CN107973815B - Asymmetric aluminum complex containing acetylacetone derivative, and preparation method and application thereof - Google Patents

Asymmetric aluminum complex containing acetylacetone derivative, and preparation method and application thereof Download PDF

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CN107973815B
CN107973815B CN201711315763.5A CN201711315763A CN107973815B CN 107973815 B CN107973815 B CN 107973815B CN 201711315763 A CN201711315763 A CN 201711315763A CN 107973815 B CN107973815 B CN 107973815B
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trifluoromethyl
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methyl
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CN107973815A (en
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王洪宾
姚伟
高爱红
张永芳
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Taishan Medical University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides

Abstract

The invention discloses an asymmetric aluminum complex containing acetylacetone derivatives, and a preparation method and application thereof, wherein the asymmetric aluminum complex has a structural formula shown in a formula I, wherein R is1Is trifluoromethyl or methyl, R2Is phenyl, trifluoromethyl or methyl. The asymmetric aluminum complex catalyst containing the acetylacetone derivative is obtained by reacting the ligand and trimethylaluminum, the preparation method is simple, the cost is low, the product yield is high, the complex has a special structure, the divalent N, N, O and O of the metal center aluminum and the ligand are coordinated, the complex can be used as a catalyst for ring-opening polymerization of cyclic lactone, the catalytic activity is high, the stereoselectivity is good, the reaction rate is high, the polymerization operation is simple, the obtained polymerization product has narrow molecular weight distribution, controllable molecular weight and high yield, and the asymmetric aluminum complex catalyst can be widely used for ring-opening polymerization of cyclic lactone and is an ideal catalyst.

Description

Asymmetric aluminum complex containing acetylacetone derivative, and preparation method and application thereof
Technical Field
The invention relates to an asymmetric aluminum complex containing acetylacetone derivatives and a preparation method thereof, and also relates to application of the asymmetric aluminum complex containing acetylacetone derivatives as a catalyst for ring-opening polymerization of cyclic lactones.
Background
Traditional plastics made from petroleum have several advantages, but have two fatal disadvantages: non-regenerability and non-degradability. Under the condition that petroleum is exhausted as a non-renewable resource, the rapid development of high polymer materials depending on petroleum raw materials is greatly restricted, the high polymer materials are difficult to degrade, and the pollution to human living environment caused by long-term accumulation of a large amount of high polymer material wastes in real life is gradually increased. It is therefore highly desirable to find renewable resources to replace petroleum.
Because polyester is non-toxic, non-irritant and has good biocompatibility, polyester is a biodegradable green environment-friendly high polymer material, and polyester materials are more and more concerned as substitutes of petroleum products. In a natural living environment, the waste polylactone material can be thoroughly decomposed into water and carbon dioxide by microorganisms in soil, is environment-friendly and is renewable. Polyesters are widely used in medical and environmental fields, such as surgical sutures, packaging, drug controlled release and tissue engineering scaffolds, etc. The excellent biocompatibility, biodegradability and sustainable development and utilization performance of the polylactone make the polylactone become a polymer material with the greatest development prospect in the 21 st century.
A convenient method for synthesizing polyester is a ring-opening polymerization method of cyclic lactone, and the synthesis method has the advantages that: controllability of polymerization, narrower molecular weight distribution. At present, most of commonly used catalysts are complexes formed by ligands and metals, in the metal complex catalysts, the selection of the ligands and the selective catalysts of the metals is very critical to the speed of ring-opening polymerization reaction and the performance of the obtained products, under the condition of the same metal, the replacement and selection of the ligands often show unexpected catalytic effects, and under the condition of the same ligand, the replacement of the metals can also generate different catalytic effects, so that the research of new catalysts with good performance is very necessary.
Disclosure of Invention
The invention provides an asymmetric aluminum complex containing acetylacetone derivatives, which can be used as a catalyst for ring-opening polymerization of cyclic lactones, and has the advantages of high catalytic activity, good stereoselectivity, good controllability of molecular weight of the obtained polymer, and good application prospect.
The invention also provides a preparation method of the asymmetric aluminum complex containing the acetylacetone derivative and application of the asymmetric aluminum complex as a catalyst for ring-opening polymerization reaction of cyclic lactone.
The invention is completed under the subsidization of the national Natural fund Commission youth project (No 21104026), and the technical scheme of the invention is as follows:
the asymmetric aluminum complex containing the acetylacetone derivative has a structural formula shown in a formula I:
Figure 514753DEST_PATH_IMAGE001
。
the asymmetric aluminum complex containing the acetylacetone derivative has excellent performance through the selection of a ligand structure and the coordination with metallic aluminumThe selection of the substituent in the body has great influence on the catalytic performance of the aluminum complex as a catalyst for the ring-opening polymerization reaction of the cyclic lactone. Wherein R is1Is trifluoromethyl or methyl, R2Excellent catalytic performance when it is phenyl, trifluoromethyl or methyl, R1、R2May be the same or different. Furthermore, from the aspects of steric hindrance, electron cloud density and the like, the strong electron-withdrawing group (trifluoromethyl) can improve the catalytic activity of the aluminum complex, the large steric hindrance group (phenyl) can increase the stereoselectivity of the aluminum complex, and when R is in the state that R is a radical1Is trifluoromethyl, R2When it is trifluoromethyl, the catalytic activity is higher, and when R is trifluoromethyl1Is trifluoromethyl, R2The stereoselectivity is higher when the phenyl is used.
The asymmetric aluminum complex containing the acetylacetone derivative is obtained by reacting a ligand with trimethylaluminum, and the preparation method comprises the following steps: adding the ligand A into an organic solvent, and then adding the ligand A into the organic solvent at-10 to 0 DEG CoAnd C, adding trimethylaluminum, naturally raising the reaction temperature to room temperature, heating for reaction, and performing vacuum drying, washing and filtering on the reaction mixture to obtain the asymmetric aluminum complex containing the acetylacetone derivative.
The formula of the reaction of the ligand A and trimethylaluminum is shown as follows, wherein the structural formula of the ligand A is shown as the following formula, R1Is trifluoromethyl or methyl, preferably trifluoromethyl; r2Is phenyl, trifluoromethyl or methyl, preferably trifluoromethyl or phenyl:
Figure RE-DEST_PATH_IMAGE002
in the above preparation method, the preparation method of the ligand A comprises the following steps: dissolving p-toluenesulfonic acid into dimethylbenzene, slowly adding ethylenediamine with equimolar amount of p-toluenesulfonic acid, adding phthalic anhydride with equimolar amount of p-toluenesulfonic acid, heating for reflux reaction, cooling to room temperature after the reaction is finished, filtering to obtain a solid, dissolving the solid into dichloromethane, slowly dropwise adding an excessive saturated sodium bicarbonate aqueous solution to remove p-toluenesulfonic acid, and separating after the reaction is finishedDrying the organic phase with anhydrous magnesium sulfate, and then spin-drying the solvent to obtain ethylene diamine protected by unilateral phthalic anhydride; dissolving ethylenediamine protected by single-side phthalic anhydride and an equimolar amount of acetylacetone derivative in methanol, heating for reflux reaction, cooling and filtering after the reaction is finished, and washing and drying the obtained solid with cold methanol to obtain a ligand A; the structural formula of the acetylacetone derivative is shown as the following formula B, wherein R1Is trifluoromethyl or methyl, preferably trifluoromethyl, R2Is phenyl, trifluoromethyl or methyl, preferably trifluoromethyl or phenyl.
Figure RE-563194DEST_PATH_IMAGE003
In the above preparation method, the ligand a and trimethylaluminum undergo an addition reaction, and the methyl group of trimethylaluminum is added to the C = O double bond in the ligand a, and the C = O double bond is changed to a C — O single bond. Is found in by nuclear magnetic characterizationIn the range of = 1.5-2.0, there is a group of CH3The characteristic peak of (A) is NC (O) (Ar) CH 3Middle CH3Characteristic peak of (2).
In the preparation method, the molar ratio of the ligand A to the trimethylaluminum is 1: 1 to 1.3, preferably 1: 1 to 1.05.
In the above preparation method, the organic solvent is one or two of dried hexane, toluene and cyclohexane, and is preferably dried hexane or toluene.
In the preparation method, the dosage of the organic solvent is 5-40 times of the total mass of the reaction raw materials (the ligand A and the trimethylaluminum).
In the preparation method, the reaction is carried out under the protection of gas, and the gas is inert gas or nitrogen.
In the preparation method, the reaction is naturally raised to room temperature and then raised to 30-110 DEG CoC by reaction, e.g. 30oC、40oC、50oC、60oC、70oC、80oC、90oC、100oC、110oC, preferably 40 to 60oC. In the range of 30 to 110oC (preferably 40-60)oC）The reaction time is 1 to 12 hours, preferably 3 to 6 hours. After the reaction, the precipitate was washed with n-hexane.
The asymmetric aluminum complex containing the acetylacetone derivative is an intermediate product for preparing the compound shown in the formula II, the asymmetric aluminum complex containing the acetylacetone derivative is sensitive to water, water is added into a reaction liquid obtained after a ligand A and trimethylaluminum react, the mixture is fully stirred to hydrolyze the aluminum complex, and the compound shown in the formula II is obtained after liquid separation, organic phase collection and solvent recovery of the organic phase, and the obtained remainder is recrystallized. Therefore, the preparation of the aluminum complex is carried out in the absence of water and a protic solvent. In addition, the asymmetric aluminum complex containing the acetylacetone derivative in the formula I can be obtained by using the compound in the formula II as a raw material and replacing the ligand A with the compound in the formula II according to the preparation method of the asymmetric aluminum complex containing the acetylacetone derivative.
Figure RE-405248DEST_PATH_IMAGE004
When the asymmetric aluminum complex containing the acetylacetone derivative is prepared by using the compound shown in the formula II, the organic solvent is one or two of dry hexane, toluene and cyclohexane, and hexane or toluene is preferred. The dosage of the organic solvent is 5-40 times of the total mass of the reaction raw materials (the compound and the trimethylaluminum in the formula II). After the reaction is finished, dried hexane is used for recrystallization, and the asymmetric aluminum complex containing the acetylacetone derivative and having high purity is obtained.
The asymmetric aluminum complex containing the acetylacetone derivative is a complex, N, N, O, O of the ligand is coordinated with aluminum, the structure of the complex is very similar to that of a classical cyclic lactone catalyst (salenAl), the catalytic effect is good, and the stereoselectivity is high. The invention also protects the application of the asymmetric aluminum complex containing the acetylacetone derivative as a catalyst for ring-opening polymerization of cyclic lactone.
The asymmetric aluminum complex containing the acetylacetone derivative is used as the catalyst for the ring-opening polymerization reaction of the cyclic lactoneWhen the agent is used, the ring-opening polymerization of various cyclic lactones can be catalyzed to obtain a series of polylactones. The cyclic lactone may be-one or two of caprolactone, lactide and glycolide, the lactide being, in turn, levolactide, meso-lactide, racemic lactide. When the asymmetric aluminum complex containing the acetylacetone derivative is used as a catalyst to carry out ring-opening polymerization of cyclic lactones, the polymer obtained by the reaction has narrow molecular mass distribution, controllable molecular weight and high yield, especially when the asymmetric aluminum complex is used for catalyzing polymerization of racemic lactide, the isotactic polylactide with high melting point is obtained, and the isotactic polylactide shows higher stereoselectivity and stereoselectivityP mUp to 0.84.
When the asymmetric aluminum complex containing the acetylacetone derivative is used as a catalyst for ring-opening polymerization of cyclic lactone, R is1Is trifluoromethyl, R2The catalytic activity is highest when the compound is trifluoromethyl; when R is1Is trifluoromethyl, R2The stereoselectivity is highest when the phenyl is used.
When the asymmetric aluminum complex containing the acetylacetone derivative is used as a catalyst, the ring-opening polymerization reaction of the cyclic lactone specifically comprises the following steps: mixing an asymmetric aluminum complex catalyst containing acetylacetone derivatives, an organic solvent, an alcohol cocatalyst and cyclic lactone, carrying out ring-opening polymerization reaction under the protection of anhydrous and oxygen-free inert gases, and treating reactants after the reaction to obtain polylactone.
In the ring-opening polymerization reaction, the molar ratio of the cyclic lactone to the asymmetric aluminum complex catalyst containing the acetylacetone derivative is 50-1500: 1, e.g., 50:1, 100: 1. 150:1, 200:1, 300:1, 400:1, 500:1, 600: 1. 800:1, 1000:1, 1200:1, 1500: 1. .
In the ring-opening polymerization reaction, the organic solvent used in the reaction is toluene or tetrahydrofuran, and toluene is preferred.
In the ring-opening polymerization reaction, the alcohol co-catalyst is benzyl alcohol. The molar ratio of the benzyl alcohol cocatalyst to the asymmetric aluminum complex catalyst containing the acetylacetone derivative is 1-3: 1.
in the ring-opening polymerization, the polymerization temperature was 20About 110 ℃ such as 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃. The stereoselectivity of the catalyst tends to be reduced and the catalytic activity tends to be improved along with the increase of the polymerization reaction temperature, and when the reaction temperature is 80 ℃, the stereoselectivity of the racemic lactide can be achievedP m= 0.66, stereoselectivity when catalyzing racemic lactide at 20 deg.CP m= 0.84。
In the ring-opening polymerization reaction, the polymerization reaction time is 1 to 1440 minutes, for example, 1 minute, 4 minutes, 10 minutes, 30 minutes, 40 minutes, 60 minutes, 120 minutes, 240 minutes, 600 minutes, 900 minutes, 1200 minutes, 1440 minutes, and the like.
In the ring-opening polymerization reaction, cold methanol or ethanol is added to purify the polylactone after the reaction, so as to obtain the purified polylactone.
The asymmetric aluminum complex containing the acetylacetone derivative has high catalytic activity when being used as a ring-opening polymerization reaction catalyst, ring opening of cyclic lactone is catalyzed in the presence of benzyl alcohol, and because the structure of the metal center aluminum of the catalyst is an asymmetric structure of NNOO coordination, isotactic polylactide with high melting point is obtained when lactide polymerization is catalyzed, and the obtained polymer is a benzyloxy-terminated polymer. In catalyzing caprolactone and glycolide, the resulting polymer is also a benzyloxy-terminated polymer.
The asymmetric aluminum complex catalyst containing the acetylacetone derivative is obtained by reacting the ligand and trimethylaluminum, the preparation method is simple, the cost is low, the product yield is high, the complex has a special structure, the divalent N, N, O and O of the metal center aluminum and the ligand are coordinated, the complex can be used as a catalyst for ring-opening polymerization of cyclic lactone, the catalytic activity is high, the stereoselectivity is good, the reaction rate is high, the polymerization operation is simple, the obtained polymerization product has narrow molecular weight distribution, controllable molecular weight and high yield, and the asymmetric aluminum complex catalyst can be widely used for ring-opening polymerization of cyclic lactone and is an ideal catalyst.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to be limiting and whose scope is indicated in the claims.
In the examples described below, the stereoselectivity of isotactic polylactide was tested using NMR homonuclear decoupled hydrogen spectroscopy.
Preparation of one-sided protected ethylenediamine (a)
Dissolving 0.50 g of p-toluenesulfonic acid into xylene, slowly adding ethylenediamine with the equimolar amount of the p-toluenesulfonic acid, adding phthalic anhydride with the equimolar amount of the p-toluenesulfonic acid, heating and refluxing for 8 hours, cooling to room temperature after the reaction is finished, filtering, washing and drying the solid to obtain the solid. Dissolving the solid into dichloromethane, slowly dropwise adding an excessive saturated aqueous solution of sodium bicarbonate to remove p-toluenesulfonic acid, reacting at room temperature, separating liquid after the reaction is finished, drying with anhydrous magnesium sulfate, and spin-drying the solvent to obtain 0.48 g of unilateral phthalic anhydride protected ethylenediamine with the yield of 87.3%. The reaction formula is as follows:
Figure 499578DEST_PATH_IMAGE005
preparation of an asymmetric ligand (A) containing an acetylacetone derivative
Asymmetric ligand A containing acetylacetone derivative is obtained by condensation reaction of single-side protected ethylenediamine and acetylacetone or its derivative, and the following examples are given for different synthetic ligands A.
Figure 29917DEST_PATH_IMAGE006
Example 1
The structural formula of the synthesized ligand is shown as the formula (A), wherein R1Is methyl; r2The reaction process is as follows: 0.30 g of the mono-edge protected ethylenediamine (a) and an equimolar amount of acetylacetone were added to 12 mL of methanol, and the mixture was heated under reflux for 12 hours, cooled and filtered after the reaction was completed, and washed with cold methanol, filtered, collected, dried, and weighed to obtain 0.35 g of a solid with a yield of 81.4%.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is methyl; r2The synthesis of the ligand, which is a methyl group, was successful.
1H NMR (400 MHz, CDCl3)10.85 (s, 1H, OH), 8.03 (d,J= 6.4Hz, 2H,Ar–H), 7.56 (d,J= 6.4Hz, 2H, Ar–H), 5.23 (s, 1H, CH), 4.25 (m, 2H, NCH 2),3.42 (m, 2H, =NCH 2), 2.08 (s, 6H, CH 3). HRESI-MS: m/z cacld. C15H16N2O3[M-H]-;271.1085, found: 271.1090.
Example 2
The structural formula of the synthesized ligand is shown as the formula (A), wherein R1Is methyl; r2Is trifluoromethyl, and the reaction process is as follows: 0.20 g of the mono-edge protected ethylenediamine (a) and an equimolar amount of trifluoroacetylacetone were added to 10mL of methanol, and the mixture was refluxed for 12 hours, cooled and filtered after the completion of the reaction and washed with cold methanol, filtered, collected, dried and weighed to obtain 0.30 g of a solid in 88.2% yield.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is methyl; r2The synthesis of the ligand, trifluoromethyl, was successful.
1H NMR (400 MHz, CDCl3)11.25 (s, 1H, OH), 8.05 (d,J= 6.6 Hz, 2H,Ar–H), 7.58 (d,J= 6.6 Hz, 2H, Ar–H), 5.62 (s, 1H, CH), 4.26 (m, 2H, NCH 2),3.45 (m, 2H, =NCH 2), 2.09 (s, 3H, CH 3)。HRESI-MS: m/z cacld. C15H12F3N2O3F[M-H]-; 325.0802, found: 325.0804.
Example 3
The structural formula of the synthesized ligand is shown as the formula (A), wherein R1Is trifluoromethyl; r2Is phenyl, and the reaction process is as follows: adding 0.25 g of single-edge protected ethylenediamine (a) and an equimolar amount of benzoyltrifluoroacetone into 20 mL of methanol, heating and refluxing for 12 hours, cooling and filtering after the reaction is finished and washing with cold methanol, filtering, collecting and dryingThe dry weight was taken to give 0.45 g of solid, 88.2% yield.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is trifluoromethyl; r2The synthesis of ligands that are phenyl groups was successful.
1H NMR (400 MHz, CDCl3)12.05 (s, 1H, OH), 8.07 (d,J= 6.8 Hz, 2H,Ar–H), 7.60 (d,J= 6.8 Hz, 2H, Ar–H), 7.56-7.47(m, 3H, Ar–H),7.19 (d,J=6.0 Hz, 2H, Ar–H), 6.47 (s, 1H, CH), 4.34 (m, 2H, NCH 2), 3.92 (m, 2H, =NCH 2)。HRESI-MS: m/z cacld. C20H15F3N2O3[M-H]-; 387.0956, found: 387.0958.
Example 4
The structural formula of the synthesized ligand is shown as the formula (A), wherein R1Is trifluoromethyl; r2Is trifluoromethyl, and the reaction process is as follows: 0.40 g of the single-edge protected ethylenediamine (a) and an equimolar amount of hexafluoroacetylacetone were added to 20 mL of methanol, and the mixture was heated under reflux for 10 hours, cooled and filtered after the completion of the reaction, and washed with cold methanol, filtered, collected, dried, and weighed to obtain 0.66 g of a solid in 82.5% yield.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is trifluoromethyl; r2The synthesis of the ligand, trifluoromethyl, was successful.
1H NMR (400 MHz, CDCl3)12.14 (s, 1H, OH), 8.76 (d,J= 7.0 Hz, 2H,Ar–H), 7.86 (d,J= 7.0 Hz, 2H, Ar–H), 6.10 (s, 1H, CH), 4.62 (m, 2H, NCH 2),3.64 (m, 2H, =NCH 2)。HRESI-MS: m/z cacld. C15H9F6N2O3F[M-H]-; 379.0518, found:379.0520.
Preparation of aluminum complexes (I) from ligand A
The aluminum complex containing the acetylacetone derivative is a complex formed by the elimination of an alkyl group and the addition of an alkyl group between the ligand A and trimethylaluminum, and the reaction formula is as follows.
Figure RE-755775DEST_PATH_IMAGE008
Example 5
The ligand has the structural formula of formula (A), wherein R1Is methyl; r2The reaction process is as follows: dissolving 0.30 g of ligand A in 10mL of dry toluene under nitrogen atmosphere, adding trimethylaluminum with the molar weight being 1.0 time of that of the ligand A at-10 ℃, heating to 90 ℃ after the reaction temperature naturally rises to room temperature for reaction for 2 hours, vacuumizing the solvent after the reaction is finished, adding dry n-hexane for washing, filtering, collecting, drying and weighing to obtain 0.31 g of solid with the yield of 86.1%.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is methyl; r2The synthesis of the aluminum complex (I) which is methyl is successful.
1H NMR (400 MHz, CDCl3)8.11 (d,J= 7.1Hz, 2H, Ar–H), 7.64 (d,J=7.1Hz, 2H, Ar–H), 5.34 (s, 1H, CH), 4.32 (m, 2H, NCH 2), 3.53 (m, 2H, =NCH 2),2.12 (s, 6H, CH 3), 1.67 (s, 3H, CH 3), –0.45 (s, 3H, AlCH3).
Anal. Calcd for C17H21AlN2O3: C 62.19, H 6.45, N 8.53. Found: C 62.16,H 6.41, N 8.55.
Example 6
The ligand has the structural formula of formula (A), wherein R1Is methyl; r2Is trifluoromethyl, and the reaction process is as follows: under nitrogen atmosphere, 0.34 g of ligand A is dissolved in 10mL of dry cyclohexane, 1.05 times of the molar weight of trimethylaluminum of the ligand A is added at 0 ℃, after the reaction temperature naturally rises to room temperature, the reaction temperature is heated to 50 ℃ for reaction for 5 hours, after the reaction is finished, the solvent is pumped out in vacuum, and dry n-hexane is added for washing, filtering, collecting, drying and weighing to obtain 0.32 g of solid with the yield of 80.0%.
Obtained byThe nuclear magnetic information of the product is as follows, from which R can be seen1Is methyl; r2The aluminum complex (I) which is trifluoromethyl is successfully synthesized.
1H NMR (400 MHz, CDCl3)8.23 (d,J= 7.1 Hz, 2H, Ar–H), 7.66 (d,J=7.1 Hz, 2H, Ar–H), 5.77 (s, 1H, CH), 4.31 (m, 2H, NCH 2), 3.56 (m, 2H, =NCH 2),2.11 (s, 3H, CH 3), 1.65 (s, 3H, CCH 3), –0.51 (s, 3H, AlCH 3).
Anal. Calcd for C17H18AlF3N2O3: C 53.41, H 4.75, N 7.33. Found: C53.46, H 4.71, N 7.40.
Example 7
The ligand has the structural formula of formula (A), wherein R1Is trifluoromethyl; r2Is phenyl, and the reaction process is as follows: 0.30 g of ligand A is dissolved in 10mL of dry hexane under nitrogen atmosphere, 1.1 times of the molar amount of trimethylaluminum of the ligand A is added at-5 ℃, the reaction temperature naturally rises to room temperature, the mixture is heated to 40 ℃ for reaction for 6 hours, and after the reaction is finished, the mixture is filtered, washed by dry n-hexane, filtered, collected, dried and weighed, so that 0.27 g of solid is obtained, and the yield is 79.4%.
The nuclear magnetic information of the obtained product is shown below, from which it can be seen that R is1Is trifluoromethyl; r2The synthesis of the aluminum complex (I) which is phenyl is successful.
1H NMR (400 MHz, CDCl3)8.23(d,J= 7.2 Hz, 2H, Ar–H), 7.72 (d,J=7.2 Hz, 2H, Ar–H), 7.68-7.52(m, 3H, Ar–H),7.32 (d,J= 7.1 Hz, 2H, Ar–H),6.52 (s, 1H, CH), 4.38 (m, 2H, NCH 2), 3.98 (m, 2H, =NCH 2) 1.68 (s, 1H, CCH 3),–0.52 (s, 3H, AlCH 3).
Anal. Calcd for C22H20AlF3N2O3: C 59.46, H 4.54, N 6.30. Found: C59.49, H 4.56, N 6.36.
Example 8
The ligand has the structural formula of formula (A), wherein R1Is trifluoromethyl; r2Is trifluoromethyl, and the reaction process is as follows: under nitrogen atmosphere, 0.32 g of ligand A is dissolved in 10mL of dry toluene, 1.05 times of the molar weight of trimethylaluminum of the ligand A is added at 0 ℃, after the reaction temperature naturally rises to room temperature, the reaction temperature is heated to 110 ℃ for reaction for 1 hour, after the reaction is finished, the solvent is pumped out in vacuum, and dry n-hexane is added for washing, filtering, collecting, drying and weighing to obtain 0.30 g of solid with the yield of 81.1%.
The nuclear magnetic information of the obtained product is shown as follows, and R can be seen from the nuclear magnetic information1Is trifluoromethyl; r2The aluminum complex (I) which is trifluoromethyl is successfully synthesized.
1H NMR (400 MHz, CDCl3)12.30 (s, 1H, OH), 8.60 (d,J= 7.2 Hz, 2H,Ar–H), 7.72 (d,J= 7.2 Hz, 2H, Ar–H), 6.04 (s, 1H, CH), 4.54 (m, 2H, NCH 2),3.72 (m, 2H, =NCH 2)，2.02 (s, 3H, CH 3)，–0.48 (s, 3H, AlCH 3)。
Anal. Calcd for C17H15AlF6N2O3: C 46.80, H 3.47, N 6.42. Found: C46.84, H 3.53, N 6.38.
Preparation of aluminum Complex (I) from ligand II
Figure 867740DEST_PATH_IMAGE008
Example 9
R1Is methyl, R2Synthesis of ligand ii as methyl: under nitrogen atmosphere, ligand A (R)1Is methyl; r2Methyl) 0.25 g is dissolved in 10mL of dry toluene, trimethylaluminum with the molar weight of 1.0 time of ligand A is added at the temperature of minus 10 ℃, the mixture is heated to 50 ℃ for reaction for 5 hours after the reaction temperature naturally rises to the room temperature, 50 microliter of water is added after the reaction is finished, the reaction is stopped, organic phase is separated and collected, anhydrous sodium sulfate is dried, and the mixture is dried by spinningSolvent to obtain crude product, and recrystallizing the crude product with methanol to obtain pure product 0.22 g with yield of 84.6%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)11.02 (s, 1H, OH), 8.10 (d,J= 7.2 Hz, 2H,Ar–H), 7.66 (d,J= 7.2 Hz, 2H, Ar–H), 5.34 (s, 1H, CH), 4.33 (m, 2H, NCH 2),3.56 (m, 2H, =NCH 2), 2.12 (s, 6H, CH 3), 1.67 (s, 3H, CH3).
HRESI-MS: m/z cacld. C16H20N2O3[M-H]-; 287.1394, found: 287.1397.
as can be seen from the above characterization results, the obtained product is R in the above formula (II)1Is methyl; r2A ligand which is a methyl group.
The ligand has the structural formula of formula (II) as above, wherein R1Is methyl; r2The reaction process is as follows: dissolving 0.25 g of ligand II in 10mL of dry toluene in a nitrogen atmosphere, adding trimethylaluminum with the molar weight being 1.1 times that of the ligand II at 0 ℃, heating to 110 ℃ after the reaction temperature naturally rises to room temperature for reaction for 1 hour, vacuumizing the solvent after the reaction is finished, adding dry n-hexane for washing, filtering, collecting, drying and weighing to obtain 0.24 g of solid with the yield of 85.7%. The structural formula of the product is shown as formula I, R1Is methyl; r2Is methyl.
Example 10
R1Is methyl, R2Ligand ii synthesis for trifluoromethyl: under nitrogen atmosphere, ligand A (R)1Is methyl; r2Trifluoromethyl) is dissolved in 10mL of dry cyclohexane, trimethylaluminum with the molar weight of 1.05 times of that of the ligand A is added at 0 ℃, the reaction temperature is naturally raised to room temperature, the reaction temperature is heated to 60 ℃ for 2 hours, 50 microliters of water is added after the reaction to stop the reaction, organic phase is separated and collected, anhydrous sodium sulfate is dried, the solvent is dried in a spinning mode to obtain a crude product, the crude product is recrystallized by methanol to obtain 0.25 g of a pure product, and the yield is 80.6%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)13.01 (s, 1H，OH), 8.27 (s, 1H, CH=N), 7.64(d, J = 7.4 Hz, 1H, Ar–H), 7.55–7.44 (m, 3H, Ar–H), 6.98–6.88 (m, 1H, Ar–H),6.81–6.72 (m, 1H, Ar–H), 4.38–4.31 (m, 2H, NCH2), 4.18–4.09 (m, 2H, NCH2),2.21 (s, 6H, ArCH3), 1.61 (s, 3H, CH3).
HRESI-MS: m/z cacld. C16H17F3N2O3[M-H]-; 341.1113, found: 341.1117.
as can be seen from the above characterization results, the obtained product is R in the above formula (II)1Is methyl; r2Is a ligand of trifluoromethyl.
The ligand has the structural formula of formula (II) as above, wherein R1Is methyl; r2Is trifluoromethyl, and the reaction process is as follows: under nitrogen atmosphere, 0.30 g of ligand II is dissolved in 10mL of dry cyclohexane, 1.0 time of the molar weight of trimethylaluminum of the ligand II is added at minus 10 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 30 ℃ for reaction for 6 hours, after the reaction is finished, the solvent is pumped out in vacuum, and dry n-hexane is added for washing, filtering, collecting, drying and weighing to obtain 0.30 g of solid with the yield of 88.2%. The structural formula of the product is shown as formula I, R1Is methyl; r2Is trifluoromethyl.
Example 11
R1Is trifluoromethyl, R2Ligand ii synthesis for phenyl: under nitrogen atmosphere, ligand A (R)1Is trifluoromethyl; r2Phenyl) 0.20 g is dissolved in 8 mL of dry hexane, trimethylaluminum with the molar weight 1.1 times of that of the ligand A is added at the temperature of minus 5 ℃, the mixture is heated to 40 ℃ after the reaction temperature naturally rises to the room temperature for reaction for 6 hours, 28 microliters of water is added after the reaction is finished to stop the reaction, the organic phase is separated and collected, anhydrous sodium sulfate is dried, the solvent is dried in a spinning mode, a crude product is obtained, the crude product is recrystallized by ethanol, 0.17g of a pure product is obtained, and the yield is 81.0%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)12.25 (s, 1H, OH), 8.14 (d,J= 7.2 Hz, 2H,Ar–H), 7.67 (d,J= 7.2 Hz, 2H, Ar–H), 7.61-7.53(m, 3H, Ar–H),7.16 (d,J=6.8 Hz, 2H, Ar–H), 6.45 (s, 1H, CH), 4.37 (m, 2H, NCH 2), 3.97 (m, 2H, =NCH 2),1.66 (s, 3H, CH3).
HRESI-MS: m/z cacld. C21H19F3N2O3[M-H]-; 403.1272, found: 403.1272.
as can be seen from the above characterization results, the obtained product is R in the above formula (II)1Is trifluoromethyl; r2Is a phenyl ligand.
The ligand has the structural formula of formula (II) as above, wherein R1Is trifluoromethyl; r2Is phenyl, and the reaction process is as follows: under nitrogen atmosphere, 0.40 g of ligand II is dissolved in 10mL of dry hexane, 1.2 times of the molar weight of trimethylaluminum of the ligand II is added at-5 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 50 ℃ for reaction for 4 hours, after the reaction is finished, the solvent is pumped out in vacuum, and dry n-hexane is added for washing, filtering, collecting, drying and weighing to obtain 0.36 g of solid with the yield of 81.8 percent. The structural formula of the product is shown as formula I, R1Is trifluoromethyl; r2Is phenyl.
Example 12
R1Is trifluoromethyl, R2Ligand ii synthesis for trifluoromethyl: under nitrogen atmosphere, ligand A (R)1Is trifluoromethyl; r2Trifluoromethyl) is dissolved in 15mL of dry toluene, trimethylaluminum with the molar weight of 1.0 time of ligand A is added at the temperature of minus 5 ℃, the temperature naturally rises to room temperature, the mixture is heated to 100 ℃ for reaction for 1 hour, 57 microliter of water is added after the reaction is finished to stop the reaction, organic phase is separated and collected, anhydrous sodium sulfate is dried, the solvent is dried in a spinning mode, a crude product is obtained, the crude product is recrystallized by ethanol, 0.35 g of pure product is obtained, and the yield is 83.3%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)12.30 (s, 1H, OH), 8.60 (d,J= 7.2 Hz, 2H,Ar–H), 7.72 (d,J= 7.2 Hz, 2H, Ar–H), 6.04 (s, 1H, CH), 4.54 (m, 2H, NCH 2),3.72 (m, 2H, =NCH 2)，2.02 (s, 3H, CH 3).
HRESI-MS: m/z cacld. C16H13F6N2O3F[M-H]-; 395.0830, found: 395.0818.
as can be seen from the above characterization results, the obtained product is R in the above formula (II)1Is trifluoromethyl; r2Is a ligand of trifluoromethyl.
The ligand has the structural formula of formula (II) as above, wherein R1Is trifluoromethyl; r2Is trifluoromethyl, and the reaction process is as follows: under nitrogen atmosphere, 0.35 g of ligand II is dissolved in 10mL of dry toluene, 1.1 times of the molar weight of trimethylaluminum of the ligand II is added at-5 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 60 ℃ for reaction for 3 hours, after the reaction is finished, the solvent is pumped out in vacuum, and dry n-hexane is added for washing, filtering, collecting, drying and weighing to obtain 0.32 g of solid with the yield of 82.1%. The structural formula of the product is shown as formula I, R1Is trifluoromethyl; r2Is trifluoromethyl.
Preparation of polyglycolide
Example 13
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Methyl), 100 μmol benzyl alcohol, 20 mL toluene, and 10 mmol glycolide, and then placed at 110oAnd C, performing oil bath, adding a small amount of water after reacting for 10 minutes to terminate the reaction, precipitating and washing the product for a plurality of times by using ethanol, and performing vacuum drying at room temperature to obtain 1.10 g of a product, wherein the yield is 94.8 percent, and the molecular weight is 2.0 ten thousand.
Example 14
Polyglycolide was prepared according to the method of example 13 except that: used ofThe catalyst is an aluminum complex shown as a formula I, R1Is methyl; r2Is trifluoromethyl. After 8 minutes of reaction, a small amount of water is added to terminate the reaction, ethanol is used for precipitation and washing for a plurality of times, and vacuum drying is carried out at room temperature, so as to obtain 1.09 g of product, the yield is 94.0%, and the molecular weight is 2.1 ten thousand.
Example 15
Polyglycolide was prepared according to the method of example 13 except that: the catalyst used is an aluminum complex of the formula I, R1Is trifluoromethyl; r2Is phenyl. After 6 minutes of reaction, a small amount of water is added to terminate the reaction, ethanol is used for precipitation and washing for a plurality of times, and vacuum drying is carried out at room temperature to obtain 1.08g of product, the yield is 93.1 percent, and the molecular weight is 2.3 ten thousand.
Example 16
Polyglycolide was prepared according to the method of example 13 except that: the catalyst used is an aluminum complex of the formula I, R1Is trifluoromethyl; r2Is trifluoromethyl. The mass of the product obtained after 5 minutes of reaction was 1.11g, the yield was 95.7%, and the molecular weight was 2.0 ten thousand.
Example 17
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is trifluoromethyl; r2Trifluoromethyl), 100 μmol benzyl alcohol, 20 mL toluene, and 10 mmol glycolide, respectively at 20oC、40oC、60oC、80oC and 100oC, reaction, adding a small amount of water after the reaction is finished, precipitating with methanol, washing for several times, and vacuum drying at room temperature.
Wherein, the reaction lasts for 16 hours at 20 ℃ to obtain 1.09 g of product, the yield is 94.0 percent, and the molecular weight is 2.2 ten thousand.
Reacting at 40 deg.c for 8 hr to obtain 1.10 g of product in 94.8% yield and molecular weight of 2.0 ten thousand.
Reacting at 60 ℃ for 4 hours to obtain 1.10 g of product, wherein the yield is 94.8 percent and the molecular weight is 2.3 ten thousand.
The reaction is carried out for 30 minutes at 80 ℃ to obtain 1.11g of product, the yield is 95.7 percent, and the molecular weight is 1.9 ten thousand.
The reaction is carried out for 12 minutes at 100 ℃ to obtain 1.11g of product, the yield is 95.7 percent, and the molecular weight is 2.2 ten thousand.
Example 18
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Methyl), 30 μmol benzyl alcohol, 10mL tetrahydrofuran and 15 mmol glycolide, then 30oC, after reacting for 15 hours, adding a small amount of water to terminate the reaction, precipitating and washing the product for a plurality of times by using methanol, and drying the product in vacuum at room temperature to obtain 1.66 g of a product, wherein the yield is 95.4 percent, and the molecular weight is 12.1 ten thousand.
Example 19
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R is R) is firstly added into an ampoule after being washed and baked by high-purity nitrogen gas in sequence1Is methyl; r2Trifluoromethyl), 20 μmol benzyl alcohol, 20 mL tetrahydrofuran, and 10 mmol glycolide, and then placed at 50oAnd C, in an oil bath, after reacting for 7 hours, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 1.11g of a product, wherein the yield is 95.7 percent, and the molecular weight is 13.2 ten thousand.
Example 20
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 200 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is trifluoromethyl; r2Phenyl group), 200 μmol benzyl alcohol, 10mL toluene and 10 mmol glycolide, and then the mixture was placed in a 70-degree flaskoAnd C, in an oil bath, after reacting for 2.5 hours, adding a small amount of water to terminate the reaction, precipitating and washing the reaction for a plurality of times by using methanol, and drying the reaction in vacuum at room temperature to obtain 1.09 g of a product, wherein the yield is 94.0 percent, and the molecular weight is 1.0 ten thousand.
Example 21
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Trifluoromethyl), 20 μmol benzyl alcohol, 15mL toluene, and 5 mmol glycolide, then 90oC, after reacting for 4 hours, adding a small amount of water to terminate the reaction, precipitating and washing the product for a plurality of times by using methanol, and drying the product in vacuum at room temperature to obtain 0.55 g of a product, wherein the yield is 94.8 percent, and the molecular weight is 5.6 ten thousand.
Preparation of poly-caprolactone
Example 22
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Methyl), 100 μmol benzyl alcohol, 10mL toluene and 10 mmol caprolactone, and then placed at 110oAnd C, in an oil bath, after reacting for 4 minutes, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 1.10 g of a product, wherein the yield is 96.5 percent, and the molecular weight is 2.2 ten thousand.
Example 23
Polycaprolactone was prepared according to the method of example 22 except that: the catalyst used is an aluminum complex of the formula I, R1Is methyl; r2Is trifluoromethyl. After reacting for 2 minutes, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and vacuum drying at room temperature to obtain 1.11g of product, wherein the yield is 97.4%, and the molecular weight is 1.9 ten thousand.
Example 24
Polycaprolactone was prepared according to the method of example 22 except that: the catalyst used is an aluminum complex of the formula I, R1Is trifluoromethyl; r2Is phenyl. After reacting for 3 minutes, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and vacuum drying at room temperature to obtain 1.11g of product, wherein the yield is 97.4%, and the molecular weight is 2.4 ten thousand.
Example 25
Polycaprolactone was prepared according to the method of example 22 except that: the catalyst used is an aluminum complex of the formula I, R1Is trifluoromethyl; r2Is trifluoromethyl. After 1.5 minutes of reaction, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and standing at room temperatureVacuum drying to obtain 1.12 g of product, yield 98.2% and molecular weight 2.0 ten thousand.
Example 26
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is trifluoromethyl; r2Trifluoromethyl), 100 μmol benzyl alcohol, 10mL toluene, and 10 mmol caprolactone, respectively, then 20oC、40oC、60oC、80oC and 100oC, reaction, adding a small amount of water after the reaction is finished, precipitating with methanol, washing for several times, and vacuum drying at room temperature.
Wherein, the reaction is carried out for 30 minutes at 20 ℃ to obtain 1.09 g of product, the yield is 95.6 percent, and the molecular weight is 2.2 ten thousand.
The reaction was carried out at 40 ℃ for 15 minutes to give 1.10 g of product, 96.5% yield, 2.4 ten thousand molecular weight.
The reaction is carried out for 10 minutes at 60 ℃ to obtain 1.11g of product, the yield is 97.4 percent, and the molecular weight is 1.9 ten thousand.
The reaction is carried out for 8 minutes at 80 ℃ to obtain 1.12 g of product, the yield is 98.2 percent, and the molecular weight is 2.1 ten thousand.
The reaction is carried out for 2 minutes at 100 ℃ to obtain 1.12 g of product, the yield is 98.2 percent, and the molecular weight is 2.0 ten thousand.
Example 27
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Methyl), 30 μmol benzyl alcohol, 10mL tetrahydrofuran and 5 mmol-caprolactone, then 30oC, after reacting for 30 minutes, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and drying in vacuum at room temperature to obtain 0.55 g of a product, wherein the yield is 96.5 percent, and the molecular weight is 5.1 ten thousand.
Example 28
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Trifluoromethyl), 30 μmol benzyl alcohol, 10mL toluene, and 10 mmol-caprolactone, and then placed at 50oAnd C, in an oil bath, after reacting for 15 minutes, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 1.11g of a product, wherein the yield is 97.4 percent, and the molecular weight is 7.2 ten thousand.
Example 29
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is trifluoromethyl; r2Is phenyl), 20 mu mol benzyl alcohol, 15mL toluene and 15 mmol-caprolactone, and then the mixture is placed at 90 DEG CoAnd C, in an oil bath, after reacting for 2 minutes, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 1.65 g of a product, wherein the yield is 96.5 percent, and the molecular weight is 16.1 ten thousand.
Example 30
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Trifluoromethyl), 100 μmol benzyl alcohol, 10mL toluene, and 5 mmol-caprolactone, and then placed at 70oAnd C, in an oil bath, after reacting for 4 minutes, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 0.54 g of a product, wherein the yield is 94.7 percent, and the molecular weight is 1.1 ten thousand.
Preparation of polylactide
Example 31
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Methyl), 100 μmol benzyl alcohol, 20 mL toluene, and 10 mmol racemic lactide, then 20oC, after 22 hours of reaction, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and drying in vacuum at room temperature to obtain 1.36 g of a product with a yield of 94.4%. The product obtained was isotactic polylactide, having a molecular weight of 2.6 ten thousand, isotactic stereoselectivitySelectivity isP m= 0.78。
Example 32
Polylactide was prepared according to the method of example 31, except that: the catalyst used is an aluminum complex of the formula I, R1Is methyl; r2Is trifluoromethyl. After 20 hours of reaction, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and vacuum drying at room temperature to obtain 1.35 g of product with the yield of 93.8%, molecular weight of 2.7 ten thousand, isotactic stereoselectivityP m= 0.81。
Example 33
Polylactide was prepared according to the method of example 31, except that: the catalyst used is an aluminum complex of the formula I, R1Is trifluoromethyl; r2Is phenyl. After 24 hours of reaction, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and vacuum drying at room temperature to obtain 1.37 g of product with the yield of 95.1%, molecular weight of 2.8 ten thousand and isotactic stereoselectivityP m= 0.84。
Example 34
Polylactide was prepared according to the method of example 31, except that: the catalyst used is an aluminum complex of the formula I, R1Is trifluoromethyl; r2Is trifluoromethyl. After reacting for 19 hours, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and vacuum drying at room temperature to obtain 1.42 g of product with the yield of 98.6%, the molecular weight of 2.6 ten thousand and isotactic stereoselectivityP m= 0.82。
Example 35
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is trifluoromethyl; r2Phenyl), 100 μmol benzyl alcohol, 10mL toluene, and 10 mmol racemic lactide, then 40oC、60oC and 80oC, reaction, adding a small amount of water after the reaction is finished, precipitating with methanol, washing for several times, and vacuum drying at room temperature.
Wherein the reaction is carried out at 40 DEG CThe reaction time is 20 hours, 1.38 g of product is obtained, the yield is 95.8 percent, the molecular weight is 2.6 ten thousand,P m= 0.79。
reacting at 60 ℃ for 15 hours to obtain 1.39 g of product, wherein the yield is 96.5 percent, the molecular weight is 2.4 ten thousand,P m= 0.72。
reacting at 80 ℃ for 13 hours to obtain 1.42 g of product, wherein the yield is 98.6 percent, the molecular weight is 2.5 ten thousand,P m= 0.66。
example 36
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 200 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Methyl), 200 μmol benzyl alcohol, 20 mL tetrahydrofuran, and 10 mmol L-lactide, then 30oC, after reacting for 20 hours, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for a plurality of times, and drying in vacuum at room temperature to obtain 1.38 g of a product, wherein the yield is 95.8 percent, and the molecular weight is 1.0 ten thousand.
Example 37
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is methyl; r2Trifluoromethyl), 10 μmol benzyl alcohol, 10mL tetrahydrofuran, and 5 mmol meso-lactide, and then placed at 50oAnd C, in an oil bath, after reacting for 13 hours, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 0.68 g of a product, wherein the yield is 94.4 percent, and the molecular weight is 10.8 ten thousand.
Example 38
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is trifluoromethyl; r2Trifluoromethyl), 30 μmol benzyl alcohol, 20 mL toluene, and 10 mmol L-lactide, and then placed at 90%oC, oil bath, adding a small amount of water to stop the reaction after 3 hours of reaction, precipitating and washing by using ethanol for a plurality of times, and drying in vacuum at room temperature to obtain 1.37 g of product with the yield of 95.1 percentAnd a sub-amount of 7.4 ten thousand.
Example 39
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (aluminum complex shown in formula I, R) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas1Is trifluoromethyl; r2Trifluoromethyl)), 20 μmol benzyl alcohol, 20 mL toluene, and 15 mmol L-lactide, and then placed at 110oAnd C, in an oil bath, after reacting for 3 hours, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 2.10 g of a product, wherein the yield is 97.2 percent, and the molecular weight is 16.9 ten thousand.
Comparative example 1
Preparation of nickel catalyst: the ligand has the structural formula as shown in formula (II), R1Is trifluoromethyl; r2Is trifluoromethyl, and the reaction process is as follows: dissolving 0.30 g of ligand in 10mL of absolute ethyl alcohol, adding nickel acetate with the molar weight being 1.0 time of that of the ligand at room temperature, heating and refluxing for 12 hours, concentrating the solvent in vacuum after the reaction is finished, adding dichloromethane to precipitate a solid, filtering, washing with hexane, and drying to obtain the nickel catalyst, wherein the structural formula of the nickel catalyst is shown as the following.
Figure 535219DEST_PATH_IMAGE009
Polylactide was prepared according to the method of example 39, except that: the catalyst used was the nickel catalyst described above. After 24 hours of reaction, a small amount of water is added to terminate the reaction, methanol is used for precipitation and washing for a plurality of times, and vacuum drying is carried out at room temperature to obtain 0.46 g of product, the yield is 21.3 percent, and the molecular weight is 3.1 ten thousand. The nickel catalyst has too low activity for lactide polymerization and is of no value.
Comparative example 2
Preparation of aluminum catalyst: the ligand has the formula (LH)2) The reaction process is as follows: dissolving 0.20 g of ligand in 10mL of toluene under the protection of anhydrous oxygen-free inert gas, adding trimethylaluminum with the molar weight being 1.0 time of that of the ligand at the temperature of-5 ℃, slowly heating to room temperature, heating to 80 ℃ for reaction for 12 hours, concentrating the solvent in vacuum after the reaction is finished, adding dry hexane to precipitate solidsFiltering, washing with hexane, and drying to obtain the aluminum catalyst, wherein the structural formula of the aluminum catalyst is LAlMe shown in the specification.
Figure 388906DEST_PATH_IMAGE010
Polylactide was prepared according to the method of example 35, except that: the catalyst used was the aluminum catalyst. Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 100 mu mol of catalyst, 100 mu mol of benzyl alcohol, 10mL of toluene and 10 mmol of racemic lactide into an ampoule after being washed and baked by high-purity nitrogen gas, and then respectively adding the mixture into a flask with the volume of 20 mu mol of catalyst, 100 mu mol of benzyl alcohol, 10mL of toluene and 10 mmol of racemic lactideoC and 80oC, reaction, adding a small amount of water after the reaction is finished, precipitating with methanol, washing for several times, and vacuum drying at room temperature.
Wherein, no product is generated after the reaction is carried out for 36 hours at 20 ℃, which indicates that the catalyst can not catalyze the polymerization of the lactide at lower temperature.
Reacting at 80 deg.C for 24 hr to obtain 1.15 g product with 79.9% yield, 1.4 ten thousand molecular weight and isotactic stereoselectivityP m= 0.53. Both stereoselectivity and activity were lower compared to the aluminum catalyst of example 35.
Comparative example 3
Polylactide was prepared according to the method of example 31, except that: the catalyst used was the catalyst used in example 10 of patent 201410609375.8. The polylactide obtained after the reaction is non-uniform stereoregular polylactide with the mass of 1.33 g, the yield of 92.4 percent, the molecular weight of 1.7 ten thousand and the non-uniform stereoregular stereoselectivityP rIs 0.71.
Comparative example 4
The ligand has a structural formula shown in formula (A), wherein R1Is methyl; r2Is trifluoromethyl, and the reaction process is as follows: dissolving 0.34 g of ligand A in 10mL of dry cyclohexane under nitrogen atmosphere, adding triisopropylaluminum with the molar weight being 1.05 times that of the ligand A at 0 ℃, heating the reaction temperature to 50 ℃ after the reaction temperature naturally rises to room temperature for reaction for 5 hours, adding 47 microliters of water after the reaction to stop the reaction, separating liquid and collecting an organic phase,the solvent was dried over anhydrous sodium sulfate to obtain a crude product, and no change was found in the obtained compound (isopropyl group did not undergo C = O addition reaction). Triisopropylaluminum failed to undergo addition reaction.
Comparative example 5
Dissolving p-toluenesulfonic acid into xylene, slowly adding 1, 3-propane diamine with equimolar amount of p-toluenesulfonic acid, adding phthalic anhydride with equimolar amount of p-toluenesulfonic acid, heating for reflux reaction, cooling to room temperature after the reaction is finished, filtering the solid, washing, and drying to obtain the solid. Dissolving the solid into dichloromethane, slowly dropwise adding an excessive saturated aqueous solution of sodium bicarbonate, reacting at room temperature, separating after the reaction is finished, drying with anhydrous magnesium sulfate, and spin-drying the solvent to obtain the unilateral phthalic anhydride protected 1, 3-propanediamine. Heating and refluxing unilateral phthalic anhydride protected propane diamine and equimolar hexafluoroacetylacetone in methanol, cooling in a refrigerator after the reaction is finished, separating out a solid, filtering, washing with cold methanol, and drying to obtain a compound LD.
Preparation of aluminum catalyst: under nitrogen atmosphere, 0.30 g of compound LD is dissolved in 10mL of dry toluene, 1.1 time of trimethylaluminum in the molar weight of the compound LD is added at minus 5 ℃, the temperature naturally rises to room temperature, the mixture is heated to 100 ℃ for reaction for 3 hours, after the reaction is finished, the solvent is pumped out in vacuum, and dried n-hexane is added for washing, filtering and drying to obtain 0.27 g of solid with the yield of 79.4 percent, and after the aluminum compound is hydrolyzed, mass spectrometry shows that the ligand can only perform addition reaction on one side to obtain LDAlMe2（HRESI-MS: m/z cacld. C16H12F6N2O3[M-H]-; 393.0676, found: 393.0670）。
Polylactide was prepared according to the method of example 31, except that: the catalyst used was the aluminum catalyst. The mass of the product obtained after the reaction is 0.66 g, the yield is 45.8%, the molecular weight is 1.1 ten thousand, and stereoselectivity is avoided.
Figure 781841DEST_PATH_IMAGE011

Claims (13)

1. An asymmetric aluminum complex containing acetylacetone derivatives, which is characterized in that: which has the structural formula shown in formula I, wherein R1Is trifluoromethyl or methyl, R2Is phenyl, trifluoromethyl or methyl;
Figure DEST_PATH_IMAGE001
。
2. the asymmetric aluminum complex containing acetylacetone derivative according to claim 1, which is characterized in that: r1Is trifluoromethyl, R2Is trifluoromethyl or phenyl.
3. A method for preparing an asymmetric aluminum complex containing an acetylacetone derivative according to claim 1, which comprises the steps of: adding the ligand A or the ligand II into an organic solvent at-10 to 0%oAdding trimethylaluminum under C, naturally raising the reaction temperature to room temperature after the addition is finished, and then raising the temperature to 30-110 DEG CoC, reacting, and then, carrying out vacuum drying on the solvent, washing and filtering to obtain the asymmetric aluminum complex containing the acetylacetone derivative shown in the formula I; the structural formulas of the ligand A and the ligand II are shown in the specification, wherein R1Are each trifluoromethyl or methyl, R2Are each phenyl, trifluoromethyl or methyl;
Figure DEST_PATH_IMAGE003
。
4. the method of claim 3, wherein: r1Are each trifluoromethyl, R2Are both trifluoromethyl or phenyl.
5. The method of claim 3, wherein: the molar ratio of the ligand A or the ligand II to the trimethylaluminum is 1: 1 to 1.3.
6. The method according to claim 5, wherein: the molar ratio of the ligand A or the ligand II to the trimethylaluminum is 1: 1 to 1.05.
7. The method of claim 3, wherein: the organic solvent is one or two of dry hexane, toluene and cyclohexane.
8. The method of claim 3, wherein: the dosage of the organic solvent is 5-40 times of the total mass of the reaction raw materials.
9. The method of claim 3, wherein: after the temperature is raised to the room temperature, the temperature is raised to 30-110 DEGoC, reacting for 1-12 hours.
10. The method of claim 9, wherein: after the temperature is raised to the room temperature, the temperature is raised to 40-60 DEGoC, reacting for 3-6 hours.
11. The method of claim 3, wherein: the reaction is carried out under the protection of inert gas.
12. Use of the asymmetric aluminum complex containing an acetylacetone derivative according to claim 1 or 2 as a catalyst for a ring-opening polymerization of a cyclic lactone.
13. Use according to claim 12, characterized in that: the cyclic lactone is levo-lactide, meso-lactide, racemic lactide, caprolactone or glycolide.
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