CN114437144B - Cobalt complex based on chiral imidazoline as framework, and synthesis method and application thereof - Google Patents

Cobalt complex based on chiral imidazoline as framework, and synthesis method and application thereof Download PDF

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CN114437144B
CN114437144B CN202210125064.9A CN202210125064A CN114437144B CN 114437144 B CN114437144 B CN 114437144B CN 202210125064 A CN202210125064 A CN 202210125064A CN 114437144 B CN114437144 B CN 114437144B
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郝新奇
侯森垚
南晨龙
王艳冰
姜辉
朱新举
宋毛平
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Zhengzhou University
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Abstract

The invention discloses a cobalt complex based on chiral imidazoline as a framework, and a synthesis method and application thereof, and the cobalt complex comprises the following steps: sequentially adding pyridine formaldehyde, (1S, 2S) diphenyl ethylenediamine, anhydrous cobalt chloride and a solvent into a reactor, magnetically stirring in an argon atmosphere for reaction, fully reacting in a metal bath, and filtering, washing and drying after the reaction is finished to obtain a target product. The bidentate cobalt complex synthesized by the invention has higher catalytic activity when being used as a catalyst for catalyzing polyisoprene.

Description

Cobalt complex based on chiral imidazoline as framework, and synthesis method and application thereof
Technical Field
The invention belongs to the technical field of synthesis and application of organic complexes, and particularly relates to a cobalt complex based on chiral imidazoline as a framework, and a synthesis method and application thereof.
Background
In the rubber field, it is recognized that natural rubber is the rubber with the best comprehensive performance, and has higher strength, elongation, elasticity and other performances, namely raw rubber, mixed rubber and vulcanized rubber. However, natural rubber is difficult to enlarge planting under the influence of longitude and latitude and climate of planting areas, and the yield of the natural rubber can not meet the increasing demands of society, so that the development of synthetic rubber plays a vital role in the construction and development of countries and society. Polyisoprene has the same monomer structure as natural rubber and is therefore favored by researchers. The polyisoprene prepared by the synthesis method is called as 'synthetic natural rubber' because of its structure similar to natural rubber, and is the best substitute rubber for natural rubber. With the development of olefin polymerization catalysts in recent years, late transition metal complexes exhibit the ability to catalyze isoprene polymerization, and late transition metal catalysts have the advantage of being more economical and stable than catalysts for isoprene polymerization commonly used in lithium-based, titanium-based and rare earth-based, and thus become a research hot spot rapidly. Researchers find that the N, N-bidentate nickel complex has isoprene polymerization catalyzing activity; the complexes of N, N-bidentate cobalt and iron also have activity to catalyze diene polymerization and are generally more active than nickel complexes. Researchers have found that the structure of further ligands tends to affect the catalytic performance of the catalyst.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a cobalt complex based on chiral imidazoline as a framework, and a synthesis method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a synthesis method of cobalt complex based on chiral imidazoline as skeleton comprises the following steps:
(1) Synthesis of chiral imidazoline ligand: sequentially adding pyridylaldehyde, (1S, 2S) diphenylethylenediamine, iodine simple substance, potassium carbonate and tertiary butanol into a reactor, heating for reaction, adding saturated solution of sodium thiosulfate for quenching after the reaction is finished, cooling to room temperature, extracting with ethyl acetate, taking an organic phase, spin-drying a solvent, and separating by column chromatography to obtain chiral imidazoline ligand;
(2) Synthesizing chiral imidazoline cobalt complex: adding a chiral imidazoline ligand into a Shi Laike bottle, replacing gas in a double-row pipe for three times, adding anhydrous cobalt chloride and a solvent into the glove box filled with argon atmosphere for reaction, and filtering, washing and drying after the reaction is finished to obtain a chiral imidazoline cobalt complex, wherein the structural formula of the chiral imidazoline cobalt complex is as follows:
Figure BDA0003500095200000021
r is a hydrogen atom, a phenyl group, a naphthyl group or a bromine atom.
Further, the ratio of the amount of pyridylaldehyde to the amount of the (1S, 2S) diphenylethylenediamine in the step (1) was 1:1.2, the ratio of the amount of pyridylaldehyde to the amount of the elemental iodine was 1:1.15, and the ratio of the amount of pyridylaldehyde to the amount of the potassium carbonate was 1:3.
Further, the temperature of the heating reaction in the step (1) was 70℃and the reaction time was 3 hours.
Further, in the step (1), petroleum ether and ethyl acetate with the volume ratio of 20:1 are adopted as eluent for column chromatography separation.
Further, step (2) was performed using a dry and clean Shi Laike bottle with a glass stopper, and the entire reaction was performed under an argon atmosphere.
Further, the mass ratio of chiral imidazoline ligand to cobalt chloride in step (2) was 1:1.
Further, the solvent in the step (2) is tetrahydrofuran which is distilled again, and the washing agent which is distilled again is used for separation.
Further, the reaction temperature in the step (2) was 25℃and the reaction time was 12 hours.
The chiral imidazoline cobalt complex prepared by the synthesis method of the invention.
The chiral imidazoline cobalt complex provided by the invention is used as a catalyst for catalyzing polyisoprene.
Preferably, the complex of formula 1 according to the present invention comprises the following complexes:
Figure BDA0003500095200000031
as an example, the complex represented by formula 1 may be selected from complexes having the following group definitions: co 1: wherein r=np; co 2: wherein r=ph; co 3: wherein r=h; co 4: where r=br.
The present invention also provides a ligand represented by the following formula 2:
Figure BDA0003500095200000032
by way of example, the complex intermediate has the structure shown in the following formula 2-1, formula 2-2, formula 2-3, or formula 2-4:
Figure BDA0003500095200000041
that is, the ligand of formula 2 is selected from the group consisting of complex intermediates defined by: l1: wherein r=np; l2: wherein r=ph; l3: wherein r=h; l4: where r=br.
The typical synthesis steps of the invention are as follows:
in a glove box filled with argon atmosphere, a certain amount of chiral imidazoline ligand is added, then a corresponding amount of cobalt chloride and solvent are added, and the mixture is reacted in a metal bath at 25 ℃ for 12 hours. After filtration, washing with redistilled n-hexane and drying, the yield of chiral imidazoline cobalt complex was calculated.
The invention has the beneficial effects that: the chiral imidazoline cobalt complex is synthesized, and has excellent effect in isoprene polymerization as a catalyst. Compared with the traditional process, the method has the remarkable advantages that: (1) The new method avoids the problems of environmental pollution, high cost and the like caused by using various transition metals in the traditional method; (2) The method adopts anhydrous cobalt chloride as a metal source (cheap and easily available); (3) The catalyst synthesized by the method has high polymerization activity in isoprene polymerization.
Drawings
FIG. 1 is L1 in example 1 1 H NMR chart.
FIG. 2 is L1 in example 1 13 C NMR chart.
FIG. 3 is L2 of example 2 1 H NMR chart.
FIG. 4 is L2 of example 2 13 C NMR chart.
FIG. 5 is L3 in example 3 1 H NMR chart.
FIG. 6 is L3 in example 3 13 C NMR chart.
FIG. 7 is a crystal diagram of Co3 in example 3.
FIG. 8 is L4 of example 4 1 H NMR chart.
FIG. 9 is L4 of example 4 13 C NMR chart.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that numerous insubstantial modifications and adaptations can be made by those skilled in the art in light of the foregoing disclosure.
Example 1
The synthesis method of the chiral imidazoline cobalt complex in the embodiment is as follows:
(1) Synthesis of L1: 6-naphtylpyridine-2-carbaldehyde (1.16 g,5.0 mmol), (1S, 2S) diphenylethylenediamine (1.16 g,5.5 mmol), elemental iodine (1.46 g,5.75 mmol) and potassium carbonate (2.07 g,15 mmol) were added to a 250mL round bottom flask, then 80mL of t-butanol was added and reacted at 70℃for 3 hours, after the completion of the reaction, a saturated solution of sodium thiosulfate was added to quench, cooled to room temperature, extracted with ethyl acetate, the organic phase was taken, the solvent was dried by spinning, and the target complex was obtained by column chromatography separation (petroleum ether/ethyl acetate=6/1).
(2) Synthesis of Co 1: the ligand compound (149.6 mg,0.5 mmol) was added to a 25mL Schlemk bottle with cobalt chloride (64.9 mg,0.5 mmol), then 10mL anhydrous tetrahydrofuran was added, and the reaction was stirred under argon at room temperature for 12h. After the reaction is finished, the product is filtered, washed by anhydrous n-hexane and dried to obtain Co 1. Dark green solid, yield: 150mg,70%; elemental analysis C 30 H 23 Cl 2 CoN 3 :C,64.88；H,4.17；N,7.57.Found:C,64.99；H,4.28；N,7.58.
Example 2
The synthesis method of the chiral imidazoline cobalt complex in the embodiment is as follows:
(1) Synthesis of L2: 6-phenylpyridine-2-carbaldehyde (916.1 mg,5.0 mmol), (1S, 2S) diphenylethylenediamine (1.16 g,5.5 mmol), elemental iodine (1.46 g,5.75 mmol) and potassium carbonate (2.07 g,15 mmol) were added to a 250mL round-bottomed flask, 80mL of t-butanol was then added, and reacted at 70℃for 3 hours, after the completion of the reaction, a saturated solution of sodium thiosulfate was added to quench, cooled to room temperature, extracted with ethyl acetate, the organic phase was taken, the solvent was dried by spinning, and the desired complex was obtained by column chromatography separation (petroleum ether/ethyl acetate=20/1).
(2) Synthesis of Co 2: the ligand compound (252.6 mg,0.5 mmol) was added to a 25mL Schlemk bottle with cobalt chloride (64.9 mg,0.5 mmol), then 10mL anhydrous tetrahydrofuran was added, and the reaction was stirred under argon at room temperature for 12h. After the reaction is finished, the product is filtered, washed by anhydrous normal hexane and dried to obtain Co 2. Indigo solid, yield: 190mg,75%; elemental analysis C 26 H 21 Cl 2 CoN 3 :C,61.80；H,4.19；N,8.32.Found:C,61.89；H,4.16；N,8.33.
Example 3
The synthesis method of the chiral imidazoline cobalt complex in the embodiment is as follows:
(1) Synthesis of L3: 2-Pyridinecarboxaldehyde (535.6 mg,5.0 mmol), (1S, 2S) diphenylethylenediamine (1.16 g,5.5 mmol), elemental iodine (1.46 g,5.75 mmol), potassium carbonate (2.07 g,15 mmol) were added to a 250mL round bottom flask, 80mL of t-butanol was then added, reacted at 70℃for 3 hours, after the completion of the reaction, a saturated solution of sodium thiosulfate was added to quench, cooled to room temperature, extracted with ethyl acetate, the organic phase was taken, the solvent was dried by spin, and the objective complex was obtained by column chromatography separation (petroleum ether/ethyl acetate=6/1).
(2) Synthesis of Co 3: the ligand conjugate (149.6 mg,0.5 mmol) was added to a 25mL Schlemk bottle with cobalt chloride (64.9 mg,0.5 mmol) followed by 10mLAnhydrous tetrahydrofuran was stirred at room temperature for 12h under argon. After the reaction is finished, the product is filtered, washed by anhydrous normal hexane and dried to obtain Co 3. Green solid, yield: 150mg,70%; elemental analysis: c (C) 20 H 17 Cl 2 CoN 3 :C,55.97；H,3.99；N,9.79.Found:C,59.70；H,5.66；N,10.29.
Example 4
The synthesis method of the chiral imidazoline cobalt complex in the embodiment is as follows:
(1) Synthesis of L4: 6-bromo-2-pyridinecarboxaldehyde (925 mg,5.0 mmol), (1S, 2S) diphenylethylenediamine (1.16 g,5.5 mmol), elemental iodine (1.46 g,5.75 mmol), potassium carbonate (2.07 g,15 mmol) were added to a 250mL round bottom flask, then 80mL of t-butanol was added and reacted at 70℃for 3 hours, after the reaction was completed, a saturated solution of sodium thiosulfate was added to quench, cooled to room temperature, extracted with ethyl acetate, an organic phase was taken, a spin-dry solvent was used, and column chromatography was carried out to separate (petroleum ether/ethyl acetate=20/1) to obtain the objective complex.
(2) Synthesis of Co 4: the ligand conjugate (189.13 mg,0.5 mmol) was added to a 25mL Schlemk bottle with cobalt chloride (64.9 mg,0.5 mmol), then 10mL anhydrous tetrahydrofuran was added and the reaction stirred under argon at room temperature for 12h. After the reaction is finished, the product is filtered, washed by anhydrous normal hexane and dried to obtain Co 4. Green solid, yield: 120mg,50%; elemental analysis: c (C) 20 H 16 BrCl 2 CoN 3 :C,47.28；H,3.17；N,8.27.Found:C,47.38；H,3.27；N,8.28.
Example 5
The compound Co3 and diethyl aluminum chloride are used for catalyzing isoprene polymerization, and the specific steps are as follows:
(1) In a glove box, co3 (3.4 mg, 8. Mu. Mmol), 5mL of toluene, 0.8mmol of AlEt were added sequentially to a Shi Laike bottle 2 Cl, and 2mL of isoprene, where Al/Co=100/1, at room temperature for 2h; dropping ethanol solution acidified by hydrochloric acid into the reaction system to quench the reaction to obtain polymer precipitate, washing with ethanol for several times, drying to constant weight, and weighing.
Polymerization activity: 8.5X10 4 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝3.0×10 4 g·mol -1 ，PDI＝2.9。
(2) The operation method is the same as (1), and the difference is that: 400. Mu. Mol of AlEt was added 2 Cl, al/co=50, polymerization activity: 8.5X10 5 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝4.5×10 4 g·mol -1 ，PDI＝3.0。
(3) The operation method is the same as (1), and the difference is that: 80. Mu. Mol of AlEt was added 2 Cl, al/co=10, polymerization activity: 7.7X10 4 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝11.5×10 4 g·mol -1 ，PDI＝1.8。
(4) The operation method is the same as (1), and the difference is that: 40. Mu. Mol of AlEt was added 2 Cl, al/co=5, polymerization activity: 7.6X10 4 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝11.1×10 4 g·mol -1 ，PDI＝1.7。
Example 6
The compound Co1 and diethyl aluminum chloride are used for catalyzing isoprene polymerization, and the specific steps are as follows:
(1) In a glove box, co1 (4.4 mg, 8. Mu. Mol), 5mL of toluene, 0.96mmol of AlEt were added sequentially to a Shi Laike bottle 2 Cl, and 2mL of isoprene, at which time Al/Co=40/1, polymerization temperature 25 ℃, 120min; dropping ethanol solution acidified by hydrochloric acid into the reaction system to quench the reaction to obtain polymer precipitate, washing with ethanol for several times, drying to constant weight, and weighing.
Polymerization activity: 8.4X10 4 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝5.3×10 4 g·mol -1 ，PDI＝2.9。
(2) The operation method is the same as (1), and the difference is that: reaction for 10min, polymerization activity: 7.9X10 5 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝1.3×10 5 g·mol -1 ，PDI＝1.7。
Example 7
The compound Co2 and diethyl aluminum chloride are used for catalyzing isoprene polymerization, and the specific steps are as follows:
(1) In a glove box, co2 (4.0 mg, 8. Mu. Mol), 5mL of toluene, 0.96mmol of AlEt were added sequentially to a Shi Laike bottle 2 Cl, and 2mL of isoprene, at which time Al/Co=40/1, polymerization temperature 25 ℃, 120min; dropping ethanol solution acidified by hydrochloric acid into the reaction system to quench the reaction to obtain polymer precipitate, washing with ethanol for several times, drying to constant weight, and weighing.
Polymerization activity: 8.4X10 4 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝4.7×10 4 g·mol -1 ，PDI＝3.1。
(2) The operation method is the same as (1), and the difference is that: reaction for 10min, polymerization activity: 6.5X10 5 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝8.7×10 4 g·mol -1 ，PDI＝2.3。
Example 8
The compound Co3 and diethyl aluminum chloride are used for catalyzing isoprene polymerization, and the specific steps are as follows:
(1) In a glove box, co3 (3.4 mg, 8. Mu. Mol), 5mL of toluene, 0.96mmol of AlEt were added sequentially to a Shi Laike bottle 2 Cl and 2mL of isoprene, at which time Al/Co=40/1, polymerization temperature was room temperature, and reaction was carried out for 10min; dropping ethanol solution acidified by hydrochloric acid into the reaction system to quench the reaction to obtain polymer precipitate, washing with ethanol for several times, drying to constant weight, and weighing.
Polymerization activity: 10.2X10 5 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝15.4×10 4 g·mol -1 ，PDI＝1.5。
Example 9
The compound Co3 and diethyl aluminum chloride are used for catalyzing isoprene polymerization, and the specific steps are as follows:
(1) In a glove box, co3 (3.4 mg, 8. Mu. Mol), 5mL of toluene, 0.96mmol of AlEt were added sequentially to a Shi Laike bottle 2 Cl, and 2mL of isoprene, at which time Al/Co=40/1, polymerization temperature 50 ℃, reaction for 30min; dropping ethanol solution acidified by hydrochloric acid into the reaction system to quench the reaction to obtain polymer precipitate, washing with ethanol for several times, drying to constant weight, and weighing.
Polymerization activity: 3.3X10 5 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝10.5×10 4 g·mol -1 ，PDI＝1.8。
(2) The operation method is the same as (1), and the difference is that: polymerization temperature 70 ℃, polymerization activity: 16.0X10 4 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝8.1×10 4 g·mol -1 ，PDI＝1.9。
Example 10
The compound Co4 and diethyl aluminum chloride are utilized to catalyze isoprene polymerization, and the specific steps are as follows:
(1) In a glove box, co4 (4.0 mg, 8. Mu. Mol), 5mL of toluene, 0.96mmol of AlEt were added sequentially to a Shi Laike bottle 2 Cl, and 2mL of isoprene, at which time Al/Co=40/1, polymerization temperature 25 ℃, 120min; dropping ethanol solution acidified by hydrochloric acid into the reaction system to quench the reaction to obtain polymer precipitate, washing with ethanol for several times, drying to constant weight, and weighing.
Polymerization activity: 8.4X10 4 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝4.5×10 4 g·mol -1 ，PDI＝3.0。
(2) The operation method is the same as (1), and the difference is that: reaction for 10min, polymerization activity: 9.5X10 5 g·mol -1 ·h -1 Polymer molecular weight: m is M n ＝3.0×10 4 g·mol -1 ，PDI＝2.9。
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. The synthesis method of the cobalt complex based on the chiral imidazoline as a framework is characterized by comprising the following steps:
(1) Synthesis of chiral imidazoline ligand: sequentially adding pyridylaldehyde, (1S, 2S) diphenylethylenediamine, iodine simple substance, potassium carbonate and tertiary butanol into a reactor, heating for reaction, adding saturated solution of sodium thiosulfate for quenching after the reaction is finished, cooling to room temperature, extracting with ethyl acetate, taking an organic phase, spin-drying a solvent, and separating by column chromatography to obtain chiral imidazoline ligand;
(2) Synthesizing chiral imidazoline cobalt complex: adding a chiral imidazoline ligand into a Shi Laike bottle, replacing gas in a double-row pipe for three times, adding anhydrous cobalt chloride and a solvent into the glove box filled with argon atmosphere for reaction, and filtering, washing and drying after the reaction is finished to obtain a chiral imidazoline cobalt complex, wherein the structural formula of the chiral imidazoline cobalt complex is as follows:
Figure DEST_PATH_IMAGE001
，
r is a hydrogen atom, a phenyl group, a naphthyl group or a bromine atom.
2. The synthesis method of the cobalt complex based on the chiral imidazoline skeleton, which is disclosed in claim 1, is characterized in that: the ratio of the amount of pyridylaldehyde to the amount of the (1S, 2S) diphenylethylenediamine in the step (1) was 1:1.2, the ratio of the amount of pyridylaldehyde to the amount of the elemental iodine was 1:1.15, and the ratio of the amount of pyridylaldehyde to the amount of the potassium carbonate was 1:3.
3. The synthesis method of the cobalt complex based on the chiral imidazoline skeleton, which is disclosed in claim 1, is characterized in that: the temperature of the heating reaction in the step (1) is 70 ℃, and the reaction time is 3 hours.
4. The synthesis method of the cobalt complex based on the chiral imidazoline skeleton, which is disclosed in claim 1, is characterized in that: in the step (1), petroleum ether and ethyl acetate with the volume ratio of 20:1 are adopted as eluent for column chromatography separation.
5. The synthesis method of the cobalt complex based on the chiral imidazoline skeleton, which is disclosed in claim 1, is characterized in that: step (2) was performed using a dry and clean Shi Laike bottle with a glass stopper, and the entire reaction was performed under an argon atmosphere.
6. The synthesis method of the cobalt complex based on the chiral imidazoline skeleton, which is disclosed in claim 1, is characterized in that: the mass ratio of chiral imidazoline ligand to cobalt chloride in step (2) is 1:1.
7. The synthesis method of the cobalt complex based on the chiral imidazoline skeleton, which is disclosed in claim 1, is characterized in that: the solvent in the step (2) is tetrahydrofuran which is vaporized again, and the washing agent which is used for separation is hexane which is vaporized again.
8. The synthesis method of the cobalt complex based on the chiral imidazoline skeleton, which is disclosed in claim 1, is characterized in that: the reaction temperature in the step (2) is 25 ℃ and the reaction time is 12h.
9. The chiral imidazoline cobalt complex prepared by the synthesis method according to any one of claims 1 to 8.
10. Use of a chiral imidazoline cobalt complex according to claim 9 as a catalyst for catalyzing polyisoprene.
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