is as follows:
Figure G2009102317602D00022
Wherein, described Ln[N (SiMe 3) 2] 3(the Li (THF) of μ-Cl) 3The document of preparation method's reference: Zhou, S.L.; Wang, S.W.; Yang, G.S.; Liu, X.Y.; Sheng, E.H.; Zhang, K.H.; Cheng, L.Polyhedron 2003,22, and 1019;
Described [NO] 2Ln[N (SiMe 3) 2] Li 2(THF) 2Chemical structural formula as follows:
Figure G2009102317602D00023
Wherein Ln is a rare earth metal, is selected from: a kind of in praseodymium, neodymium, samarium, ytterbium or the yttrium; [NO] represents the amido aryloxy ligands, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is selected from: a kind of in the saturated alkyl of hydrogen, C1～C4 or the halogen, R 2And R 3Be selected from respectively: a kind of in the methyl or the tertiary butyl.
In the technique scheme, described rare gas element is selected from: a kind of in argon gas or the nitrogen.
In the technique scheme, temperature of reaction is-10 ℃～0 ℃ in the step (1), and the reaction times was at least 1 hour; Temperature of reaction is 40 ℃～50 ℃ in the step (2), and the reaction times was at least 12 hours.
In the technique scheme, in the step (1), according to the ratio of amount of substance, amido phenol part is 1: 1 with the ratio of n-Butyl Lithium material, in the step (2), and according to the ratio of amount of substance, step (1) products therefrom and Ln[N (SiMe 3) 2] 3(the Li (THF) of μ-Cl) 3Ratio be 2: 1.
The process of above-mentioned reaction schematically as follows shown in:
Figure G2009102317602D00031
Further in the technical scheme, above-mentioned product is separated purification, the concrete steps of separating purification are: remove and desolvate, use the toluene extraction, the centrifugal precipitation of removing concentrates clear liquid, and the adding normal hexane leaves standstill crystallization under the normal temperature, can obtain [NO] 2Ln[N (SiMe 3) 2] Li 2(THF) 2Crystal.
In the technique scheme, the productive rate of amido aryloxy rare earth metal amide is 85%～90%.
The compound that technique scheme prepares can be used as the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide, and obtains open in application number is 200910181279.7 Chinese invention patent ublic specification of application.
The present invention is claimed a kind of amino aryloxy rare earth metal amide simultaneously, and the chemical formula of described amino aryloxy rare earth metal amide is: [NO] 2Ln[N (SiMe 3) 2] Li 2(THF) 2, chemical structural formula is as follows:
Figure G2009102317602D00032
Wherein Ln is a rare earth metal, is selected from: a kind of in praseodymium, neodymium, samarium, ytterbium or the yttrium; [NO] represents the amido aryloxy ligands, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), R 2And R 3Be selected from respectively: a kind of in the methyl or the tertiary butyl; X is selected from: a kind of in the halogen.
The present invention's claimed above-mentioned amino aryloxy rare earth metal amide of while is as the application of catalysis L-rac-Lactide polymeric single component catalyst.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the method for synthetic amido aryloxy rare earth metal amide of the present invention, under mild conditions, be applicable to multiple amido phenol part, than application number the method in 200910181279.7 the Chinese invention patent application, method productive rate of the present invention is higher, and separation and purification is simpler.
2. synthetic method craft of the present invention is simple, and the part of employing is applicable to various rare earth metals.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: preparation [NO] 2Nd[N (SiMe 3) 2] Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a methyl, R 2, R 3It all is the tertiary butyl.
(1) with 1.61 gram [NO] H 2(4.95 mmole) is dissolved in tetrahydrofuran (THF), and adding contains nThe hexane solution of BuLi (4.95 mmole) ,-10 ℃ of stirring reactions one hour add Nd[N (SiMe again 3) 2] 3(the Li (THF) of μ-Cl) 3The tetrahydrofuran solution of (2.48 mmole), system are blue, and 50 ℃ of stirring reactions spend the night;
(2) take out and desolvate, add 30 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and adds 4.00 milliliters of hexanes, concentrated solution to 12 milliliter, and ambient temperature overnight is separated out blue colored crystal 2.48 and is restrained (2.24 mmole), productive rate 90%.
Embodiment two: preparation [NO] 2Yb[N (SiMe 3) 2] Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a methyl, R 2, R 3It all is the tertiary butyl.
(1) with 0.72 gram [NO] H 2(2.21 mmole) is dissolved in tetrahydrofuran solution, and adding contains nThe hexane solution of BuLi (2.21 mmole) ,-10 ℃ of stirring reactions one hour add Yb[N (SiMe again 3) 2] 3(the Li (THF) of μ-Cl) 3The tetrahydrofuran solution of (1.10 mmole), system are yellow, and 50 ℃ of stirring reactions spend the night;
(2) take out and desolvate, add 20 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and adds 3.00 milliliters of hexanes, concentrated solution to 13 milliliter, and ambient temperature overnight is separated out glassy yellow crystal 1.07 and is restrained (0.94 mmole), and productive rate is 85%.
Embodiment three, preparation [NO] 2Sm[N (SiMe 3) 2] Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a fluorine, R 2, R 3It all is the tertiary butyl.
(1) with 1.66 gram [NO] H 2(5.04 mmole) is dissolved in tetrahydrofuran solution, and adding contains nThe hexane solution of BuLi (5.04 mmole) ,-10 ℃ of stirring reactions one hour add 2.52 mmole Sm[N (SiMe again 3) 2] 3(the Li (THF) of μ-Cl) 3Tetrahydrofuran solution, system is yellow, 50 ℃ of stirring reactions spend the night;
(2) take out and desolvate, add 40 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and adds 5.00 milliliters of hexanes, and concentrated solution to 20 milliliter is separated out a large amount of yellow crystals 1.88 and restrained (2.17 mmole) under the room temperature, and productive rate is 86%.
Embodiment four, preparation [NO] 2Yb[N (SiMe 3) 2] Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a fluorine, R 2, R 3It all is the tertiary butyl.
(1) with 2.14 gram [NO] H 2(6.50 mmole) is dissolved in tetrahydrofuran (THF), and adding contains nThe hexane solution of BuLi (6.50 mmole) ,-10 ℃ of stirring reactions one hour add Y[N (SiMe again 3) 2] 3(the Li (THF) of μ-Cl) 3In the tetrahydrofuran solution of (3.25 mmole), system is yellow, and 50 ℃ of stirring reactions spend the night;
(2) take out and desolvate, add 30 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and adds 5.00 milliliters of hexanes, and concentrated solution to 18 milliliter is separated out a large amount of yellow crystals 2.63 and restrained (2.76 mmole) under the room temperature, and productive rate is 85%.
Embodiment five: preparation [NO] 2Nd[N (SiMe 3) 2] Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a chlorine, R 2, R 3It all is the tertiary butyl.
(1) with 1.63 gram [NO] H 2(4.72 mmole) is dissolved in tetrahydrofuran (THF), and adding contains nThe hexane solution of BuLi (4.72 mmole) ,-10 ℃ of stirring reactions one hour add Nd[N (SiMe again 3) 2] 3(the Li (THF) of μ-Cl) 3The tetrahydrofuran solution of (2.36 mmole), system are blue, and 50 ℃ of stirring reactions spend the night;
(2) take out and desolvate, add 30 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and adds 5.00 milliliters of hexanes, concentrated solution to 16 milliliter, and ambient temperature overnight is separated out blue colored crystal 5.05 and is restrained (2.08 mmole), productive rate 88%.
Embodiment six: preparation [NO] 2Sm[N (SiMe 3) 2] Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a chlorine, R 2, R 3It all is the tertiary butyl.
(1) with 1.49 gram [NO] H 2(4.31 mmole) is dissolved in tetrahydrofuran (THF), and adding contains nThe hexane solution of BuLi (4.31 mmole) ,-10 ℃ of stirring reactions one hour add Sm[N (SiMe again 3) 2] 3(the Li (THF) of μ-Cl) 3The tetrahydrofuran solution of (2.15 mmole), system are yellow, and 50 ℃ of stirring reactions spend the night;
(2) take out and desolvate, add 30 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and adds 4.00 milliliters of hexanes, concentrated solution to 12 milliliter, and ambient temperature overnight is separated out yellow crystals 4.58 and is restrained (1.87 mmole), productive rate 87%.
Embodiment seven: preparation [NO] 2Yb[N (SiMe 3) 2] Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a bromine, R 2, R 3It all is the tertiary butyl.
(1) with 1.63 gram [NO] H 2(4.18 mmole) is dissolved in tetrahydrofuran (THF), and adding contains nThe hexane solution of BuLi (4.18 mmole) ,-10 ℃ of stirring reactions one hour add Yb[N (SiMe again 3) 2] 3(the Li (THF) of μ-Cl) 3The tetrahydrofuran solution of (2.09 mmole), system are yellow, and 50 ℃ of stirring reactions spend the night;
(2) take out and desolvate, add 25 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and adds 4.00 milliliters of hexanes, concentrated solution to 12 milliliter, and ambient temperature overnight is separated out yellow crystals 4.65 and is restrained (1.82 mmole), productive rate 87%.
Embodiment eight: preparation [NO] 2Nd[N (SiMe 3) 2] Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a bromine, R 2, R 3It all is the tertiary butyl.
(1) with 1.40 gram [NO] H 2(3.59 mmole) is dissolved in tetrahydrofuran (THF), and adding contains nThe hexane solution of BuLi (3.59 mmole) ,-10 ℃ of stirring reactions one hour add Nd[N (SiMe again 3) 2] 3(the Li (THF) of μ-Cl) 3The tetrahydrofuran solution of (1.79 mmole), system are blue, and 50 ℃ of stirring reactions spend the night;
(2) take out and desolvate, add 35 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and adds 4.00 milliliters of hexanes, concentrated solution to 15 milliliter, and ambient temperature overnight is separated out blue colored crystal 3.89 and is restrained (1.54 mmole), productive rate 86%.
Embodiment nine: [NO] 2NdN (SiMe 3) 2Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a bromine, R 2, R 3It all is the tertiary butyl.The ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add L-rac-Lactide 1.29 grams (8.97 mmole), add 7.71 milliliters of toluene, add catalyzer after 5 minutes 1.26 milliliter (5.6 * 10 at 70 ℃ of oil bath constant temperature -3Mmole), 70 ℃ of polymerizations 4 hours are with the alcohol termination reaction that contains 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance gets polylactide 0.90 to constant weight after the vacuum-drying and restrains productive rate 82%.The theoretical molecular of polymkeric substance is 18.9 ten thousand [M n(calcd)=144 * 1600 * 82%], GPC actual measurement number-average molecular weight (M n) be 7.38 ten thousand, molecular weight distribution (M w/ M n) be 1.30.
Embodiment ten: [NO] 2NdN (SiMe 3) 2Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a fluorine, R 2, R 3It all is the tertiary butyl.The ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add L-rac-Lactide 0.98 gram (6.78 mmole), add 5.50 milliliters of toluene, add catalyzer after 5 minutes 1.28 milliliter (4.3 * 10 at 70 ℃ of oil bath constant temperature -3Mmole), 70 ℃ of polymerizations 4 hours are with the alcohol termination reaction that contains 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance gets polylactide 0.90 to constant weight after the vacuum-drying and restrains productive rate 85%.The theoretical molecular of polymkeric substance is 19.6 ten thousand [M n(calcd)=144 * 1600 * 85%], GPC actual measurement number-average molecular weight (M n) be 5.93 ten thousand, molecular weight distribution (M w/ M n) be 1.42.
Embodiment 11: [NO] 2NdN (SiMe 3) 2Li 2(THF) 2, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is a chlorine, R 2, R 3It all is the tertiary butyl.The ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add L-rac-Lactide 1.06 grams (7.36 mmole), add 6.00 milliliters of toluene, add catalyzer after 5 minutes 1.36 milliliter (4.6 * 10 at 70 ℃ of oil bath constant temperature -3Mmole), 70 ℃ of polymerizations 4 hours are with the alcohol termination reaction that contains 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance gets polylactide 0.87 to constant weight after the vacuum-drying and restrains productive rate 82%.The theoretical molecular of polymkeric substance is 18.9 ten thousand [M n(calcd)=144 * 1600 * 82%], GPC actual measurement number-average molecular weight (M n) be 6.28 ten thousand, molecular weight distribution (M w/ M n) be 1.30.

Claims (7)

1. the preparation method of an amino aryloxy rare earth metal amide is characterized in that, may further comprise the steps:
(1) under the anhydrous and oxygen-free condition, in the inert atmosphere, amido phenol part and n-Butyl Lithium generation permutoid reaction generate the lithium salts of amido aryloxy;
(2) with the lithium salts and the Ln[N (SiMe of step (1) products therefrom amido aryloxy 3) 2] 3(the Li (THF) of μ-Cl) 3Prepared in reaction in the mixing solutions of tetrahydrofuran (THF) and hexane [NO] 2Ln[N (SiMe 3) 2] Li 2(THF) 2
Wherein, the volume ratio of tetrahydrofuran (THF) and hexane is 10: 1～15: 1 in the mixing solutions of tetrahydrofuran (THF) and hexane;
Wherein, described amino phenol part is [NO] H 2, its chemical structural formula is as follows:
Figure F2009102317602C00011
The chemical structural formula of the lithium salts of described amido aryloxy is as follows:
Described [NO] 2Ln[N (SiMe 3) 2] Li 2(THF) 2Chemical structural formula as follows:
Figure F2009102317602C00013
Wherein Ln is a rare earth metal, is selected from: a kind of in praseodymium, neodymium, samarium, ytterbium or the yttrium; [NO] represents the amido aryloxy ligands, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), X is selected from: a kind of in the saturated alkyl of hydrogen, C1～C4 or the halogen, R 2And R 3Be selected from respectively: a kind of in the methyl or the tertiary butyl.
2. preparation method according to claim 1 is characterized in that, described rare gas element is selected from: a kind of in argon gas or the nitrogen.
3. preparation method according to claim 1 is characterized in that, temperature of reaction is-10 ℃～0 ℃ in the step (1), and the reaction times was at least 1 hour; Temperature of reaction is 40 ℃～50 ℃ in the step (2), and the reaction times was at least 12 hours.
4. preparation method according to claim 1 is characterized in that, in the step (1), according to the ratio of amount of substance, amido phenol part is 1: 1 with the ratio of n-Butyl Lithium material, in the step (2), according to the ratio of amount of substance, step (1) products therefrom and Ln[N (SiMe 3) 2] 3(the Li (THF) of μ-Cl) 3Ratio be 2: 1.
5. preparation method according to claim 1 is characterized in that, above-mentioned product is separated purification, separates the concrete steps of purifying to be: remove and desolvate, the extraction of use toluene, the centrifugal precipitation of removing concentrates clear liquid, add normal hexane, leave standstill crystallization under the normal temperature, can obtain [NO] 2Ln[N (SiMe 3) 2] Li 2(THF) 2Crystal.
6. amino aryloxy rare earth metal amide, the chemical formula of described amino aryloxy rare earth metal amide is: [NO] 2Ln[N (SiMe 3) 2] Li 2(THF) 2, chemical structural formula is as follows:
Figure F2009102317602C00021
Wherein Ln is a rare earth metal, is selected from: a kind of in praseodymium, neodymium, samarium, ytterbium or the yttrium; [NO] represents the amido aryloxy ligands, [NO]=p-X-C 6H 4NCH 2(3-R 2-5-R 3-C 6H 2-2-O), R 2And R 3Be selected from respectively: a kind of in the methyl or the tertiary butyl, it is characterized in that: X is selected from: a kind of in the halogen.
7. the described amino aryloxy rare earth metal amide of claim 6 is as the application of catalysis L-rac-Lactide polymeric single component catalyst.
CN2009102317602A 2009-12-02 2009-12-02 Preparation method of amino aryloxy rare earth metal amide Expired - Fee Related CN101805373B (en)

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CN103626806A (en) * 2013-11-06 2014-03-12 苏州大学 Rare-earth metal arylamine group compound as well as preparation method and application thereof

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US5235031A (en) * 1992-03-13 1993-08-10 E. I. Du Pont De Nemours And Company Polymerization of lactide
CN1175601A (en) * 1996-09-04 1998-03-11 中国科学院成都有机化学研究所 Method for ring-opening polymerization of lactone by catalysis of rare-earth compound
CN1156510C (en) * 2001-10-26 2004-07-07 中国科学院长春应用化学研究所 Process for catalyzing ring-opening polymerization of lactide by 2-valence cyclopentadienyl rare-earth complex

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CN103626806A (en) * 2013-11-06 2014-03-12 苏州大学 Rare-earth metal arylamine group compound as well as preparation method and application thereof
CN103626806B (en) * 2013-11-06 2016-02-03 苏州大学 A kind of Rare-earth metal arylamine group compound and its preparation method and application

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