CN115368411A - Zinc complex and preparation method thereof - Google Patents

Zinc complex and preparation method thereof Download PDF

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CN115368411A
CN115368411A CN202110546875.1A CN202110546875A CN115368411A CN 115368411 A CN115368411 A CN 115368411A CN 202110546875 A CN202110546875 A CN 202110546875A CN 115368411 A CN115368411 A CN 115368411A
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zinc
complex
alkyl
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aromatic
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CN115368411B (en
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张文娟
曹芙蓉
张海霞
张泽宇
孙文华
蒋友淑
王锐
王云
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Beijing Institute Fashion Technology
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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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/60—Quinoline or hydrogenated quinoline ring systems
    • 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
    • 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
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof

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Abstract

The invention provides a zinc complex, which comprises a hydrogenated quinoline unit and a secondary amino group, wherein zinc is coordinated with a nitrogen atom in the zinc complex. The complex has good air stability and moisture stability, high activity, can rapidly catalyze the ring-opening polymerization of the cyclic ester in batches, is convenient to store and use, and has good industrial application prospect.

Description

Zinc complex and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a zinc complex with N ^ N coordination and a preparation method thereof, and the complex is used for catalyzing ring opening of cyclic ester.
Background
In recent years, researchers find that biodegradable polyesters can achieve mechanical properties similar to those of polymers produced by using petroleum as raw materials, have good biocompatibility, can be completely converted into water and carbon dioxide under specific conditions, and can be used as powerful substitutes for petroleum products. At present, the biodegradable polyester is applied to bioengineering, medical drugs, food packaging, building materials, agricultural appliances and daily life. However, it has many problems such as high production cost, large amount of catalyst used, and uneven product quality.
The main production way of the biodegradable polyester is to use a catalyst to catalyze the ring-opening polymerization of cyclic ester to obtain the biodegradable polyester. Among them, metal complexes have been widely studied because they have excellent catalytic performance in the ring opening of cyclic esters and the operation process of polymerization is simple. The existing catalysts can be classified into: zinc complex system, iron complex system, aluminum complex system, magnesium complex system, indium complex system, alkali metal complex system, rare earth metal complex system, and the like. However, most of the catalytic systems for the polymerization of cyclic esters are extremely sensitive to air and water, and the storage and use conditions are harsh, so that the industrialization is difficult. There is a high demand for catalysts with high activity and air stability.
The zinc element is one of indispensable elements in human body, has biocompatibility and safety and low price, and the zinc metal compound has better catalytic activity and certain stereoselectivity in the process of catalyzing the ring-opening polymerization of the cyclic ester. At present, there are many reports on zinc metal compounds, and the zinc metal compounds are mainly classified into the following categories according to the structure of ligands: n, N-coordinated zinc compounds (polyhedron, 2012,682-687, j.coord.chem.,2017, 3837-3858), N-coordinated zinc compounds (j.organomet chem.,2010,1155-1162, angelw.chem.int.ed.2016, 55, 8680-8685), N, O-coordinated compounds (Dalton trans.,2010,39,7897-7910, eur.polym.j.,2020,122,109302), and the like. Meanwhile, a small amount of phosphorus-containing zinc complexes have been reported (Dalton Trans.,2010,39,8748-8758, chem. Eur.J.2012,18,2349-2360 Dalton Trans.,2015,44,12376-12387), and these phosphorus atom-containing catalysts have low activity and the like in general.
Reports that catalysts developed so far can catalyze ring-opening polymerization of cyclic esters efficiently in a short time are rare, and these compounds are very sensitive to air and humid environments. Therefore, there is a need for further development of a zinc catalyst having high activity and good stability, which can provide a polymer product having excellent properties under mass production conditions.
Disclosure of Invention
In order to solve the problems, the invention provides a zinc complex, a ligand of the complex comprises a hydrogenated quinoline unit and a secondary amino group, the zinc complex has good air stability and moisture stability, can quickly catalyze ring-opening polymerization of batch caprolactone and other cyclic esters, has a simple process, is convenient to store and transport, has high catalysis efficiency, and has a good industrial application prospect, and thus the invention is completed.
It is an object of the first aspect of the invention to provide a zinc complex comprising a hydroquinoline unit and a secondary amine group, preferably further comprising an aromatic phosphine unit. In the zinc complex, zinc is coordinated with a nitrogen atom in a hydrogenated quinoline unit and a secondary amine group.
Preferably, the zinc complex comprises the structure of formula (1):
Figure BDA0003073831790000031
wherein R is selected from hydrogen, alkyl, halogenated group or aromatic group, preferably selected from hydrogen and C 1 -C 5 Alkyl, fluoro, chloro, bromo, phenyl, alkylphenyl, alkoxyphenyl of (a), more preferably hydrogen, methyl, isopropyl, chloro or phenyl;
m is the number of ligands to which zinc binds, is 1 or 2, preferably 1;
the formula (1) is combined with anions to obtain the neutral zinc complex, and the anions can be any combinable anions such as chloride ions, bromide ions, nitrate ions, acetate ions and the like.
More preferably, the zinc complex is:
zn1: r is hydrogen (H), m is 1, and the anion is chloride;
zn2: r is methyl (Me), m is 1, and the anion is chloride;
zn3: r is isopropyl (iPr), m is 1, and the anion is chloride;
zn4: r is chlorine (Cl), m is 1, and the anion is chloride; or
Zn5: r is phenyl (Ph), m is 1, and the anion is chloride.
The second aspect of the present invention is directed to provide a preparation method of the zinc complex, wherein the method is to prepare the zinc complex by reacting a ligand compound with a zinc salt.
The ligand compound is a compound containing a hydrogenated quinoline unit and a secondary amine group, and preferably, further contains an aromatic phosphine unit. Preferably, the ligand compound has the following general structural formula:
Figure BDA0003073831790000041
wherein,
r is selected from hydrogen, alkyl, halo or aryl, preferably selected from hydrogen, C 1 -C 5 Alkyl, fluoro, chloro, bromo, phenyl, alkylphenyl, alkoxyphenyl of (a), more preferably hydrogen, methyl, isopropyl, chloro or phenyl;
g is an aromatic phosphine group, preferably a phenylphosphino group or a diphenylphosphino group, more preferably a diphenylphosphino group;
n is 1 to 6, preferably 2 to 4, more preferably 2 or 3.
The zinc salt is an ionizable zinc salt.
The zinc complex and the preparation method thereof provided by the invention have the following excellent effects:
(1) The ligand of the zinc complex provided by the invention contains a hydrogenated quinoline unit, a secondary amino group and an aromatic phosphine unit, has good stability even in a humid air environment, is convenient to transport and store, is more beneficial to safe and effective use in a production process, and is beneficial to industrial production.
(2) The zinc complex has good catalytic activity, can complete polymerization of cyclic ester, especially caprolactone, in a short time, has a small using amount, and can complete batch synthesis of polyester.
(3) The zinc complex has simple preparation process and low synthesis cost, can be prepared at room temperature, and is beneficial to reducing the cost of the catalyst.
(4) The zinc complex provided by the invention can catalyze cyclic ester polymerization to realize molecular weight controllable polymerization, the molecular weight distribution is narrow, a high-quality polymerization product is obtained, and the biological safety is good, so that the application field of polyester is widened, and particularly the application in biomedicine is realized.
Detailed Description
The present invention will now be described in detail by way of specific embodiments, and features and advantages of the present invention will become more apparent and apparent from the following description.
The zinc complex provided by the invention takes organic molecules comprising a hydrogenated quinoline unit and a secondary amino group as ligands, has good stability even in a humid and air environment, has good catalytic activity, can catalyze the ring-opening polymerization of cyclic ester in batches, and particularly can meet the requirements of industrial development and application of caprolactone polymers.
In a first aspect the present invention provides a zinc complex comprising a hydroquinoline unit and a secondary amine group, preferably further comprising an aromatic phosphine unit. In the zinc complex, zinc is coordinated to a nitrogen atom in a hydrogenated quinoline unit and a secondary amine group.
Preferably, the ligand of the zinc complex has the following general structural formula:
Figure BDA0003073831790000051
wherein,
r is selected from hydrogen, alkyl, halo or aryl, preferably selected from hydrogen, C 1 -C 5 Alkyl, fluoro, chloro, bromo, phenyl, alkylphenyl, alkoxyphenyl of (a), more preferably hydrogen, methyl, isopropyl, chloro or phenyl;
g is an aromatic phosphine group, preferably a phenylphosphino group or a diphenylphosphino group, more preferably a diphenylphosphino group;
n is 1 to 6, preferably 2 to 4, more preferably 2 or 3.
Preferably, the zinc complex comprises the structure of formula (1):
Figure BDA0003073831790000061
wherein R is selected from hydrogen, alkyl, halogenated group or aromatic group, preferably selected from hydrogen and C 1 -C 5 Alkyl, fluoro, chloro, bromo, phenyl, alkylphenyl, alkoxyphenyl of (a), more preferably hydrogen, methyl, isopropyl, chloro or phenyl;
m is the number of ligands to which zinc binds, is 1 or 2, preferably 1;
the formula (1) is combined with anions to obtain the neutral zinc complex, and the anions can be any combinable anions such as chloride ions, bromide ions, nitrate ions, acetate ions and the like.
More preferably, the zinc complex is:
zn1: r is hydrogen (H), m is 1, and the anion is chloride;
zn2: r is methyl (Me), m is 1, and the anion is chloride;
zn3: r is isopropyl (iPr), m is 1, and the anion is chloride;
zn4: r is chlorine (Cl), m is 1, and the anion is chloride; or
Zn5: r is phenyl (Ph), m is 1, and the anion is chloride.
In the zinc complexes of the invention, the zinc atom is d 10 An electronic structure of the electronic device is disclosed,is sp 3 And the hybridization is carried out, electrons fill the whole d orbit, so that the complex has good stability and can still keep chemical stability in air or a humid environment. Has good activity in the environment of cyclic ester polymerization, and can quickly catalyze the ring-opening reaction of batch cyclic ester, especially caprolactone and lactide. Therefore, the method is beneficial to industrial production.
The zinc complex is used as a catalyst to catalyze the cyclic ester polymerization, such as the ring-opening polymerization of caprolactone, lactide and glycolide, and particularly the ring-opening polymerization of caprolactone has high activity and can prepare the polycyclic ester with controllable molecular weight and narrow molecular weight distribution.
The second aspect of the invention provides a preparation method of the zinc complex, and the method is to prepare the zinc complex by reacting a ligand compound with a zinc salt.
The ligand compound is a compound comprising a hydrogenated quinoline unit and a secondary amine group, and preferably, further comprises an aromatic phosphine unit. Preferably, the ligand compound has the following general structural formula:
Figure BDA0003073831790000071
wherein R, G and n are as described in the first aspect.
The ligand compound is prepared from raw materials including hydrogenated quinolinone compounds and aromatic phosphino alkyl amine compounds.
The hydrogenated quinolinone compound is dihydroquinolinone or dihydroquinolinone with 2-position substituent, and the substituent is selected from hydrogen, alkyl, halogenated group or aromatic group, preferably selected from hydrogen and C 1 -C 5 And more preferably hydrogen, methyl, isopropyl, chlorine substituents or phenyl.
Preferably, the hydrogenated quinolinone compound is selected from compounds represented by formula (2):
Figure BDA0003073831790000072
wherein R is as described in the first aspect.
In the aromatic phosphinoalkylamine compounds, the aromatic phosphine group is preferably a phenylphosphino group or a diphenylphosphino group, and more preferably a diphenylphosphino group; alkyl is C 1 -C 6 Alkyl, preferably C 2 -C 4 Alkyl, more preferably ethylene or propylene, such as 2-diphenylphosphinoethylamine, diphenylphosphinomethane, 3-diphenylphosphinopropylamine.
The molar ratio of the hydrogenated quinolinone compound to the aromatic phosphinoalkylamine compound is 1 (0.8-1.4), preferably 1 (1.0-1.2).
The reaction is carried out in the presence of a catalyst, wherein the catalyst is selected from one or more of sodium borohydride, p-toluenesulfonic acid, sodium triacetyl borohydride, formic acid and acetic acid, preferably selected from sodium borohydride or sodium triacetyl borohydride, and more preferably selected from sodium triacetyl borohydride.
The reaction is to add the hydrogenated quinolinone compound and the aromatic phosphino alkyl amine compound into a solvent for reaction, wherein the solvent is selected from halogenated hydrocarbon solvents, such as 1,2-dichloroethane. The reaction is carried out under a protective atmosphere, such as a nitrogen atmosphere.
After the reaction is finished, adding saturated bicarbonate solution to quench the reaction, such as sodium bicarbonate, extracting an organic layer by using an ester solvent, such as ethyl acetate, combining the organic layers after the extraction is finished, removing the solvent of the organic layer, and separating by using an aluminum oxide chromatographic column to obtain the ligand compound.
The zinc salt is an ionizable zinc salt selected from zinc chloride, zinc nitrate, zinc bromide, zinc acetate, and the like, such as zinc chloride.
In the method, the ligand compound and the zinc salt are added into a solvent and stirred for reaction, and preferably, a zinc salt solution is added into a ligand compound solution, and is preferably dropwise added.
The reaction solvent is selected from one or more of water, alcohol solvents and ether solvents, preferably one or more of water, methanol, ethanol, isopropanol and diethyl ether, and more preferably ethanol.
The concentration of the ligand compound solution is 0.05 to 0.7mol/L, preferably 0.15 to 0.5mol/L, and more preferably 0.25 to 0.35mol/L. The concentration of the zinc salt solution is 0.1-1.40mol/L, preferably 0.30-1.00mol/L, and more preferably 0.55-0.70mol/L.
The molar ratio of the ligand compound to the zinc salt is 1 (0.6-1.6), preferably 1 (0.8-1.4), and more preferably 1 (1.0-1.2). In a preferred mode of the present invention, the ligand compound and the zinc salt are reacted in nearly equimolar amounts, for example, if excessive ligand or zinc salt exists in the reaction system, the excessive ligand or zinc salt is difficult to remove after the reaction is finished, which affects the subsequent reaction.
The reaction temperature is 15-38 ℃, and preferably 20-30 ℃; the reaction time is 6-18h, preferably 10-14h.
And after the reaction is finished, filtering the reaction liquid, preferably, filtering the reaction liquid at the temperature of lower than 20 ℃, washing the obtained precipitate, wherein the washing liquid is a cold reaction solvent, and drying the precipitate to obtain the zinc complex.
The zinc complex provided by the invention has good stability to air and water, good biological safety and biocompatibility in the using process, and high catalytic cyclic ester ring-opening polymerization activity, is used for mass catalytic production of the cyclic ester, obtains the cyclic ester with good biological safety, controllable molecular weight and narrow molecular weight distribution, and has good popularization application prospect.
When the zinc complex is used for catalyzing the ring-opening polymerization of lactide, the ring-opening reaction of lactide monomer with the molar weight being 250 times that of the catalyst can be completed within 30min, and the monomer conversion rate can reach more than 99 percent at most.
When the zinc complex is used for catalyzing the ring-opening polymerization of caprolactone, the epsilon-caprolactone monomer polymerization with the molar weight of 250-5000 times that of the catalyst can be completed within 10min, and the highest number average molecular weight can reach 8 multiplied by 10 4 g/mol, the molecular weight distribution index is within the range of 1.00-1.55, and the highest monomer conversion rate can reach more than 99%.
Examples
The monomer conversions of the cyclic esters obtained in the following examples were all determined 1 H NMR measurement.
Example 1
In a schleck bottle, 8mmol of 2-diphenylphosphinylethylamine and 9mmol of 6, 7-dihydro-5H-quinolin-8-one are added, then 16mmol of sodium triacetoxyborohydride is added, the reaction system is replaced by a nitrogen atmosphere, 80mL of dry 1,2-dichloroethane is added, and the mixture is stirred at room temperature for 6 hours, so that white solids in the reaction system gradually disappear. After the reaction is finished, quenching the mixture by using saturated sodium bicarbonate solution, separating an organic layer, extracting an aqueous layer by using ethyl acetate for three times, combining the obtained organic layers, removing the solvent, and separating and purifying the obtained crude product by using petroleum ether and ethyl acetate through alumina column chromatography to obtain the N- (2- (diphenylphosphino) ethyl) -5,6,7,8-tetrahydroquinolinone-8-amine.
In a flask, 1.18g N- (2- (diphenylphosphino) ethyl) -5,6,7,8-tetrahydroquinolin-one-8-amine (about 3.28 mmol) was dissolved in 10ml ethanol and then 0.45g ZnCl was contained 2 A solution of 5ml of ethanol (about 3.28 mmol) was added dropwise to the flask, stirred at room temperature for 12 hours, and filtered. Washed three times with cold ethanol and dried in a vacuum oven for 12 hours, resulting in 1.39g of zinc complex Zn1 with a yield of 85%.
The structural characterization data are as follows:
1 H NMR(C 3 D 7 NO,300MHz):δppm 8.53-8.51(d,J＝4.5Hz,1H,Py),7.95-7.62(d,J＝7.5Hz,1H,CH),7.62-7.41(m,12H,Ph+Py),4.08(s,1H,CH),3.23(br,s,1H,CH),3.06-2.75(m,4H,CH 2 ),2.53-2.50(d,J＝8.4,2H,CH 2 ),2.07-2.01(d,J＝15.3,1H,CH),1.90-1.73(m,2H,CH 2 )。
13 C NMR(C 3 D 7 NO,75MHz):δ154.69,145.46,141.30,138.14,137.11,135.30,132.98,132.79,132.56,132.37,129.17,128.98,128.85,128.81,128.79,128.75,124.55。
31 P NMR(C 3 D 7 NO , 162MHz):δ-21.62。
example 2
N- (2- (diphenylphosphino) ethyl) -2-methyl-5,6,7,8-tetrahydroquinolin-8-amine was prepared as in example 1, except that: 2-methyl-6,7-dihydro-5H-quinolin-8-one was used instead of 6,7-dihydro-5H-quinolin-8-one.
The zinc complex Zn2 was prepared as in example 1, with the only difference that: n- (2- (diphenylphosphino) ethyl) -2-methyl-5,6,7,8-tetrahydroquinolin-one-8-amine was used instead of N- (2- (diphenylphosphino) ethyl) -5,6,7,8-tetrahydroquinolin-one-8-amine, yield 68%.
The structural characterization data is as follows:
1 H NMR(C 3 D 7 NO,400MHz):δppm 7.86-7.84(d,J＝7.6Hz,1H,Py),7.61(s,2H,Py),7.48-7.41(m,10H,Ph),4.01(s,1H,CH),3.51(s,H,CH),3.28(s,1H,CH),2.91-2.85(m,4H,CH 2 ),2.75(s,3H,CH 3 ),2.53-2.46(m,2H,CH 2 ),2.01(s,1H,CH),1.85-1.74(m,2H,CH 2 )。
13 C NMR(C 3 D 7 NO,100MHz):δ155.40,154.02,142.03,138.72,138.59,137.51,137.38,133.10,132.91,132.64,132.45,132.35,129.30,129.08,129.04,128.99,128.97,128.92,125.74,58.69,44.95,44.68,27.98,27.85,27.33,26.64,23.05,20.72。
31 P NMR(C 3 D 7 NO , 162MHz):δ-20.88。
example 3
N- (2- (diphenylphosphino) ethyl) -2-isopropyl-5,6,7,8-tetrahydroquinolin-8-amine was prepared as in example 1, except that: 2-isopropyl-6,7-dihydro-5H-quinolin-8-one instead of 6,7-dihydro-5H-quinolin-8-one.
The zinc complex Zn3 was prepared as in example 1, with the only difference that: n- (2- (diphenylphosphino) ethyl) -2-isopropyl-5,6,7,8-tetrahydroquinolin-one-8-amine was used instead of N- (2- (diphenylphosphino) ethyl) -5,6,7,8-tetrahydroquinolin-one-8-amine, yield 75%.
The structural characterization data are as follows:
1 H NMR(C 3 D 7 NO,400MHz):δppm 7.97-7.95(d,J＝8.4Hz,1H,Py),7.67-7.65(d,J＝8.0Hz,1H,Py),7.58-7.40(m,10H,Ph),4.04-4.01(d,J＝9.2Hz,1H,CH),3.21-3.14(m,1H,CH),3.04-2.96(m,1H,CH),2.90-2.80(m,3H,CH,CH 2 ),2.52-2.51(m,2H,CH 2 ),2.05-2.02(m,1H,CH),1.86-1.73(m,2H,CH 2 )。
13 C NMR(C 3 D 7 NO,100MHz):δ164.81,142.33,138.57,138.44,137.27,132.29,132.49,132.31,129.11,128.91,128.86,128.82,128.79,128.75,120.82,58.41,44.66,36.54,27.70,27.58,27.30,26.51,23.06,21.57,20.53。
31 P NMR(C 3 D 7 NO , 162MHz):δ-17.34。
example 4
2- (diphenylphosphino) ethyl) -2-chloro-5,6,7,8-tetrahydroquinolin-8-amine was prepared as in example 1, except that: 2-chloro-6,7-dihydro-5H-quinolin-8-one instead of 6,7-dihydro-5H-quinolin-8-one.
The zinc complex Zn4 was prepared as in example 1, with the only difference that: n- (2- (diphenylphosphino) ethyl) -2-chloro-5,6,7,8-tetrahydroquinolin-one-8-amine was used instead of N- (2- (diphenylphosphino) ethyl) -5,6,7,8-tetrahydroquinolin-one-8-amine, yield 75%.
The structural characterization data are as follows:
1 H NMR(C 3 D 7 NO,400MHz):δppm 7.94-7.92((d,J＝8.0Hz,1H,Py),7.60-7.58(d,J＝7.6Hz,1H,Py),7.51-7.40(m,10H,Ph),4.02(s,1H,CH),3.58-3.55(m.1H,CH),3.27(s,1H,CH),3.06-2.78(m,2H,CH 2 ),2.51-2.48(d,J＝12.8Hz,2H,CH 2 ),2.05-2.02(d,J＝12.8Hz,H,CH),1.86-1.75(m,2H,CH 2 ),13.8-1.33(m,6H,CH 3 )。
13 C NMR(C 3 D 7 NO,100MHz):δ156.65,146.91,143.81,138.55,138.42,137.64,137.51,134.01,132.93,132.74,132.52,132.34,129.09,128.89,128.84,128.80,128.77,128.73,124.42,58.04,44.58,44.32,27.85,27.72,27.15,26.46,20.03。
31 P NMR(C 3 D 7 NO , 162MHz):δ-17.38。
example 5
N- (2- (diphenylphosphino) ethyl) -2-phenyl-5,6,7,8-tetrahydroquinolin-8-amine was prepared as in example 1, except that: 2-phenyl-6,7-dihydro-5H-quinolin-8-one was used instead of 6,7-dihydro-5H-quinolin-8-one.
The zinc complex Zn5 was prepared as in example 1, with the only difference that: n- (2- (diphenylphosphino) ethyl) -5,6,7,8-tetrahydroquinolin one-8-amine was replaced with N- (2- (diphenylphosphino) ethyl) -2-phenyl-5,6,7,8-tetrahydroquinolin one-8-amine, 73% yield.
The structural characterization data is as follows:
1 H NMR(C 3 D 7 NO,400MHz):δppm 8.05-7.38(m,17H,Py+Ph),4.15(d,J＝4.4,1H,CH),3.21-3.08(m,2H,CH 2 ),2.94-2.84(m,3H,CH,CH 2 ),3.54-2.52(d,J＝4.4,1H,CH),2.43-2.37(m,1H,CH),2.08-2.05(d,J＝12.4,1H,CH),1.84-1.82(m,2H,CH 2 )。
13 C NMR(C 3 D 7 NO,100MHz):δ156.31,138.59,138.45,138.33,132.88,132.68,132.33,130.98,130.88,130.57,130.48,129.03,129.01,128.86,128.80,128.76,128.73,128.69,128.37,128.23,58.03,44.08,27.71,26.83,20.21。
31 P NMR(C 3 D 7 NO , 162MHz):δ-17.25。
example 6
In a glove box under nitrogen atmosphere, a tetrahydrofuran solution (20. Mu. Mol) of Zn1 in an amount of 10. Mu. Mol of zinc complex and trimethylsilyllithium in an amount of 40. Mu. L0.5M was charged into a 100ml Schlenk bottle, and 1ml of n-hexane was added as a solvent and aged at room temperature for 0.5 hour.
Then adding 2.5mmol of rac-lactide (racemic lactide), placing the reaction vessel in a water bath kettle at 50 ℃ for reaction for 15min, directly taking reaction liquid after the reaction is finished to detect the monomer conversion rate of caprolactone, wherein the monomer conversion rate of lactide is more than 99%.
Example 7
In a glove box under nitrogen atmosphere, a tetrahydrofuran solution (20. Mu. Mol) of Zn1 in an amount of 10. Mu. Mol of zinc complex and trimethylsilyllithium in an amount of 40. Mu. L0.5M was charged into a 100ml Schlenk bottle, and 1ml of n-hexane was added as a solvent and aged at room temperature for 0.5 hour.
Then adding 2.5mmol of L-lactide (L-lactide), placing the reaction vessel in a water bath kettle at 50 ℃ for reaction for 15min, directly taking reaction liquid after the reaction is finished to detect the monomer conversion rate of caprolactone, wherein the monomer conversion rate of lactide is more than 99%.
The present invention has been described in detail with reference to specific embodiments and/or illustrative examples, but the description is not intended to limit the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. A zinc complex, characterized in that it comprises hydroquinoline units and secondary amine groups, preferably also aromatic phosphine units, and in that zinc is coordinated to the nitrogen atoms of the hydroquinoline units and secondary amine groups.
2. The complex of claim 1, wherein the ligand of the zinc complex has the following general structural formula:
Figure FDA0003073831780000011
wherein R is selected from hydrogen, alkyl, halogenated group or aromatic group; g is an aromatic phosphine group; n is 1 to 6.
3. The complex of claim 1, wherein the zinc complex comprises the structure of formula (1):
Figure FDA0003073831780000012
wherein R is selected from hydrogen, alkyl, halogenated group or aromatic group; m is the number of ligands combined with zinc and is 1 or 2;
the formula (1) is combined with anions to obtain the neutral zinc complex, and the anions are any combinable anions.
4. The complex of claim 1, wherein R is selected from hydrogen and C 1 -C 5 Alkyl, fluoro, chloro, bromo, phenyl, alkylphenyl, alkoxyphenyl groups; m is 1.
5. The complex of claim 1, wherein the zinc complex is:
zn1: r is hydrogen, m is 1, and the anion is chloride;
zn2: r is methyl, m is 1, and the anion is chloride;
zn3: r is isopropyl, m is 1, and the anion is chloride;
zn4: r is chlorine, m is 1, and the anion is chloride; or
Zn5: r is phenyl, m is 1, and the anion is chloride.
6. A process for preparing a complex according to any one of claims 1 to 5, wherein the process comprises reacting a ligand compound with a zinc salt to prepare a zinc complex.
7. The method of claim 6,
the ligand compound is prepared from raw materials including hydrogenated quinolinone compounds and aromatic phosphino alkyl amine compounds;
the zinc salt is an ionizable zinc salt.
8. The method of claim 7,
the hydrogenated quinolinone compound is dihydroquinolinone or dihydroquinolinone with a 2-position substituent, and the substituent is selected from hydrogen, alkyl, halogenated group or aromatic group;
in the aromatic phosphinoalkylamine compounds, an aromatic phosphine groupIs phenylphosphino or diphenylphosphino; alkyl is C 1 -C 6 An alkyl group.
9. The method according to one of claims 6 to 8,
in the method, a ligand compound and a zinc salt are added into a solvent and stirred to react, preferably, a zinc salt solution is added into a ligand compound solution;
the concentration of the ligand compound solution is 0.05-0.7mol/L, and the concentration of the zinc salt solution is 0.1-1.40mol/L.
10. The process according to any one of claims 6 to 8, wherein the reaction solvent is selected from one or more of water, alcohol solvents and ether solvents, preferably one or more of water, methanol, ethanol, isopropanol and diethyl ether.
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