CN103447091B - The method of four tooth pyridine radicals schiff base metal complexes, its preparation method and cyclic carbonate - Google Patents

The method of four tooth pyridine radicals schiff base metal complexes, its preparation method and cyclic carbonate Download PDF

Info

Publication number
CN103447091B
CN103447091B CN201310400893.4A CN201310400893A CN103447091B CN 103447091 B CN103447091 B CN 103447091B CN 201310400893 A CN201310400893 A CN 201310400893A CN 103447091 B CN103447091 B CN 103447091B
Authority
CN
China
Prior art keywords
formula
reaction
base metal
metal complexes
schiff base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310400893.4A
Other languages
Chinese (zh)
Other versions
CN103447091A (en
Inventor
盛兴丰
秦玉升
王献红
王佛松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhongke Yinghua Changchun Technology Co ltd
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN201310400893.4A priority Critical patent/CN103447091B/en
Publication of CN103447091A publication Critical patent/CN103447091A/en
Application granted granted Critical
Publication of CN103447091B publication Critical patent/CN103447091B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Pyridine Compounds (AREA)

Abstract

The invention provides the preparation method that one has four tooth pyridine radicals schiff base metal complexes of structure shown in formula (I) or formula (II), its preparation method and cyclic carbonate.Under the existence of four tooth pyridine radicals schiff base metal complexes provided by the invention and co-catalyst quaternary ammonium salt, carbon dioxide and epoxides carry out cycloaddition reaction, prepare cyclic carbonate.In the process of cycloaddition reaction, four tooth pyridine radicals schiff base metal complexes have higher catalytic activity as major catalyst, improve the reaction rate of cycloaddition reaction, but also there is good selectivity of product, improve the productive rate of cyclic carbonate in product.Experimental result shows, the selectivity of product of four tooth pyridine radicals schiff base metal complexes provided by the invention is greater than 99%, the generation cyclic carbonate that cycloaddition reaction is single.

Description

The method of four tooth pyridine radicals schiff base metal complexes, its preparation method and cyclic carbonate
Technical field
The present invention relates to technical field of organic synthesis, particularly relate to the method for four tooth pyridine radicals schiff base metal complexes, its preparation method and cyclic carbonate.
Background technology
Since the thirties in 20th century, cyclic carbonate chemistry was born, it has become a subject day by day causing chemist to pay close attention to.Cyclic carbonate is very important chemical intermediate, ring-opening polymerisation can obtain the Merlon of HMW; Or a kind of important chemical products, it has good biological degradability and dissolubility, is good clean type polar solvent, can be used as the electrolyte of cosmetic additive agent, food additives, high-energy-density battery and electric capacity and metal extraction agent etc.
The synthetic method of cyclic carbonate mainly contains the cycloaddition reaction etc. of phosgenation, ester-interchange method and carbon dioxide and epoxides.The wherein cycloaddition reaction of carbon dioxide and epoxides, be with carbon dioxide and epoxides for raw material, carry out under uniform temperature, certain pressure and catalysts conditions.Because the low in raw material price of this cycloaddition reaction, accessory substance are few, and adopt carbon dioxide to be reaction raw materials, be conducive to reducing greenhouse effects, protection of the environment and meet the requirement of Green Chemistry and sustainable development, so Application comparison of this reaction is extensive.
Prior art, in order to improve the reactivity of carbon dioxide and epoxides cycloaddition reaction, is devoted to develop the catalyst with higher catalytic activity.As published heterogeneous catalyst, comprise metal oxide, the molecular sieve of modification and clay class, high score subclass material etc.Heterogeneous catalyst is easier to be removed from product, but they exist the problems such as catalytic activity low, selective low, reaction time long and severe reaction conditions.In order to the cycloaddition reaction of carbon dioxide and epoxides can be realized under relatively mild condition, prior art has developed homogeneous catalyst, as metal complex, especially with the tetradentate schiff base metal complex that cobalt, chromium etc. are activated centre, higher catalytic activity is embodied under relatively mild reaction condition, but theirs is selective low, has the generation of the accessory substances such as Merlon in cycloaddition reaction product.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is a kind of provide four tooth pyridine radicals schiff base metal complexes, its preparation method and prepare cyclic carbonate method.Four tooth pyridine radicals schiff base metal complexes provided by the invention have higher selective, make CO 2single cyclic carbonate is generated with epoxides cycloaddition reaction.
The invention provides a kind of four tooth pyridine radicals schiff base metal complexes, there is structure shown in formula (I) or formula (II):
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9or R 10independently selected from the aryl of the aliphatic group of hydrogen, halogen, aliphatic group, replacement, aryl or replacement;
M is metallic element;
Described A has structure shown in formula (III), formula (IV) or formula (V):
Wherein, D 1, D 2, D 3or D 4independently selected from the aliphatic group of hydrogen, halogen, aliphatic group, replacement, the aryl containing heteroatomic aliphatic group, aryl, replacement or heteroaryl;
represent the connecting key of A and N;
In formula (IV), n is the positive integer of 1 ~ 4.
Preferably, described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9or R 10be the aryl of 1 ~ 3 or the phenyl ring quantity of halogen substiuted independently selected from hydrogen, chlorine, the C atomicity aliphatic group that is 1 ~ 5, the C atomicity replacement aliphatic group that is 1 ~ 5, phenyl ring quantity be the aryl of 1 ~ 3.
Preferably, described D 1, D 2, D 3or D 4be the aryl of 1 ~ 3 or the phenyl ring quantity of halogen substiuted independently selected from hydrogen, chlorine, the C atomicity aliphatic group that is 1 ~ 5, the C atomicity Heteroaliphatic groups that is 1 ~ 5, phenyl ring quantity be the aryl of 1 ~ 3.
Preferably, described M is zinc, magnesium, manganese or iron.
The present invention also provides a kind of method preparing four tooth pyridine radicals schiff base metal complexes, comprises the following steps:
The compound with structure shown in formula (VI) is reacted in a solvent with the diamine compounds with structure shown in formula (VII), obtains the first intermediate product;
Wherein, X 1, X 2, X 3or X 4independently selected from the aryl of the aliphatic group of hydrogen, halogen, aliphatic group, replacement, aryl or replacement;
Wherein, described A has structure shown in formula (III), formula (IV) or formula (V):
Wherein, D 1, D 2, D 3or D 4independently selected from the aliphatic group of hydrogen, halogen, aliphatic group, replacement, the aryl containing heteroatomic aliphatic group, aryl, replacement or heteroaryl;
represent the connecting key of A and N;
In formula (IV), n is the positive integer of 1 ~ 4;
Described first intermediate product and metal chloride are reacted in organic solvent, obtains the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (I);
Or
Described first intermediate product and reducing agent are reacted in a solvent, obtains the second intermediate product;
Described second intermediate product and metal chloride are reacted in organic solvent, obtains the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (II);
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9or R 10independently selected from the aryl of the aliphatic group of hydrogen, halogen, aliphatic group, replacement, aryl or replacement;
M is metallic element.
Preferably, the compound of structure shown in described formula (VI) is 0.5 ~ 5:1 with the mol ratio of the diamine compounds with structure shown in formula (VII).
Preferably, the compound of structure shown in described formula (VI) is 20 DEG C ~ 40 DEG C with the temperature of the diamine compounds reaction with structure shown in formula (VII);
The compound of structure shown in described formula (VI) is 2h ~ 5h with the time of the diamine compounds reaction with structure shown in formula (VII).
Preferably, the temperature that described first intermediate product and reducing agent react is 20 DEG C ~ 40 DEG C;
The time that described first intermediate product and reducing agent react is 5h ~ 15h.
Preferably, the temperature that described first intermediate product and metal chloride react is 20 DEG C ~ 40 DEG C;
The temperature that described second intermediate product and metal chloride react is 20 DEG C ~ 40 DEG C.
Present invention also offers a kind of method preparing cyclic carbonate, comprise the following steps:
Under the effect of major catalyst and co-catalyst, carbon dioxide and epoxides are carried out cycloaddition reaction, obtains cyclic carbonate;
The four tooth pyridine radicals schiff base metal complexes that described major catalyst prepares for method described in four tooth pyridine radicals schiff base metal complexes described in technique scheme or technique scheme;
Described co-catalyst is quaternary ammonium salt.
Preferably, the mol ratio of described major catalyst, co-catalyst and epoxides is 1:(0.5 ~ 1.5): (500 ~ 5000);
The pressure of described carbon dioxide is 1MPa ~ 6MPa.
Preferably, the reaction temperature of described cycloaddition reaction is 50 DEG C ~ 140 DEG C;
The reaction time of described cycloaddition reaction is 1h ~ 24h.
The invention provides a kind of four tooth pyridine radicals schiff base metal complexes, there is structure shown in formula (I) or formula (II).Four tooth pyridine radicals schiff base metal complexes provided by the invention can the cycloaddition reaction of catalysis carbon dioxide and epoxides, has higher catalytic activity and selectivity of product.Under the existence of four tooth pyridine radicals schiff base metal complexes and co-catalyst quaternary ammonium salt, carbon dioxide and epoxides cycloaddition reaction prepare cyclic carbonate.In cycloaddition reaction process, the four tooth pyridine radicals schiff base metal complexes as major catalyst have higher catalytic activity, and have higher selective to product, inhibit the generation of Merlon, improve the content of cyclic carbonate in product.Experimental result shows, carbon dioxide and epoxides are under the effect of four tooth pyridine radicals schiff base metal complexes and co-catalyst quaternary ammonium salt, and the selective of product is greater than 99%, and the productive rate of the cyclic carbonate obtained is 20% ~ 100%.
Further, the activated centre of the present invention using zinc, magnesium, manganese or ferrous metal element as four tooth pyridine radicals schiff base metal complexes, toxic metals content overproof in the cyclic carbonate effectively preventing catalysis from generating, is conducive to applying of cyclic carbonate ester material.
Detailed description of the invention
The invention provides a kind of four tooth pyridine radicals schiff base metal complexes, there is structure shown in formula (I) or formula (II):
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9or R 10independently selected from the aryl of the aliphatic group of hydrogen, halogen, aliphatic group, replacement, aryl or replacement, preferably, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9or R 10be the aryl of 1 ~ 3 or the phenyl ring quantity of halogen substiuted independently selected from hydrogen, chlorine, the C atomicity aliphatic group that is 1 ~ 5, the C atomicity replacement aliphatic group that is 1 ~ 5, phenyl ring quantity be the aryl of 1 ~ 3; More preferably, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9or R 10independently selected from hydrogen, chlorine, methyl, trifluoromethyl or 4-chlorphenyl;
Described M is metallic element, is preferably zinc, magnesium, manganese or iron; The present invention is preferably using the zinc of cheap, environmental protection, magnesium, manganese or iron as activated centre, not containing toxic metals in the cyclic carbonate prepared with the four tooth pyridine radicals schiff base metal complex catalysis carbon dioxide obtained and the addition reaction of epoxides initial ring, cyclic carbonate can being made directly to use when not needing removing catalyst, efficiently solving toxic metals residue problem in cyclic carbonate ester material.
In the present invention, described A has structure shown in formula (III), formula (IV) or formula (V):
Wherein, D 1, D 2, D 3or D 4independently selected from the aliphatic group of hydrogen, halogen, aliphatic group, replacement, the aryl containing heteroatomic aliphatic group, aryl, replacement or heteroaryl; Preferably, D 1, D 2, D 3or D 4be the aryl of 1 ~ 3 or the phenyl ring quantity of halogen substiuted independently selected from hydrogen, chlorine, the C atomicity aliphatic group that is 1 ~ 5, the C atomicity Heteroaliphatic groups that is 1 ~ 5, phenyl ring quantity be the aryl of 1 ~ 3, more preferably, D 1, D 2, D 3or D 4independently selected from hydrogen, chlorine, methyl, ethyoxyl, phenyl or 4-chlorphenyl.
represent the connecting key of A and N;
In formula (IV), n is the degree of polymerization, and n is the positive integer of 1 ~ 4, is preferably 1 ~ 3, is more preferably n=1.
In the present invention, R is worked as 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9and R 10be hydrogen, A has structure shown in formula (III), D simultaneously 1, D 2, D 3and D 4be hydrogen, when M is Fe, four tooth pyridine radicals schiff base metal complexes have structure shown in formula (VIII) or formula (IX) simultaneously:
In the present invention, R is worked as 1, R 2, R 4, R 5, R 7, R 8, R 9and R 10be hydrogen simultaneously, R 3and R 6be that Cl, A have structure shown in formula (V), D simultaneously 1and D 4for hydrogen, D 2and D 3for Cl, M be Fe time, four tooth pyridine radicals schiff base metal complexes have structure shown in formula (X) or formula (XI):
In the present invention, R is worked as 1, R 2, R 4, R 5, R 7, R 8, R 9and R 10be hydrogen simultaneously, R 3and R 6be methyl, A has structure shown in formula (IV), D simultaneously 1and D 2for hydrogen, D 3and D 4for phenyl, when n=1, M are Mg, four tooth pyridine radicals schiff base metal complexes have structure shown in formula (XII) or formula (XIII):
In the present invention, R is worked as 1, R 2, R 3, R 6, R 7, R 8, R 9and R 10be hydrogen simultaneously, R 4and R 5be trifluoromethyl, A has structure shown in formula (IV), D simultaneously 1, D 2and D 3for hydrogen, D 4for methyl, when n=1, M are Zn, four tooth pyridine radicals schiff base metal complexes have structure shown in formula (XIV) or formula (XV):
In the present invention, R is worked as 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9and R 10be hydrogen, A has structure shown in formula (V), D simultaneously 1, D 2and D 3for hydrogen, D 4for ethyoxyl, when M is Fe, four tooth pyridine radicals schiff base metal complexes have structure shown in formula (XVI) or formula (XVII):
In the present invention, R is worked as 2, R 3, R 4, R 5, R 6, R 7, R 9and R 10be hydrogen simultaneously, R 1and R 8be 4-chlorphenyl, A has structure shown in formula (IV), D simultaneously 1and D 2for hydrogen, D 3and D 4for 4-chlorphenyl, when n=1, M are Mn, four tooth pyridine radicals schiff base metal complexes have structure shown in formula (XVIII) or formula (XIX):
The invention provides a kind of method preparing four tooth pyridine radicals schiff base metal complexes, comprise the following steps:
The compound with structure shown in formula (VI) is reacted in a solvent with the diamine compounds with structure shown in formula (VII), obtains the first intermediate product;
Wherein, X 1, X 2, X 3or X 4independently selected from the aryl of the aliphatic group of hydrogen, halogen, aliphatic group, replacement, aryl or replacement;
Wherein, described A has structure shown in formula (III), formula (IV) or formula (V):
Wherein, D 1, D 2, D 3or D 4independently selected from the aliphatic group of hydrogen, halogen, aliphatic group, replacement, the aryl containing heteroatomic aliphatic group, aryl, replacement or heteroaryl;
for representing the connecting key of A and N;
In formula (IV), n is the positive integer of 1 ~ 4;
Described first intermediate product and metal chloride are reacted in organic solvent, obtains four tooth pyridine radicals schiff base metal complexes of structure shown in formula (I);
Or
Described first intermediate product and reducing agent are reacted in a solvent, obtains the second intermediate product;
Described second intermediate product and metal chloride are reacted in organic solvent, obtains the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (II);
Wherein, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9or R 10independently selected from the aryl of the aliphatic group of hydrogen, halogen, aliphatic group, replacement, aryl or replacement;
M is metallic element.
The compound with structure shown in formula (VI) reacts with the diamine compounds with structure shown in formula (VII) by the present invention in a solvent, obtains the first intermediate product.In the present invention, in formula (VI), X 1, X 2, X 3or X 4independently selected from the aryl of the aliphatic group of hydrogen, halogen, aliphatic group, replacement, aryl or replacement, preferably, X 1, X 2, X 3or X 4be the aryl of 1 ~ 3 or the phenyl ring quantity of halogen substiuted independently selected from hydrogen, chlorine, the C atomicity aliphatic group that is 1 ~ 5, the C atomicity replacement aliphatic group that is 1 ~ 5, phenyl ring quantity be the aryl of 1 ~ 3; More preferably, X 1, X 2, X 3or X 4independently selected from hydrogen, chlorine, methyl, trifluoromethyl or 4-chlorphenyl;
Concrete, work as X 1, X 2, X 3and X 4when being H simultaneously, described in there is structure shown in formula (VI) compound be 2-pyridine carboxaldehyde; Work as X 1, X 2and X 4be H, X simultaneously 3during for Cl, described in there is structure shown in formula (VI) compound be 4-Chloro-2-Pyridyle formaldehyde; Work as X 1, X 2and X 4be H, X simultaneously 3during for methyl, described in there is structure shown in formula (VI) compound be 4-methyl-2-pyridine carboxaldehyde; Work as X 1, X 2and X 3be H, X simultaneously 4during for trifluoromethyl, described in there is structure shown in formula (VI) compound be 3-trifluoromethyl-2-pyridine carboxaldehyde; Work as X 2, X 3and X 4be H, X simultaneously 1during for 4-chlorphenyl, described in there is structure shown in formula (VI) compound be 6-(4-chlorphenyl)-2-pyridine carboxaldehyde.The present invention does not have special restriction to the described source with the compound of structure shown in formula (VI), adopts the compound with structure shown in formula (VI) well known to those skilled in the art.
In the present invention, the A in described formula (VII) is the A in formula described in technique scheme (I) or formula (II), does not repeat them here; Concrete, when A has structure shown in formula (III), D 1, D 2, D 3and D 4when being hydrogen simultaneously, described in there is structure shown in formula (VII) diamine compounds be 1,2-cyclohexanediamine; When A has structure shown in formula (V), D 1and D 4for hydrogen, D 2and D 3during for Cl, described in there is structure shown in formula (VII) diamine compounds be 4,5-dichloro o-phenylenediamine; When A has structure shown in formula (IV), D 1and D 2for hydrogen, D 3and D 4for phenyl, during n=1, described in there is structure shown in formula (VII) diamine compounds be 1,2-diphenyl ethylene diamine; When A has structure shown in formula (IV), D 1, D 2and D 3for hydrogen, D 4for methyl, during n=1, described in there is structure shown in formula (VII) diamine compounds be 1,2-propane diamine; When A has structure shown in formula (V), D 1, D 2and D 3for hydrogen, D 4during for ethyoxyl, described in there is structure shown in formula (VII) diamine compounds be 4-ethyoxyl o-phenylenediamine; When A has structure shown in formula (IV), D 1and D 2for hydrogen, D 3and D 4for 4-chlorphenyl, during n=1, described in there is structure shown in formula (VII) diamine compounds be 1,2-bis-(4-chlorphenyl)-1,2-ethylenediamine.The present invention does not have special restriction to the described source with the diamine compounds of structure shown in formula (VII), adopt the diamine compounds with structure shown in formula (VII) well known to those skilled in the art, obtain as bought by market.
The kind of the present invention to described solvent does not have special restriction, and adopting well known to those skilled in the artly can provide the solvent of reaction medium for the compound with structure shown in formula (VI) and the diamine compounds with structure shown in formula (VII).In the present invention, described solvent is preferably alcohol compound, is more preferably one or more in methyl alcohol, ethanol and propyl alcohol, most preferably is methyl alcohol, is the most preferably absolute methanol.
In the present invention, the described compound with structure shown in formula (VI) is preferably 0.5 ~ 5:1 with the mol ratio of the diamine compounds with structure shown in formula (VII), be more preferably 1 ~ 3:1, most preferably be 1.8 ~ 2.5:1, be the most preferably 2:1; The consumption of the present invention to described solvent does not have special restriction, the compound with structure shown in formula (VI) can be dissolved with the diamine compounds with structure shown in formula (VII), in the present invention, described have the compound of structure shown in formula (VI) and the mass ratio of solvent is preferably 1:1 ~ 25, is more preferably 1:2 ~ 20.
The compound with structure shown in formula (VI) preferably adds in solvent with the diamine compounds with structure shown in formula (VII) by the present invention, stirs and reacts, obtain the first intermediate product.The present invention does not have special restriction to described stirring, adopts stirring technique scheme well known to those skilled in the art.In the present invention, described in there is structure shown in formula (VI) compound and reaction time of the diamine compounds with structure shown in formula (VII) be preferably 2h ~ 5h, be more preferably 3.5h ~ 4.5h; The reaction temperature of the described compound with structure shown in formula (VI) and the diamine compounds with structure shown in formula (VII) is preferably 20 DEG C ~ 40 DEG C, is more preferably 25 DEG C ~ 35 DEG C.
After completing the reaction of the compound with structure shown in formula (VI) and the diamine compounds with structure shown in formula (VII), the reaction solution obtained preferably is carried out post processing by the present invention, obtains the first intermediate product.The present invention preferably removes the solvent in reaction solution, is washed by the solid matter obtained, and obtains the first intermediate product.The present invention does not have special restriction to the described method except desolventizing and washing, adopts the technical scheme removing desolventizing and washing well known to those skilled in the art.The present invention preferably vacuumizes except desolventizing described reaction solution, then washs the solid matter obtained with ether compound, and described ether compound is preferably ether.
After the present invention obtains the first intermediate product, described first intermediate product and metal chloride react by the present invention in organic solvent, obtain the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (I).
In the present invention, described first intermediate product and metal chloride react in organic solvent, obtain the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (I).The source of the present invention to described metal chloride does not have special restriction, adopts metal chloride well known to those skilled in the art.In the present invention, described metal chloride is preferably iron chloride, magnesium chloride, manganese chloride or zinc chloride.The present invention does not have special restriction to the kind of described organic solvent and source, adopts organic solvent well known to those skilled in the art.In the present invention, described organic solvent is preferably carrene.
Described first intermediate product preferably dissolves by the present invention in organic solvent, again by the solution of the first intermediate product that obtains and metal chloride mix and blend, react, obtain the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (I).The present invention does not have special restriction to described stirring, adopts stirring technique scheme well known to those skilled in the art.In the present invention, the time that described first intermediate product and metal chloride react is preferably 5h ~ 15h, is more preferably 8h ~ 14h, most preferably is 10h ~ 13h; The temperature that described first intermediate product and metal chloride react is preferably 20 DEG C ~ 40 DEG C, is more preferably 25 DEG C ~ 35 DEG C.In the present invention, described metal chloride consumption is preferably excessive, namely at least meets the first intermediate product and reacts completely with it.
After completing the reaction of described first intermediate product and metal chloride, the reaction solution obtained preferably is carried out post processing by the present invention, obtains the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (I).The reaction solution of described first intermediate product and metal chloride preferably filters by the present invention, obtains filtrate and solid; Described filtrate is mixed with ether compound, produces precipitation, after filtration, obtain the four tooth pyridine radicals schiff base metal complexes with formula (I) described structure.In the present invention, described ether compound is preferably ether.
Present invention also offers the preparation method that one has four tooth pyridine radicals schiff base metal complexes of structure shown in formula (II), comprise the following steps:
The first intermediate product technique scheme obtained and reducing agent react in a solvent, obtain the second intermediate product;
Described second intermediate product and metal chloride are reacted in organic solvent, obtains the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (II).
Described first intermediate product preferably dissolves by the present invention, the first intermediate product solution cooling then will obtained, then adds reducing agent wherein, stirs, reacts, obtain the second intermediate product.In the present invention, the temperature of described cooling is preferably-5 DEG C ~ 5 DEG C, is more preferably-2 DEG C ~ 2 DEG C, most preferably is 0 DEG C.
In the present invention, described reducing agent is preferably NaBH 4, one or more in ascorbic acid and hydrazine hydrate, be more preferably NaBH 4.In the present invention, the compound that described solvent is preferably adopted as structure shown in formula described in technique scheme (VI) and the reaction of diamine compounds with structure shown in formula (VII) provide the solvent of reaction medium, do not repeat them here.In the present invention, the mass ratio of described reducing agent and the first intermediate product is preferably 1:0.5 ~ 3, is more preferably 1:1 ~ 2.
First intermediate product and reducing agent preferably, under the condition stirred, react by the present invention.The present invention does not have special restriction to stirring, adopts stirring technique scheme well known to those skilled in the art.In the present invention, the reaction time of described first intermediate product and reducing agent is preferably 8h ~ 15h, is more preferably 9h ~ 14h, most preferably is 10h ~ 13h; The reaction temperature of described first intermediate product and reducing agent is preferably 20 DEG C ~ 40 DEG C, is more preferably 25 DEG C ~ 35 DEG C.
After completing the reaction of described first intermediate product and reducing agent, the present invention preferably will obtain reaction solution and carry out post processing, obtain the second intermediate product.The present invention preferably adopts the solvent in the method removing reaction solution vacuumized; Extractant and water is added in the solid obtained; Collect organic phase; Aqueous phase extracts with extractant again; Drier is adopted to carry out drying after the organic phase obtained being merged; Cross and filter drier, solvent removed in vacuo, obtain the second intermediate product.In the present invention, described extractant preferably adopts carrene; Described drier preferably adopts anhydrous magnesium sulfate.
After obtaining the second intermediate product, described second intermediate product and metal chloride react by the present invention in organic solvent, obtain the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (II).
The present invention adopts the metal chloride described in technique scheme and described second intermediate product to react, and kind and the consumption of described metal chloride do not repeat them here.The present invention adopts the first intermediate product described in technique scheme and the organic solvent in metal chloride course of reaction, does not repeat them here.In the present invention, described metal chloride consumption is preferably excessive, namely at least meets the second intermediate product and reacts completely with it.
Described second intermediate product preferably dissolves by the present invention in organic solvent, again the solution of the second intermediate product obtained is mixed with metal chloride, stirring is reacted, and obtains the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (II).Described second intermediate product dissolves by the present invention in organic solvent.The present invention does not have special restriction to described dissolving, adopts dissolving technology scheme well known to those skilled in the art.The present invention does not have special restriction to described stirring, adopts stirring technique scheme well known to those skilled in the art.In the present invention, the reaction time of described second intermediate product and metal chloride is preferably 8h ~ 15h, is more preferably 9h ~ 14h, most preferably is 10h ~ 13h; The reaction temperature of described second intermediate product and metal chloride is preferably 20 DEG C ~ 40 DEG C, is more preferably 25 DEG C ~ 35 DEG C.
After completing the reaction of described second intermediate product and metal chloride, the reaction solution obtained preferably is carried out post processing by the present invention, obtains the four tooth pyridine radicals schiff base metal complexes with structure shown in formula (II).The reaction solution of described second intermediate product and metal chloride preferably filters by the present invention, obtains filtrate and solid; Described filtrate is mixed with ether compound, produces precipitation, after filtration, obtain the four tooth pyridine radicals schiff base metal complexes with formula (II) described structure.In the present invention, described ether compound is preferably ether.
The invention provides a kind of method preparing cyclic carbonate, comprise the following steps:
Under the effect of major catalyst and co-catalyst, carbon dioxide and epoxides are carried out cycloaddition reaction, obtains cyclic carbonate;
The four tooth pyridine radicals schiff base metal complexes that described major catalyst prepares for method described in four tooth pyridine radicals schiff base metal complexes described in technique scheme or technique scheme;
Described co-catalyst is quaternary ammonium salt.
Carbon dioxide, epoxides, major catalyst and co-catalyst preferably add in autoclave by the present invention, carry out cycloaddition reaction, obtain cyclic carbonate; Be more preferably in glove box, described major catalyst, co-catalyst and epoxides be added in advance through dewatering, in deoxygenation processing reaction still, then reactor is shifted out glove box, and then be filled with CO in described reactor 2, carry out cycloaddition reaction.
In the present invention, the four tooth pyridine radicals schiff base metal complexes that prepare for method that four tooth pyridine radicals schiff base metal complexes described in technique scheme or technique scheme provide of described major catalyst.
In the present invention, described co-catalyst is quaternary ammonium salt, be preferably one or more in TBAB (TBAB), 4-propyl bromide, tetraethylammonium bromide, 4 bromide and tetramethyl ammonium chloride, be more preferably TBAB (TBAB).
In the present invention, described carbon dioxide is preferably the gaseous carbon dioxide that purity reaches 99.99%; The pressure of described carbon dioxide is preferably 1MPa ~ 6MPa, is more preferably 1.5MPa ~ 5MPa, most preferably is 2MPa ~ 4MPa.
The present invention does not have special restriction to the source of described epoxides and kind, adopts epoxides well known to those skilled in the art, obtains as bought by market.In the present invention, described epoxides is preferably one or more in oxirane, expoxy propane, 7-oxa-bicyclo[4.1.0, styrene oxide, epoxychloropropane, ethylene glycol diglycidylether, butanediol diglycidyl ether and neopentylglycol diglycidyl ether, is more preferably one or more in expoxy propane, 7-oxa-bicyclo[4.1.0, epoxychloropropane and ethylene glycol diglycidylether.
In the present invention, the mol ratio of described major catalyst, co-catalyst and epoxides is preferably 1:(0.5 ~ 1.5): (500 ~ 5000); Be more preferably 1:(0.8 ~ 1.2): (600 ~ 4000); Most preferably be 1:(0.9 ~ 1.1): (700 ~ 3000); The most be preferably 1:1:(800 ~ 1500).
In the present invention, the reaction temperature of described cycloaddition reaction is preferably 50 DEG C ~ 140 DEG C, is more preferably 60 DEG C ~ 130 DEG C, most preferably is 80 DEG C ~ 110 DEG C; The reaction time of described cycloaddition reaction is preferably 1h ~ 24h, is more preferably 2h ~ 20h, most preferably is 3h ~ 15h, is the most preferably 4h ~ 8h.
After cycloaddition reaction terminates, reactor is preferably cooled to room temperature by the present invention, bleeds off carbon dioxide wherein, obtains cyclic carbonate.
Four tooth pyridine radicals schiff base metal complexes provided by the invention have structure shown in formula (I) or formula (II).Under the existence of four tooth pyridine radicals schiff base metal complexes provided by the invention and co-catalyst quaternary ammonium salt, carbon dioxide and epoxides carry out cycloaddition reaction, prepare cyclic carbonate.In the process of cycloaddition reaction, four tooth pyridine radicals schiff base metal complexes have higher catalytic activity as major catalyst, improve the reaction rate of cycloaddition reaction, but also have good selectivity of product, reach more than 99%, improve the productive rate of cyclic carbonate in product.Further, the present invention is using nontoxic zinc, magnesium, manganese or iron as activated centre, and toxic metals content overproof in the cyclic carbonate that can effectively prevent catalysis from generating, is conducive to applying of cyclic carbonate ester material.
In order to further illustrate the present invention; below in conjunction with embodiment, the preparation method to four tooth pyridine schiff base metal complexes provided by the invention, its preparation method and cyclic carbonate is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
Add in 50mL absolute methanol by 5.63g2-pyridine carboxaldehyde and 3.00g1,2-cyclohexanediamine, after the mixed solution that obtains at room temperature stirring reaction 4h, the solvent in vacuum removing reaction solution, obtains product by after the solid washed with ether obtained.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in formula (XX);
The present invention calculates, and shown in formula described in the present embodiment (XX), the productive rate of the compound of structure is 75%.
The compound of structure 2.00g formula (XX) Suo Shi is dissolved in carrene, adds excessive ferrous chloride wherein.Reaction system at room temperature stirs spends the night, and filters.Add ether and produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, called after CAT.1.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.1-Cl] +molecular weight is 383.2; Theory calculate obtains [VIII-Cl] +molecular weight is 383.1, [VIII-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (VIII).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (VIII).
Embodiment 2
Shown in the formula (XX) 2.00g embodiment 1 obtained, the compound of structure is dissolved in 25mL absolute methanol, the solution of the compound of the structure described formula (XX) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h.Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, excessively filters magnesium sulfate, solvent removed in vacuo, obtain product.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in formula (XXI);
The present invention calculates, and the productive rate described in the present embodiment with the compound of structure shown in formula (XXI) is 95%.
The compound of structure formula described in 2.00g (XXI) Suo Shi is dissolved in carrene, adds excessive ferrous chloride wherein.The mixed solution obtained at room temperature is stirred and spends the night.The product obtained is filtered, in the filtrate obtained, adds ether produce precipitation, obtain four tooth pyridine radicals schiff base metal complexes after filtration, called after CAT.2.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.2-Cl] +molecular weight is 387.3; Theory calculate obtains [IX-Cl] +molecular weight is 387.1, [IX-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (IX).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (IX).
Embodiment 3
By 4.8g4-Chloro-2-Pyridyle formaldehyde and 3.00g4,5-dichloro o-phenylenediamine joins in 50mL absolute methanol, after the mixed solution that obtains at room temperature stirring reaction 4h, the solvent in vacuum removing reaction solution, obtains product by after the solid washed with ether obtained.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in formula (XXII);
The present invention calculates, and the productive rate described in the present embodiment with the compound of structure shown in formula (XXII) is 75%.
The compound of structure formula described in 2.00g (XXII) Suo Shi is dissolved in carrene, adds and wherein add excessive ferrous chloride.Reaction system at room temperature stirs spends the night, and filters.Add ether and produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, called after CAT.3.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.3-Cl] +molecular weight is 513; Theory calculate obtains [X-Cl] +molecular weight is 512.9, [X-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (X).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (X).
Embodiment 4
Shown in the formula (XXII) 2.00g embodiment 3 obtained, the compound of structure is dissolved in 25mL absolute methanol, the solution of the compound of the structure described formula (XXII) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h.Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, filtration, solvent removed in vacuo, obtains product.
The present invention will obtain product and carry out Structural Identification, and result shows, the product that the present embodiment obtains has structure shown in formula (XXIII);
The present invention calculates, and the productive rate described in the present embodiment with the compound of structure shown in formula (XXIII) is 95%.
The compound of structure formula described in 2.00g (XXIII) Suo Shi is dissolved in carrene, adds excessive ferrous chloride wherein.The mixed solution obtained at room temperature is stirred and spends the night.The product obtained is filtered, in the filtrate obtained, adds ether produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, called after CAT.4.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, and result shows in theory, [CAT.4-Cl] +molecular weight is 517; Theory calculate obtains [XI-Cl] +molecular weight is 516.9, [XI-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (XI).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (XI).
Embodiment 5
By 3.42g4-methyl-2-pyridine carboxaldehyde and 3.00g1,2-diphenyl-1,2-ethylenediamine joins in 50mL absolute methanol, after the mixed solution that obtains at room temperature stirring reaction 4h, solvent in vacuum removing reaction solution, obtains product by after the solid washed with ether obtained.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in formula (XXIV);
The present invention calculates, and the productive rate described in the present embodiment with the compound of structure shown in described formula (XXIV) is 75%.
The compound of structure formula described in 2.00g (XXIV) Suo Shi is dissolved in carrene, adds excessive magnesium dichloride wherein.Reaction system at room temperature stirs spends the night, and filters.Add ether and produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, called after CAT.5.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.5-Cl] +molecular weight is 477.4; Theory calculate obtains [XII-Cl] +molecular weight is 477.2, [XII-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (XII).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (XII).
Embodiment 6
Shown in the formula (XXIV) 2.00g embodiment 5 obtained, the compound of structure is dissolved in 25mL absolute methanol, the solution of the compound of the structure described formula (XXIV) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h.Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, filtration, solvent removed in vacuo, obtains product.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in described formula (XXV);
The present invention calculates, and has the productive rate 95% of the compound of structure shown in formula (XXV) described in the present embodiment.
The compound of structure formula described in 2.00g (XXV) Suo Shi is dissolved in carrene, adds excessive magnesium dichloride wherein.The mixed solution reaction system obtained at room temperature is stirred and spends the night.The product obtained is filtered, in the filtrate obtained, adds ether produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, called after CAT.6.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.6-Cl] +molecular weight is 481.3; Theory calculate obtains [XIII-Cl] +molecular weight is 481.2, [XIII-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (XIII).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (XIII).
Embodiment 7
By 14.2g3-trifluoromethyl-2-pyridine carboxaldehyde and 3.00g1,2-propane diamine joins in 50mL absolute methanol, after the mixed solution that obtains at room temperature stirring reaction 4h, the solvent in vacuum removing reaction solution, obtains product by after the solid washed with ether obtained.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in formula (XXVI);
The present invention calculates, and shown in formula described in the present embodiment (XXVI), the productive rate of the compound of structure is 75%.
The compound of structure formula described in 2.00g (XXVI) Suo Shi is dissolved in carrene, adds excessive zinc dichloride wherein.Reaction system at room temperature stirs spends the night, and filters.Add ether and produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, called after CAT.7.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.7-Cl] +molecular weight is 487; Theory calculate obtains [XIV-Cl] +molecular weight is 487, [XIV-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (XIV).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (XIV).
Embodiment 8
Shown in the formula (XXVI) 2.00g embodiment 7 obtained, the compound of structure is dissolved in 25mL absolute methanol, the compound reaction solution of the structure described formula (XXVI) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h.Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, filtration, solvent removed in vacuo, obtains product.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in formula (XXVII);
The present invention calculates, and the productive rate described in the present embodiment with the compound of structure shown in formula (XXVII) is 95%.
The compound of structure formula described in 2.00g (XXVII) Suo Shi is dissolved in carrene, adds excessive zinc dichloride wherein.The mixed solution obtained at room temperature is stirred and spends the night.The product obtained is filtered, in the filtrate obtained, adds ether produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, called after CAT.8.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.8-Cl] +molecular weight is 491; Theory calculate obtains [XV-Cl] +molecular weight is 491, [XV-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (XV).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (XV).
Embodiment 9
4.22g2-pyridine carboxaldehyde and 3.00g4-ethyoxyl o-phenylenediamine are joined in 50mL absolute methanol, after the mixed solution that obtains at room temperature stirring reaction 4h, solvent in vacuum removing reaction solution, obtains product by after the solid washed with ether obtained.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in formula (XXVIII);
The present invention calculates, and shown in formula described in the present embodiment (XXVIII), the productive rate of the compound of structure is 75%.
The compound of structure formula described in 2.00g (XXVIII) Suo Shi is dissolved in carrene, adds excessive ferrous chloride.Reaction system at room temperature stirs spends the night, and filters.Add ether and produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, called after CAT.9.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.9-Cl] +molecular weight is 421; Theory calculate obtains [XVI-Cl] +molecular weight is 421, [XVI-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (XVI).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (XVI).
Embodiment 10
Shown in the formula (XXVIII) 2.00g embodiment 9 obtained, the compound of structure is dissolved in 25mL absolute methanol, the solution of the compound of the structure described formula (XXVIII) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h.Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, filtration, solvent removed in vacuo, obtains product.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in formula (XXIX);
The present invention calculates, and shown in formula described in the present embodiment (XXIX), the productive rate of the compound of structure is 95%.
Shown in the described formula (XXIX) obtained by 2.00g, the compound of structure is dissolved in carrene, adds excessive ferrous chloride wherein.The reaction solution obtained at room temperature is stirred and spends the night.The product obtained is filtered, in the filtrate obtained, adds ether produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, called after CAT.10.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.10-Cl] +molecular weight is 425; Theory calculate obtains [XVII-Cl] +molecular weight is 425, [XVII-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (XVII).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (XVII).
Embodiment 11
By 3.42g6-(4-chlorphenyl)-2-pyridine carboxaldehyde and 3.00g1,2-bis-(4-chlorphenyl)-1,2-ethylenediamine joins in 50mL absolute methanol, at room temperature after stirring reaction 4h, solvent in vacuum removing reaction solution, obtains product by after the solid washed with ether obtained.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in formula (XXX);
The present invention calculates, and shown in formula described in the present embodiment (XXX), the productive rate of the compound of structure is 75%.
The compound of structure formula described in 2.00g (XXX) Suo Shi is dissolved in carrene, adds excessive manganous chloride.Reaction system at room temperature stirs spends the night, and filters.Adding ether has precipitation to produce, the four tooth pyridine radicals schiff base metal complexes quantitatively obtained after filtration, called after CAT.11.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.11-Cl] +molecular weight is 768; Theory calculate obtains [XVIII-Cl] +molecular weight is 768, [XVIII-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (XVIII).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (XVIII).
Embodiment 12
Shown in the formula (XXX) 2.00g embodiment 11 obtained, the compound of structure is dissolved in 25mL absolute methanol, the solution of the compound of the structure described formula (XXX) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h.Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, filtration, solvent removed in vacuo, obtains product.
The product obtained is carried out Structural Identification by the present invention, and result shows, the product that the present embodiment obtains has structure shown in formula (XXXI);
The present invention calculates, and shown in formula described in the present embodiment (XXXI), the productive rate of the compound of structure is 95%.
The compound of structure formula described in 2.00g (XXXI) Suo Shi is dissolved in carrene, adds excessive manganous chloride wherein.The mixed solution obtained at room temperature is stirred and spends the night.The product obtained is filtered, in the filtrate obtained, adds ether produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, called after CAT.12.
The four tooth pyridine radicals schiff base metal complexes obtained are carried out mass spectrometric measurement by the present invention, result display [CAT.12-Cl] +molecular weight is 772; Theory calculate obtains [XIX-Cl] +molecular weight is 772, [XIX-Cl] +the ionic group obtained after four tooth pyridine radicals schiff base metal complexes of structure lose a Cl shown in expression (XIX).These four tooth pyridine radicals schiff base metal complexes showing that the present embodiment synthesizes have structure shown in formula (XIX).
Embodiment 13
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.1 and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 130 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and expoxy propane only occurs in reaction, and single generation propylene carbonate, conversion ratio is 56.5%.
Embodiment 14
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.2 and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 130 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and expoxy propane only occurs in reaction, and single generation propylene carbonate, conversion ratio is 95%.
Embodiment 15
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.1,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and expoxy propane only occurs in reaction, and single generation propylene carbonate, conversion ratio is 98.6%.
Embodiment 16
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.2,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and expoxy propane only occurs in reaction, and single generation propylene carbonate, conversion ratio is 95.3%.
Embodiment 17
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.1,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 130 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and expoxy propane only occurs in reaction, and single generation propylene carbonate, conversion ratio is 100%.
Embodiment 18
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.2,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 130 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and expoxy propane only occurs in reaction, and single generation propylene carbonate, conversion ratio is 100%.
Embodiment 19
In glove box; under inert gas shielding condition; the 7-oxa-bicyclo[4.1.0 of 0.11mmolCAT.1,0.11mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 20h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxy 7-oxa-bicyclo[4.1.0 only occurs in reaction, and single generation cyclohexene carbonate, conversion ratio is 22.8%.
Embodiment 20
In glove box; under inert gas shielding condition; the 7-oxa-bicyclo[4.1.0 of 0.11mmolCAT.2,0.11mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 20h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and 7-oxa-bicyclo[4.1.0 only occurs in reaction, and single generation cyclohexene carbonate, conversion ratio is 49.5%.
Embodiment 21
In glove box; under inert gas shielding condition; the epoxychloropropane of 0.075mmolCAT.1,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxychloropropane only occurs in reaction, and single generation chloropropene carbonic ester, conversion ratio is 86.1%.
Embodiment 22
In glove box; under inert gas shielding condition; the epoxychloropropane of 0.075mmolCAT.2,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxychloropropane only occurs in reaction, and single generation chloropropene carbonic ester, conversion ratio is 96.7%.
Embodiment 23
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.1 and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 140 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 64.5%.
Embodiment 24
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.1 and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 50 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 7%.
Embodiment 25
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.1,0.075mmol and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 1.5MPa, temperature is controlled stirring reaction 2h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 91%.
Embodiment 26
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.2,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 1MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 95%.
Embodiment 27
In glove box; under inert gas shielding condition; the expoxy propane of 0.015mmolCAT.3,0.015mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 6MPa, temperature is controlled stirring reaction 1h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 27%.
Embodiment 28
In glove box; under inert gas shielding condition; the expoxy propane of 0.15mmolCAT.4,0.15mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 87%.
Embodiment 29
In glove box; under inert gas shielding condition; the epoxychloropropane of 0.075mmolCAT.5,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 85%.
Embodiment 30
In glove box; under inert gas shielding condition; the epoxychloropropane of 0.075mmolCAT.6,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 96%.
Embodiment 31
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.7,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 67%.
Embodiment 32
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.8,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 76%.
Embodiment 33
In glove box; under inert gas shielding condition; the 7-oxa-bicyclo[4.1.0 of 0.075mmolCAT.9,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 24h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 21%.
Embodiment 34
In glove box; under inert gas shielding condition; the 7-oxa-bicyclo[4.1.0 of 0.075mmolCAT.10,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 24h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 45%.
Embodiment 35
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.11,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 76%.
Embodiment 36
In glove box; under inert gas shielding condition; the expoxy propane of 0.075mmolCAT.12,0.075mmolTBAB and 75mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 82%.
Embodiment 37
In glove box; under inert gas shielding condition; the ethylene glycol diglycidylether of 0.060mmolCAT.1,0.060mmolTBAB and 30mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 64%.
Embodiment 38
In glove box; under inert gas shielding condition; the ethylene glycol diglycidylether of 0.060mmolCAT.2,0.060mmolTBAB and 30mmol drying is added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 4MPa, temperature is controlled stirring reaction 4h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 100%.
Comparative example
In glove box; under inert gas shielding condition; by 0.30mmol [N; N-bis-(quinoline-2-methine)-1; 2-cyclohexanediamine] frerrous chloride, 0.30mmolTBAB and 30mmol drying expoxy propane be added in advance through dewatering, in the 15mL autoclave of deoxygenation process, rapidly by having the CO of pressure adjusting function after autoclave being taken out glove box 2supply line is filled with CO in reactor 2to 1.5MPa, temperature is controlled stirring reaction 2h at 100 DEG C.After reaction terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide wherein, get appropriate reaction stoste and carry out 1h-NMR tests.
1h-NMR test result shows, and the cycloaddition reaction of carbon dioxide and epoxides only occurs in reaction, and single generation cyclic carbonate, conversion ratio is 82%.
As seen from the above embodiment, four tooth pyridine radicals schiff base metal complexes provided by the invention have structure shown in formula (I) or formula (II).Under co-catalyst quaternary ammonium salt exists, carbon dioxide and epoxides cycloaddition reaction are prepared in the process of cyclic carbonate, four tooth pyridine radicals schiff base metal complexes have higher catalytic activity as major catalyst, improve the reaction rate of cycloaddition reaction and have product higher selective, inhibit the generation of Merlon, improve the content of cyclic carbonate in product.Further, the present invention is using nontoxic zinc, magnesium, manganese or iron as activated centre, and toxic metals content overproof in the cyclic carbonate effectively preventing catalysis from generating, is conducive to applying of cyclic carbonate ester material.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (1)

1. prepare a method for four tooth pyridine radicals schiff base metal complexes, comprise the following steps:
The compound of structure 2.00g formula (XXII) Suo Shi is dissolved in 25mL absolute methanol, the solution of the compound of the structure described formula (XXII) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h; Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, filtration, solvent removed in vacuo, obtains product, and described product has structure shown in formula (XXIII);
The compound of structure formula described in 2.00g (XXIII) Suo Shi is dissolved in carrene, adds excessive ferrous chloride wherein; The mixed solution obtained at room temperature is stirred and spends the night; The product obtained filtered, in the filtrate obtained, add ether produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, described four tooth pyridine radicals schiff base metal complexes have structure shown in formula (XI):
Or the compound of structure 2.00g formula (XXIV) Suo Shi is dissolved in 25mL absolute methanol, the solution of the compound of the structure described formula (XXIV) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h; Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, filtration, solvent removed in vacuo, obtains product, and described product has structure shown in formula (XXV);
The compound of structure formula described in 2.00g (XXV) Suo Shi is dissolved in carrene, add excessive magnesium dichloride wherein, the mixed solution reaction system obtained at room temperature is stirred and spends the night, the product obtained is filtered, in the filtrate obtained, add ether produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, described four tooth pyridine radicals schiff base metal complexes have structure shown in formula (XIII);
Or the compound of structure 2.00g formula (XXVI) Suo Shi is dissolved in 25mL absolute methanol, the compound reaction solution of the structure described formula (XXVI) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h; Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, filtration, solvent removed in vacuo, obtains product, and described product has structure shown in formula (XXVII);
The compound of structure formula described in 2.00g (XXVII) Suo Shi is dissolved in carrene, add excessive zinc dichloride wherein, the mixed solution obtained at room temperature is stirred and spends the night, the product obtained is filtered, in the filtrate obtained, add ether produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, described four tooth pyridine radicals schiff base metal complexes have structure shown in formula (XV);
Or the compound of structure 2.00g formula (XXVIII) Suo Shi is dissolved in 25mL absolute methanol, the solution of the compound of the structure described formula (XXVIII) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h; Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, filtration, solvent removed in vacuo, obtains product, and described product has structure shown in formula (XXIX);
Shown in the described formula (XXIX) obtained by 2.00g, the compound of structure is dissolved in carrene, adds excessive ferrous chloride wherein; The reaction solution obtained at room temperature is stirred and spends the night; The product obtained filtered, in the filtrate obtained, add ether produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, described four tooth pyridine radicals schiff base metal complexes have structure shown in formula (XVII);
Or the compound of structure 2.00g formula (XXX) Suo Shi is dissolved in 25mL absolute methanol, the solution of the compound of the structure described formula (XXX) obtained Suo Shi is cooled to 0 DEG C, slowly adds 2.59gNaBH wherein 4, reaction system is warming up to room temperature and continues stirring reaction 12h; Solvent in vacuum removing reaction solution, adds 100mL carrene in the solid obtained and 50mL water extracts, and collects organic phase; Aqueous phase uses 100mL dichloromethane extraction 2 times again, organic phase is merged rear anhydrous magnesium sulfate drying, filtration, solvent removed in vacuo, obtains product, and described product has structure shown in formula (XXXI);
The compound of structure formula described in 2.00g (XXXI) Suo Shi is dissolved in carrene, adds excessive manganous chloride wherein; The mixed solution obtained at room temperature is stirred and spends the night; The product obtained filtered, in the filtrate obtained, add ether produce precipitation, the four tooth pyridine radicals schiff base metal complexes obtained after filtration, described four tooth pyridine radicals schiff base metal complexes have structure shown in formula (XIX);
CN201310400893.4A 2013-09-05 2013-09-05 The method of four tooth pyridine radicals schiff base metal complexes, its preparation method and cyclic carbonate Active CN103447091B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310400893.4A CN103447091B (en) 2013-09-05 2013-09-05 The method of four tooth pyridine radicals schiff base metal complexes, its preparation method and cyclic carbonate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310400893.4A CN103447091B (en) 2013-09-05 2013-09-05 The method of four tooth pyridine radicals schiff base metal complexes, its preparation method and cyclic carbonate

Publications (2)

Publication Number Publication Date
CN103447091A CN103447091A (en) 2013-12-18
CN103447091B true CN103447091B (en) 2016-03-30

Family

ID=49730166

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310400893.4A Active CN103447091B (en) 2013-09-05 2013-09-05 The method of four tooth pyridine radicals schiff base metal complexes, its preparation method and cyclic carbonate

Country Status (1)

Country Link
CN (1) CN103447091B (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103641811B (en) * 2013-12-20 2015-05-20 苏州大学张家港工业技术研究院 Method for preparing cyclic carbonate
CN103789789B (en) * 2014-02-11 2016-06-29 华东师范大学 Electrochemical synthesis has the method for optically active Styrene carbonate
CN108069894A (en) * 2016-11-11 2018-05-25 天津工业大学 A kind of new Salen ligands synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde and preparation method thereof
TWI601571B (en) * 2016-12-07 2017-10-11 財團法人工業技術研究院 Catalyst and method for synthesizing cyclic carbonate by the same
CN107778473B (en) * 2017-10-30 2019-11-08 河南工程学院 A kind of catalyst for carbon dioxide and 7-oxa-bicyclo[4.1.0 copolyreaction preparation polycyclohexene
CN107722254B (en) * 2017-10-30 2019-11-08 河南工程学院 The catalyst and catalysis process for preparing fatty poly-ester carbonate are reacted with cyclohexene oxide for carbon dioxide
CN107778470B (en) * 2017-10-30 2019-11-08 河南工程学院 A kind of catalyst being used to prepare polycyclohexene
CN107722253B (en) * 2017-10-30 2019-11-22 河南工程学院 A kind of catalyst for carbon dioxide and cyclohexene oxide copolyreaction preparation polycyclohexene
CN107586382B (en) * 2017-10-30 2020-08-28 河南理工大学 Zinc catalyst for preparing poly (trimethylene carbonate)
CN107778472B (en) * 2017-10-30 2019-11-22 河南工程学院 It is a kind of to prepare the catalyst of polycyclohexene for being catalyzed carbon dioxide and 7-oxa-bicyclo[4.1.0 copolyreaction
CN107641197B (en) * 2017-10-30 2019-11-22 河南工程学院 It is a kind of using carbon dioxide and 7-oxa-bicyclo[4.1.0 as the copolyreaction catalyst of monomer
KR102588584B1 (en) * 2018-09-18 2023-10-12 피티티 엑스플러레이션 앤드 프로덕션 퍼블릭 컴퍼니 리미티드 Catalytic systems and related methods for producing cyclic carbonates
US20220379290A1 (en) * 2019-09-30 2022-12-01 Ptt Global Chemical Public Company Limited Catalyst composition for cyclic carbonate production from co2 and epoxides
CN111662422B (en) * 2020-06-19 2021-06-01 山东大学 Metal complex covalent organic framework material and preparation method and application thereof
CN113416147A (en) * 2021-06-28 2021-09-21 上海应用技术大学 Schiff base-metal organic complex and preparation method and application thereof
CN114716371B (en) * 2022-03-10 2023-09-26 上海应用技术大学 N-containing active center metal organic catalyst for synthesizing cyclic carbonate, and preparation method and application thereof
CN117143067B (en) * 2023-08-09 2024-05-07 山东农业大学 Metal complex in CO catalysis2Use of cyclisation for the preparation of cyclic carbonates

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013004874A1 (en) * 2011-07-06 2013-01-10 Universitat De Girona Method for the catalytic oxidation of water using iron catalysts

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012139994A1 (en) * 2011-04-13 2012-10-18 Basf Se Process for coupling epoxides and carbon dioxide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013004874A1 (en) * 2011-07-06 2013-01-10 Universitat De Girona Method for the catalytic oxidation of water using iron catalysts

Non-Patent Citations (17)

* Cited by examiner, † Cited by third party
Title
"A One-Component Iron Catalyst for Cyclic Propylene Carbonate Synthesis";Joachim E. Dengler et al;《European Journal of Inorganic chemistry》;20101214;第337-339页和摘要 *
"Assessing the impact of inductive electronic effects on the metrical parameters and reactivity of a series of ferrous complexes";Cristina M. Coates et al;《Inorganica Chimica Acta》;20090831;第363卷;第201页 *
"Cobalt Chloride Complexes of N3 and N4 Donor Ligands";T. Martijn Kooistra et al;《European Journal of Inorganic chemistry》;20031231;第648-655页 *
"Easy-to-handle ionic transition metal complexes in the formation of carbonates from epoxides and CO2: A N4-ligand system based on N,N-bis(2-pyridinecarboxamide)-1,2-benzene";M. Adolph et al;《Polyhedron》;20120913;第48卷;第92~98页 *
"Efficient water oxidation catalysts based on readily available iron coordination complexes";Julio Lloret Fillol et al;《NATURE CHEMISTRY》;20111231;第3卷;第808页 *
"H2O2-Dependent Fe-Catalyzed Oxidations:Control of the Active Species";Yasmina Mekmouche et al;《European Journal of Inorganic chemistry》;20011231;第40卷(第5期);第950页 *
"Hydrocarbon chlorination promoted by manganese and iron complexes with methylated derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine";Christian R. Goldsmith et al;《Journal of Molecular Catalysis A: Chemical》;20101113;第335卷;第25、27页 *
"Incorporation of Hydrogen-Bonding Functionalities into the Second Coordination Sphere of Iron-Based Water-Oxidation Catalysts";Wesley A. Hoffert et al;《European Journal of Inorganic chemistry》;20130409;第22-23卷;第3849页 *
"Iron Complexes Containing the Ligand N,N’-Bis(6-methyl-2-pyridylmethyl)-N,N’-bis(2-pyridylmethyl)ethane-1,2-diamine";Veronique Balland et al;《European Journal of Inorganic chemistry》;20031231;第2530页 *
"Iron Coordination Chemistry with New Ligands Containing Triazole and Pyridine Moieties. Comparison of the Coordination Ability of the N-Donors";Nathalie Segaud et al;《Inorganic Chemistry》;20130109;第52卷;第692页 *
"Manganese(II) complexes of pyridyl-appended diazacyclo-alkanes: Effect of ligand backbone ring size on catalytic olefin oxidation";Natarajan Saravanan et al;《Inorganica Chimica Acta》;20120128;第385卷;第101页和第104页 *
"Mechanistic Tuning of Hydrocarbon Oxidations with H2O2, Catalyzed by Hexacoordinate Ferrous Complexes";Yasmina Mekmouche et al;《European Journal of Inorganic chemistry》;20040601;第3164和3165页 *
"Robust Iron Coordination Complexes with N‑Based Neutral Ligands As Efficient Fenton-Like Catalysts at Neutral pH";Maite Canals et al;《Environmental Science & Technology》;20130729;第47卷;第9919和9922页 *
"Steric Modifications Tune the Regioselectivity of the Alkane Oxidation Catalyzed by Non-Heme Iron Complexes";Yu He et al;《Inorganic Chemistry》;20111109;第50卷;第12652和12654页 *
"Structural characterization of manganese and iron complexes with methylated derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine reveals unanticipated conformational flexibility";Cristina M. Coates et al;《Dalton Trans.》;20111231;第40卷;第4048~4058页 *
"The influence of inductive ligand electronics on the metrical parameters and redox potentials of a series of manganese(II) compounds";Cristina M. Coates et al;《Inorganica Chimica Acta》;20090712;第362卷;第4798页和第4801页 *
Syntheses, Crystal Structures, and Spectroscopic and Magnetic Properties of [Mn2III(H2L1)(Cl4Cat)4â2H2O]：Temperature-Dependent Valence;Nizamuddin Shaikh et al;《Inorganic Chemistry》;20051125;第44卷(第26期);第9716页 *

Also Published As

Publication number Publication date
CN103447091A (en) 2013-12-18

Similar Documents

Publication Publication Date Title
CN103447091B (en) The method of four tooth pyridine radicals schiff base metal complexes, its preparation method and cyclic carbonate
Kurisingal et al. Binary metal-organic frameworks: Catalysts for the efficient solvent-free CO2 fixation reaction via cyclic carbonates synthesis
Zou et al. Highly efficient conversion of CO2 at atmospheric pressure to cyclic carbonates with in situ-generated homogeneous catalysts from a copper-containing coordination polymer
Wang et al. Central-metal exchange, improved catalytic activity, photoluminescence properties of a new family of d 10 coordination polymers based on the 5, 5′-(1 H-2, 3, 5-triazole-1, 4-diyl) diisophthalic acid ligand
Prasad et al. Paving way for sustainable earth-abundant metal based catalysts for chemical fixation of CO2 into epoxides for cyclic carbonate formation
Kilic et al. Synthesis and characterization of novel positively charged organocobaloximes as catalysts for the fixation of CO2 to cyclic carbonates
Paul et al. Amide functionalized metal–organic frameworks for diastereoselective nitroaldol (Henry) reaction in aqueous medium
CN110105321A (en) A kind of method of eutectic ionic liquid catalysis carbon dioxide synthesizing annular carbonate
CN112495431B (en) Method for synthesizing cyclic carbonate by mild catalysis of multi-site ionic liquid
Ulusoy et al. Structural, spectral, electrochemical and catalytic reactivity studies of a series of N2O2 chelated palladium (II) complexes
CN112409190B (en) Method for efficiently synthesizing cyclic carbonate by using amine salt ionic liquid as catalyst
Gu et al. Non-noble-metal metal–organic-framework-catalyzed carboxylative cyclization of propargylic amines with atmospheric carbon dioxide under ambient conditions
Kang et al. Stable metal-organic frameworks with high catalytic performance in the cycloaddition of CO 2 with aziridines
CN104650026A (en) Method for preparing propylene carbonate
CN107175133A (en) A kind of silicon dioxide carried copper dipyridyl catalyst and preparation method thereof
Yadav et al. Ferrocene-functionalized dithiocarbamate zinc (II) complexes as efficient bifunctional catalysts for the one-pot synthesis of chromene and imidazopyrimidine derivatives via Knoevenagel condensation reaction
Chen et al. Construction of stable MOFs integrated with open metal sites and amine groups for CO2 capture and conversion
KR101368349B1 (en) Method of preparation of glycerol carbonate by using the metal organic frameworks as catalysts
CN107199051B (en) A kind of copper heterogeneous catalyst of pyridine coordination and preparation method thereof
Le et al. Construction of Acylamide-functionalized MOFs for efficient catalysis on the conversion of CO2
Ge et al. A solid Zn complex catalyst for efficient transformation of CO2 to cyclic carbonates at mild conditions
CN103566970A (en) Chromium, zinc or copper complexed conjugated microporous polymer catalysts, as well as preparation method and application thereof
CN104926782A (en) Method for preparing cyclic carbonate using isothiourea salt ionic liquid
Zhang et al. Construction of Co/Ni-based coordination polymers with three-dimensional isostructural frameworks and multiple catalytic applications
CN104592425B (en) A kind of cycloheptatriene base rare-earth metal catalyst, preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20210414

Address after: 130012 5218 Longhu Road, north new hi-tech, Changchun, Jilin

Patentee after: Changchun applied chemical science and Technology General Corporation of Chinese Academy of Sciences

Address before: 130022 No. 5625 Renmin Street, Jilin, Changchun

Patentee before: Changchun Institute of Applied Chemistry Chinese Academy of Sciences

CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: 130012 5218 Longhu Road, north new hi-tech, Changchun, Jilin

Patentee after: Zhongke Yinghua (Changchun) Technology Co.,Ltd.

Address before: 130012 5218 Longhu Road, north new hi-tech, Changchun, Jilin

Patentee before: Changchun applied chemical science and Technology General Corporation of Chinese Academy of Sciences