CN108503848A - A kind of Salen-Rh (II) coordination polymer and its preparation method and application - Google Patents
A kind of Salen-Rh (II) coordination polymer and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to the preparing technical fields of organometallic complex, specifically disclose a kind of Salen Rh (II) coordination polymer and its preparation method and application.The structure of Salen Rh (II) coordination polymer is as shown in formula (i) or formula (ii), wherein R1For H, CH3Or C (CH3)3.Salen Rh (II) coordination polymers prepared by the present invention can preferably apply to be catalyzed diazonium compound decomposition as catalyst, catalyst stability is good, usage amount is small, reaction efficiency is high, and catalyst can realize the separation of catalyst and product through simple process, and the catalyst circulation of recycling uses repeatedly, its catalytic performance is not decreased obviously, and is the green catalyst of a kind of great industrial value.
Description
Technical field
The present invention relates to the preparing technical field of organometallic complex more particularly to a kind of Salen-Rh (II) polycomplexations
Close object and its preparation method and application.
Background technology
From Curtius since synthesis α-diazonium carbonyls in 1883 for the first time, the synthesis application of diazonium compound
There is larger development, the metallic catalysts such as various copper, rhodium for especially synthesizing in recent years are widely used in diazonium compound
Catalytic decomposition so that this type organic is widely used in organic synthesis.Diazonium compound is in transition metal etc.
Under the action of catalyst, it is decomposed to form the active metal carbene intermediate of height, metal carbene is a kind of very important organic
Synthetic intermediate not only has and higher reactivity but also has good selectivity, therefore they are in organic synthesis
With highly important status.Metal copper catalyst is earliest as the catalyst for being catalyzed diazo decomposition, metal copper catalyst
Although reactivity is high, reaction selectivity is poor, thus is gradually abandoned by people.Diazo compounds are catalytically decomposed in metal rhodium (II)
Object has the advantages that efficient, highly selective, causes the extensive concern of people.Common rhodium catalyst mainly has carboxylic acid rhodium catalysis
Agent and amide rhodium catalyst.Different from metallic copper, the bridged bond carboxylic acid of the metal rhodium catalyst of divalent or the variation of amide ligands can
The reactivity and selectivity decomposed with control.But rhodium metal resource scarcity is non-renewable and expensive so that rhodium salt is catalyzed
The production cost of agent is higher, and existing rhodium catalyst is the homogeneous catalyst of solubility mostly at present, it is difficult to from reaction system
It separates so that catalyst can not recycle, this not only limits the application of metal rhodium catalyst, and heavy metal rhodium
Direct emission can also cause secondary pollution to environment.Therefore, it develops a kind of catalytic activity height and metal rhodium can be recycled is urged
Agent has a very important significance.
Invention content
The technical problem to be solved in the present invention is to provide a kind of Salen-Rh (II) coordination polymer, Salen is N, N-bis
(salicylidine) abbreviation of ethylene-diamine [N, N'- ethylene two (salicylidene imines)], is diimine class chemical combination
The general designation of object, Salen class compounds are to contain N, O coordinations with what diamine compounds were condensed to yield by salicylide or derivatives thereof
The organic ligand of atom.Salen-Rh (II) coordination polymer provided by the invention aims to solve the problem that existing catalysis diazonium compound point
The catalyst activity of solution reaction needs to be further increased, production cost height, is not easily recycled the problem of utilization.
In order to solve the above technical problems, technical solution provided by the invention is：
A kind of Salen-Rh (II) coordination polymer, the structure such as formula (I) of Salen-Rh (II) coordination polymer or
Shown in formula (II)：
Wherein, R1For H ,-CH3Or-C (CH3)3。
Formula (I) and formula (II) indicate the repetitive unit of polymer architecture, and connection is corresponding in turn to up and down between repetitive unit.
(I) upper end in repetitive unit in formulaWith upper end in a upper repetitive unitConnection, repetitive unit
Middle lower endWith lower end in a upper repetitive unitConnection.(II) upper end in repetitive unit in formulaWith upper repetitive unit upper endIt connects, lower end in repetitive unitWith upper repetitive unit lower endConnection.
Salen-Rh (II) coordination polymer provided by the present invention is between metal ion and organic ligand through self assembly
The structure novel of formation and the Metal-organic complex haveing excellent performance have bimetallic activated centre, are lived by bimetallic
Property center coordinative role can effectively be catalyzed a variety of chemical reactions, two metal catalytic activity centers can be simultaneously to substrate
It is activated, to accelerate reaction speed and improve reaction selectivity.It can preferably apply to catalysis weight as catalyst
Nitrogen compound decomposition, catalyst stability is good, usage amount is small, reaction efficiency is high, and catalyst can be realized through simple process and be urged
The separation of agent and product, and the catalyst circulation recycled, using repeatedly, catalytic performance is not decreased obviously, and is a kind of great
The green catalyst of industrial value.
The present invention also provides a kind of preparation methods of Salen-Rh (II) coordination polymer, include the following steps：
Step a：Salen ligands are prepared, salicylaldehyde derivatives are dissolved in methanol, mixed solution is obtained, the mixing is molten
Liquid is added dropwise in the methanol solution of (1R, 2R)-cyclohexanediamine, is stirred to react under the conditions of 15~25 DEG C to get such as formula (III)
Shown in Salen ligands；
Wherein, the structural formula of salicylaldehyde derivatives is：
R1For H ,-CH3、-C(CH3)3；R2For-COOH or
Step b：Salen-Rh (II) organometallic complex is prepared, the Salen ligands are dissolved in alcohol solvent, are added
Enter rhodium acetate, be stirred at reflux reaction, be subsequently cooled to -5~-10 DEG C, insulated and stirred 1~2 hour filters, and air blast drying obtains formula
(IV) Salen-Rh shown in (II) organometallic complex：
R1For H ,-CH3Or-C (CH3)3；R2For-COOH or
Step c：Prepare Salen-Rh (II) coordination polymer：
(1) work as R2ForWhen, the Salen-Rh (II) organometallic complex is dissolved in dimethylformamide
In methanol mixed solution, terephthalic acid (TPA) is added, fully after dissolving, cadmium nitrate is added, then agitating and heating reaction cools down
To -5~-10 DEG C, insulated and stirred 1~2 hour filters drying, obtains Salen-Rh (I) coordination polymer shown in formula (II).
(2) work as R2For-COOH when, by the Salen-Rh (II) organometallic complex be dissolved in dimethylformamide and
In potassium hydroxide aqueous solution, 4,4'-Bipyridine is added after mixing, the dimethyl sulphoxide solution of cadmium nitrate is added, stirring adds
Thermal response, is subsequently cooled to -5~-10 DEG C, and insulated and stirred 1~2 hour filters drying, obtains Salen-Rh shown in formula (II)
(II) coordination polymer.
The preparation method of Salen-Rh (II) coordination polymer provided by the invention, step is simple, and cost is relatively low, operation side
Just, it is convenient for industrialized production and application.
The present invention also provides above-mentioned Salen-Rh (II) coordination polymers in catalytic decomposition diazonium compound reaction
Using.
Preferably, application of Salen-Rh (II) coordination polymers in catalytic decomposition diazonium compound reaction,
Reaction includes the following steps：
It using diazotate a as reaction substrate, is dissolved in dichloromethane, after dissolving fully, stops stirring, described in addition
Salen-Rh (II) coordination polymer, agitating and heating back flow reaction 4h, the dichloromethane through cyclization target product b is obtained by filtration are molten
Liquid.Its reaction equation is：
Diazonium compound, which is catalytically decomposed to form metal carbene and then carry out N-H, is inserted into completion cyclization, is among drug
The higher synthetic method of a kind of important and applying frequency in body synthesis.Utilize Salen-Rh provided by the invention (II) polycomplexation
It closes object and decomposes diazonium compound as catalyst, dosage is few, and catalytic activity is high, and yield is high, and passes through after reaction
The recycling of catalyst may be implemented in filtering, recycles multiple catalytic activity without being decreased obviously, therefore can reduce cost,
It reduces environmental pollution.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The basic conception of the embodiment of the present invention is：The catalysis that structure by modifying Salen complexs changes catalyst is lived
Property, while realizing the recoverable of catalyst.
The embodiment of the present invention is described in detail below.
The embodiment of the present invention provides a kind of Salen-Rh (II) coordination polymer, Salen-Rh (II) coordination polymer
Structure as shown in formula (i) or formula (ii)：
Wherein, R1For H ,-CH3Or-C (CH3)3。
Salen-Rh (II) coordination polymer provided by the invention, using Salen compounds as ligand, by Salen
The ortho position of the hydroxyl of ligand connects different functional groups and is modified, and changes its property in steric hindrance and electronic effect etc.,
And then the catalytic property of central coordinated metal is influenced, while aligning connection carboxyl or pyridyl group in hydroxyl makes mononuclear complex be formed
Coordination polymer enables catalyst to recycle, and helps to reduce production cost, reduces the pollution of environment, be advantageously implemented
Sustainable production.
The preparation method that the embodiment of the present invention additionally provides the Salen-Rh (II) coordination polymer includes the following steps：
Step a：Salen ligands are prepared, salicylaldehyde derivatives are dissolved in methanol, ligand solution is obtained, the ligand is molten
Liquid is added dropwise in the methanol solution of (1R, 2R)-cyclohexanediamine, is stirred to react under the conditions of 15~25 DEG C to get such as formula (III)
Shown in Salen ligands；
Wherein, the structural formula of salicylaldehyde derivatives is：
R1For H ,-CH3、-C(CH3)3；R2For-COOH or
Step b：Salen-Rh (II) organometallic complex is prepared, the salen ligands are dissolved in alcohol solvent, are added
Enter rhodium acetate, be stirred at reflux reaction, be subsequently cooled to -5~-10 DEG C, insulated and stirred 1~2 hour filters, and air blast drying obtains formula
(IV) Salen-Rh shown in (II) organometallic complex；
R1For H ,-CH3Or-C (CH3)3；R2For-COOH or
Step c：Prepare Salen-Rh (II) coordination polymer：
(1) work as R2ForWhen, the Salen-Rh (II) organometallic complex is dissolved in dimethylformamide
In methanol mixed solution, terephthalic acid (TPA) is added, fully after dissolving, cadmium nitrate is added, then agitating and heating reaction cools down
To -5~-10 DEG C, insulated and stirred 1~2 hour filters drying, obtains Salen-Rh (I) coordination polymer shown in formula (II).
(2) work as R2For-COOH when, by the Salen-Rh (II) organometallic complex be dissolved in dimethylformamide and
In potassium hydroxide aqueous solution, 4,4'-Bipyridine is added after mixing, the dimethyl sulphoxide solution of cadmium nitrate is added, stirring adds
Thermal response, is subsequently cooled to -5~-10 DEG C, and insulated and stirred 1~2 hour filters drying, obtains Salen-Rh shown in formula (II)
(II) coordination polymer.
Preferably, the molar ratio of salicylaldehyde derivatives and (1R, the 2R)-cyclohexanediamine is 1 in step a:2.
Preferably, in step b Salen ligands and alcohol solvent mass ratio 1:10~30, Salen ligand and rhodium acetate
Molar ratio 1:0.5~1, the time of back flow reaction is 4~12h.
Preferably, work as R in step c2For-COOH when, Salen-Rh (II) organometallic complexs and potassium hydroxide mole
Than 1:2~3, Salen-Rh (II) organometallic complex and dimethylformamide mass ratio 1:100~150, water and dimethyl
Formamide volume ratio is 1:4~8, Salen-Rh (II) organometallic complex and 4,4'-Bipyridine molar ratio 1:1~4,
Salen-Rh (II) organometallic complexs and cadmium nitrate molar ratio 1:2~4, be stirred to react the time be 2~3h, temperature be 30~
60℃。
Preferably, work as R in step c2ForWhen pyridyl group, Salen-Rh (II) organometallic complexs with to benzene
Dioctyl phthalate molar ratio 1:0.5~2, Salen-Rh (II) organometallic complex and dimethylformamide mass ratio 1:15~30,
Methanol and dimethylformamide volume ratio 1:8~12, Salen-Rh (II) organometallic complex and cadmium nitrate molar ratio 1:1~
4, it is 2~3h to be stirred to react the time, and temperature is 30~60 DEG C.
Preparation method is simple for Salen-Rh (II) coordination polymer provided by the present invention, catalyst high income,
And catalyst can protect non-renewable rare precious metals resource, while catalyst will not give environment band with cycle applications
It bears, is a kind of catalyst manufacturing process of environment-friendly and green.
It is anti-in catalytic decomposition diazonium compound that the embodiment of the present invention additionally provides above-mentioned Salen-Rh (II) coordination polymers
Application in answering.
Preferably, application of Salen-Rh (II) coordination polymers in catalytic decomposition diazonium compound reaction,
Reaction includes the following steps：
It using diazotate a as reaction substrate, is dissolved in dichloromethane, after dissolving fully, stops stirring, described in addition
Salen-Rh (II) coordination polymer, agitating and heating back flow reaction 4h, the dichloromethane through cyclization target product b is obtained by filtration are molten
Liquid.Its reaction equation is：
Preferably, the diazotate a and the Salen-Rh (II) coordination polymers molar ratio 1:0.0005~
The mass ratio of 0.0025, diazotate a and dichloromethane is 1:3~5.
Preferably, filtration temperature is 25~35 DEG C, product section can be made to be precipitated if filtration temperature is too low, blocks filter paper or filter
Cloth；If filtration temperature is excessively high, the volatilization of dichloromethane solvent can be made to accelerate, while also easy ting produce side reaction.
Salen-Rh (II) coordination polymers that the present invention improves, which have catalytic decomposition diazonium compound reaction, preferably urges
Change effect, and reaction condition is mild, post-processing is simple, is a kind of valuable diazonium compound cleavage reaction catalyst.
In order to better illustrate the present invention, illustrated below by embodiment is further.
Embodiment 1
The preparation of (R, R)-(-)-N, N '-two (5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine：
A clean reaction bulb is taken, is added 200ml methanol, 5.7g (1R, 2R)-cyclohexanediamine, after stirring and dissolving, by 9.95g
5- (4- pyridyl groups) salicylide is dissolved in 200ml methanol solvates, is slowly added dropwise in above-mentioned reaction bulb, return stirring reaction
2h is added cold water 120ml, is cooled to 0~5 DEG C, continues to stir 1h, filters, washed with 50ml methanol, obtains bright yellow solid production
Object 20.3g, yield 85.5%.1H-NMR(600MHz,CDCl3):2.08-1.54 (m, 8H), 3.30 (2H, m), 7.37 (2H, d),
7.51 (2H, d), 7.55 (2H, d), 7.83 (2H, s), 7.92 (4H, d), 8.57 (4H, d).
(R, R)-(-)-N, N '-two (5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine-Rh (II) organic metal
The preparation of complex：
It measures 100ml ethyl alcohol to be added in clean reaction bulb, opens electric stirring, 4.76g (R, R)-(-)-N, N '-two is added
(5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine stirs 1 hour and dissolves, 2.2g rhodium acetates are added, stirs 0.5 hour
After mixing, back flow reaction 6h, stirring slow cooling keep temperature to stir 1~2 hour, filter, air blast to -5~-10 DEG C
Drying, obtains yellow target product 5.6g, yield 97%.
(R, R)-(-)-N, N '-two (5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine-Rh (II) coordination polymerization
The preparation of object:
It takes in a clean reaction bulb, 120ml dimethylformamides and 10ml methanol is added, opens electric stirring, is added
5.78g (R, R)-(-)-N, N '-two (5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine-Rh organometallic complexs,
After stirring evenly, be added 1.66g terephthalic acid (TPA)s, 30 DEG C stirring 15min, be added 4.7g cadmium nitrates, be warming up to 50 DEG C stirring 2~
3h, slow cooling keep temperature to stir 1~2 hour, filter to -5~-10 DEG C, and air blast drying obtains buff target product
7.49g, yield 77.1%.Shown in its structural formula such as formula (1)：
It is catalyzed diazotate and decomposes completion N-H insertion cyclizations：
A clean reaction bulb is taken, 45g diazotate a and 100ml dichloromethane is added, opens electric stirring, stirring and dissolving
Afterwards, Salen-Rh (II) coordination polymer catalyst 0.57g prepared by above-described embodiment is added, after stirring evenly, temperature rising reflux
4h is stirred, following cyclization, cyclization target product external standard 39.8g, yield 95.5% are completed.
Embodiment 2
The preparation of (R, R)-(-)-N, N '-two (3- methyl -5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine：
A clean reaction bulb is taken, is added 200ml methanol, 5.7g (1R, 2R)-cyclohexanediamine, after stirring and dissolving, by 21.3g
3- methyl -2- hydroxyls -5- (4- pyridyl groups) benzaldehyde is dissolved in 200ml methanol solutions, is slowly added dropwise in above-mentioned reaction bulb, reflux
It is stirred to react 2h, cold water 100ml is added, is cooled to 0~5 DEG C, continues to stir 1h, filters, washed with 50ml methanol, obtain yellow
Solid product 22.4g, yield 88.9%.1H-NMR(600MHz,CDCl3):δ1.51(6H,s),2.07-1.56(m,8H),3.38
(2H,m),7.22(2H,d),7.35(4H),7.48(2H,d),8.33(2H,s),8.61(4H,d)。
(R, R)-(-)-N, N '-two (3- methyl -5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine-Rh (II) has
The preparation of machine metal complex：
It measures 100ml ethyl alcohol to be added in clean reaction bulb, opens electric stirring, 5g (R, R)-(-)-N, N '-two (3- is added
Methyl -5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine, stirs 1 hour and dissolves, 1.1g rhodium acetates, stirring 0.5 is added
Hour, back flow reaction 6h, stirring slow cooling kept temperature to stir 1~2 hour to -5~-10 DEG C, suction filtration after mixing,
Air blast is dried, and yellow target product 5.77g, yield 95.4% are obtained.
(R, R)-(-)-N, N '-two (3- methyl -5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine-Rh (II) matches
The preparation of position polymer：
Take a clean reaction bulb, 120ml dimethylformamides and 10ml methanol be added, open electric stirring, be added 6g (R,
R)-(-)-N, N '-two (3- methyl -5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine-Rh organometallic complexs, are stirred
Mix uniformly after, be added 0.83g terephthalic acid (TPA)s, 30 DEG C stirring 15min, be added 2.4g cadmium nitrates, be warming up to 50 DEG C stirring 2~
3h, slow cooling keep temperature to stir 1~2 hour, filter to -5~-10 DEG C, and air blast drying obtains buff target product
7.1g, yield 70.6%.Shown in its structural formula such as formula (2)：
It is catalyzed diazotate and decomposes completion N-H insertion cyclizations：
A clean reaction bulb is taken, 45g diazotate a and 170ml dichloromethane is added, opens electric stirring, stirring and dissolving
Afterwards, Salen-Rh (II) coordination polymer catalyst 0.29g prepared by above-described embodiment is added, after stirring evenly, temperature rising reflux
4h is stirred, following cyclization, cyclization target product external standard 38.5g, yield 92.4% are completed.
Embodiment 3
The preparation of (R, R)-(-)-N, N '-two (3- tertiary butyls 5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine：
A clean reaction bulb is taken, is added 200ml methanol, 5.7g (1R, 2R)-cyclohexanediamine, after stirring and dissolving, by 38.25g
The 220ml methanol solutions of 3- tertiary butyl -2- hydroxyls -5- (4- pyridyl groups) benzaldehyde, are slowly added dropwise in above-mentioned reaction bulb, return
Stream is stirred to react 2h, and cold water 100ml is added, is cooled to 0~5 DEG C, continues to stir 1h or so, filters, washed, obtained with 50ml methanol
To yellow solid product 26.8g, yield 91.3%.1H-NMR(600MHz,CDCl3):δ1.45(18H,s),2.10-1.56(m,
8H), 3.42 (2H, m), 7.28 (2H, d, J=2.4Hz), 7.36 (4H, d, J=6.0Hz), 7.53 (2H, d, J=2.4Hz),
8.37 (2H, s), 8.59 (4H, d, J=6.0Hz).IR (KBr, pellet, cm-1):3428,2934,1632,1594,1443,
1273,1170,1076,820,624cm-1。
(R, R)-(-)-N, N '-two (3- tertiary butyls 5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine-Rh (II)
The preparation of organometallic complex complex：
It measures 120ml to be added in ethyl alcohol cleaning reaction bulb, opens electric stirring, 5.9g (R, R)-(-)-N, N '-two is added
(3- tertiary butyls 5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine is stirred 1 hour and is dissolved, 1.76g rhodium acetates are added, stir
Mix 0.5 hour after mixing, back flow reaction 6h, stirring slow cooling keeps temperature to stir 1~2 hour to -5~-10 DEG C,
It filters, air blast drying obtains yellow target product 6.13g, yield 88.9%.
(R, R)-(-)-N, N '-two (3- tertiary butyls 5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine-Rh (II)
The preparation of coordination polymer：
A clean reaction bulb is taken, 120ml dimethylformamides and 10ml methanol is added, opens electric stirring, 6.9g is added
(R, R)-(-)-N, N '-two (3- tertiary butyls -5- (4 '-pyridyl group) salicylidene base) -1,2- cyclohexanediamine-Rh powder, stirring are equal
After even, 0.42g (0.01mol) terephthalic acid (TPA) is added, 30 DEG C of stirring 15min are added 1.2g cadmium nitrates, are warming up to 50 DEG C of stirrings
2~3h, slow cooling keep temperature to stir 1~2 hour, filter to -5~-10 DEG C, and air blast drying obtains buff target product
7.15g, yield 65.9%.IR (KBr, pellet, cm-1):3430,2899,2163,1621,1612,1443,1288,1164,
1079,837,659,633cm-1。
Coordination polymer is in 1621cm-1For C=N double bond vibration peaks, the 1632cm with ligand-1It compares, is moved to low frequency
15cm-1, illustrate the nitrogen of imine linkage and the d orbital electron formation coordinate bond of rhodium metal.The characteristic absorption band of pyridine should appear in
1598,1421,803,599cm-1Equal positions, and these absorption bands have been moved to 1617,1443,837 in coordination polymer,
659cm-1Etc., show that the nitrogen-atoms in pyridine forms coordinate bond with transition metal cadmium.Shown in its structural formula such as formula (3)：
It is catalyzed diazotate and decomposes completion N-H insertion cyclizations：
A clean reaction bulb is taken, 45g diazotate a and 135ml dichloromethane is added, opens electric stirring, stirring and dissolving
Afterwards, Salen-Rh (II) coordination polymer catalyst 0.13g prepared by above-described embodiment is added, after stirring evenly, temperature rising reflux
4h is stirred, following cyclization, cyclization target product external standard 35.2g, yield 84.6% are completed.
Embodiment 4
The preparation of (R, R)-(-)-N, N '-two (5- carboxyl salicylidenes base) -1,2- cyclohexanediamine：
A clean reaction bulb is taken, is added 30ml methanol, 5.7g (1R, 2R)-cyclohexanediamine, after stirring and dissolving, by 8.3g5-
Carboxylsalicylidene is dissolved in 70ml methanol solutions, is slowly added dropwise in above-mentioned reaction bulb, and return stirring reacts 2h, is cooled to 0~5
DEG C, continue to stir growing the grain 1h or so, filter, the washing of 10ml methanol obtains yellow solid product 17.2g (0.042mol), yield
83.9%.1H-NMR(CDCl3):δ1.46-1.99(8H,m),3.55(2H,s),7.08(2H,d),7.70(2H,d),7.82
(2H,s),8.58(2H,s)；IR(KBr,pellet,cm-1):2937,1618,1522,1481,1453,1400,1370,1356,
1299,1278,1151,1039,890,694,461.
(R, R)-(-)-N, N '-two (5- carboxyl salicylidenes base) -1,2- cyclohexanediamine-Rh (II) organometallic complex
It prepares：
It measures 150ml ethyl alcohol to be added in clean reaction bulb, opens electric stirring, 4.1g (R, R)-(-)-N, N '-two is added
(5- carboxyl salicylidenes base) -1,2- cyclohexanediamine stirs 1 hour and dissolves, 2.2g rhodium acetates are added, and it is equal to stir mixing in 0.5 hour
After even, back flow reaction 6h, stirring slow cooling keeps temperature to stir 1~2 hour to -5~-10 DEG C, filters, and air blast drying obtains
To yellow green target product 4.27g, yield 80.2%.IR(KBr,pellet,cm-1):2928,1600,1593,1549,
1431,1396,1337,1190,1127,1048,788,721,569,457.
The preparation of (R, R)-(-)-N, N '-two (5 carboxyl salicylidene base) -1,2- cyclohexanediamine-Rh (II) coordination polymer:
A clean reaction bulb is taken, 360ml dimethylformamides and 30ml 1wt% potassium hydroxide aqueous solutions is added, opens electricity
Dynamic stirring, is added 2.5g (R, R)-(-)-N, N '-two (5 carboxyl salicylidene base) -1,2- cyclohexanediamine-Rh (II) organometallic ligand
Object is closed, after stirring evenly, 0.78g4,4 '-bipyridyls is added, 2.4g cadmium nitrates are dissolved in 60ml dimethyl by 30 DEG C of stirring 15min
It in sulfoxide solvent, is added in above-mentioned reaction bulb, is warming up to 50 DEG C of 2~3h of stirring, slow cooling keeps temperature to -5~-10 DEG C
Stirring 1~2 hour filters, and air blast drying obtains buff target product 3.2g, yield 74%.IR(KBr,pellet,cm-1):
3410,2935,1714,1650,1607,1557,1373,1239,1187,1124,1156,864,795,724,650,513,
419。
(R, R)-(-)-N, N '-two (5- carboxyl salicylidenes base) -1,2- cyclohexanediamine-Rh (II) organometallic complexs C
=N double bond stretching vibration absorption frequencies are 1600cm-1, with (R, R)-(-)-N, N '-two (5- carboxyl salicylidenes base) -1,2- hexamethylenes
Diamines absorption frequency is 1618cm-1It compares, 18cm is moved to low frequency-1, illustrate that imine nitrogen atom is coordinated bonding with Rh, occur
Red shift.457cm in (R, R)-(-)-N, N '-two (5- carboxyl salicylidenes base) -1,2- cyclohexanediamine-Rh complex infrared spectrums-1
It stretches peak for Rh-O keys, and in 1549cm-1And 1431cm-1There is carboxyl stretching vibration peak at place, (R, R)-(-)-N, N '-two (5 carboxylics
Base salicylidene base) -1,2- cyclohexanediamine-Rh coordination polymers are in 1687cm-1The disappearance of place's carboxyl association absorption peak illustrates to be coordinated
Carboxyl participates in the formation of coordinate bond in polymer.Shown in its structure such as formula (4)：
It is catalyzed diazotate and decomposes completion N-H insertion cyclizations：
A clean reaction bulb is taken, 45g diazotate a and 100ml dichloromethane is added, opens electric stirring, stirring and dissolving
Afterwards, Salen-Rh (II) coordination polymer catalyst 0.51g prepared by above-described embodiment is added, after stirring evenly, temperature rising reflux
4h is stirred, following cyclization, cyclization target product external standard 37.6g, yield 90.4% are completed.
Catalyst is recovered by filtration in reaction solution after reaction is terminated while hot, and catalyst is after dichloromethane foam washing, air blast
It air-dries, recycling, carries out catalysis diazotate decomposition reaction again, reuse 3 times, yield 34.7g, yield 84.3% is urged
The rate of recovery of agent is 95%.
Embodiment 5
The preparation of (R, R)-(-)-N, N '-two (3- methyl -5- carboxyl salicylidenes base) -1,2- cyclohexanediamine：
A clean reaction bulb is taken, is added 30ml methanol, 5.7g (1R, 2R)-cyclohexanediamine, after stirring and dissolving, by 18g3- first
Base -5- carboxylsalicylidenes are dissolved in 70ml methanol, are slowly added dropwise in above-mentioned reaction bulb, and return stirring reacts 2h, is cooled to 0
~5 DEG C, continues to stir 1h, filter, washed with 10ml methanol, obtain yellow solid product 19.1g, yield 87.5%.1H-NMR
(CDCl3):δ 1.42 (6H, s), 1.51-2.07 (8H, m), 3.46 (2H, s), 7.67 (2H, d), 7.80 (2H, s), 8.58 (2H,
s)。
(R, R)-(-)-N, N '-two (3- methyl -5- carboxyl salicylidenes base) -1,2- cyclohexanediamine-Rh (II) organic metal
The preparation of complex
It measures 150ml ethyl alcohol to be added in clean reaction bulb, opens electric stirring, 4.4g (R, R)-(-)-N, N '-two is added
(3- methyl -5- carboxyl salicylidenes base) -1,2- cyclohexanediamine stirs 1 hour and dissolves, 1.1g rhodium acetates are added, stirs 0.5 hour
After mixing, back flow reaction 6h, stirring slow cooling keep temperature to stir 1~2 hour, filter, air blast to -5~-10 DEG C
Drying, obtains yellow green target product 4.07g, yield 75.6%.
(R, R)-(-)-N, N '-two (3- methyl -5- carboxyl salicylidenes base) -1,2- cyclohexanediamine-Rh (II) coordination polymerization
The preparation of object
A clean reaction bulb is taken, 360ml dimethylformamides are added and 30ml 1wt% potassium hydroxide aqueous solutions open electricity
Dynamic stirring, 2.7g (R, R)-(-)-N, N '-two (- 5 carboxyl salicylidene base of 3- methyl) -1,2- cyclohexanediamine-Rh (II), which is added, to be had
After stirring evenly, 0.39g4,4 '-bipyridyls is added in machine metal complex, and 1.2g cadmium nitrates are dissolved in by 30 DEG C of stirring 15min
It in 60ml dimethyl sulfoxide solvents, is added in above-mentioned reaction bulb, is warming up to 50 DEG C of 2~3h of stirring, slow cooling to -5~-10
DEG C, it keeps temperature to stir 1~2 hour, filters, air blast drying obtains buff target product 3.3g, yield 71.4%.Its structure
As shown in formula (5)：
It is catalyzed diazotate and decomposes completion N-H insertion cyclizations：
A clean reaction bulb is taken, 45g diazotate a and 135ml dichloromethane is added, opens electric stirring, stirring and dissolving
Afterwards, Salen-Rh (II) coordination polymer catalyst 0.27g prepared by above-described embodiment is added, after stirring evenly, temperature rising reflux
4h is stirred, following cyclization, cyclization target product external standard 35.3g, yield 84.9% are completed.
Embodiment 6
The preparation of (R, R)-(-)-N, N '-two (3- tertiary butyl -5- carboxyl salicylidenes base) -1,2- cyclohexanediamine
A clean reaction bulb is taken, is added 30ml methanol, 5.7g (1R, 2R)-cyclohexanediamine, after stirring and dissolving, by 33g 3-
Tertiary butyl -5- carboxylsalicylidenes are dissolved in 70ml methanol solvates, are slowly added dropwise in above-mentioned reaction bulb, return stirring reaction
2h is cooled to 0~5 DEG C, continues to stir 1h or so, filters, washed with 10ml methanol, obtain yellow solid product 24.8g, yield
95%.1H-NMR(CDCl3):δ1.31(18H,s),1.46-1.99(8H,m),3.57(2H,s),7.68(2H,s),7.80(2H,
s),8.58(2H,s)。
(R, R)-(-)-N, N '-two (3- tertiary butyl -5- carboxyl salicylidenes base) -1,2- cyclohexanediamine-Rh (II) organic gold
The preparation of metal complex
It measures 150ml ethyl alcohol to be added in clean reaction bulb, opens electric stirring, 5.2g (R, R)-(-)-N, N '-two is added
(3- tertiary butyl -5- carboxyl salicylidenes base) -1,2- cyclohexanediamine is stirred 1 hour and is dissolved, and 1.76g rhodium acetates, stirring 0.5 is added
Hour, back flow reaction 6h, stirring slow cooling kept temperature to stir 1~2 hour to -5~-10 DEG C, suction filtration after mixing,
Air blast is dried, and yellow green target product 4.36g, yield 70% are obtained.
(R, R)-(-)-N, N '-two (3- tertiary butyl -5- carboxyl salicylidenes base) -1,2- cyclohexanediamine-Rh (II) polycomplexation
Close the preparation of object
A clean reaction bulb is taken, 360ml dimethylformamides are added and 30ml 1wt% potassium hydroxide aqueous solutions open electricity
Dynamic stirring, is added 3.1g (R, R)-(-)-N, N '-two (- 5 carboxyl salicylidene base of 3- tertiary butyls) -1,2- cyclohexanediamine-Rh powder,
After stirring evenly, 1.56g4,4 '-bipyridyls is added, 1.8g cadmium nitrates are dissolved in 60ml dimethyl sulfoxide (DMSO)s by 30 DEG C of stirring 15min
Solution is added in above-mentioned reaction bulb, is warming up to 50 DEG C of 2~3h of stirring, slow cooling to -5~-10 DEG C, keep temperature stirring 1~
It 2 hours, filters, air blast drying obtains buff target product 3.97g, yield 79.4%.Shown in its structure such as formula (6)：
It is catalyzed diazotate and decomposes completion N-H insertion cyclizations：
A clean reaction bulb is taken, 45g diazotate a and 170ml dichloromethane is added, opens electric stirring, stirring and dissolving
Afterwards, Salen-Rh (II) coordination polymer catalyst 0.12g prepared by above-described embodiment is added, after stirring evenly, temperature rising reflux
4h is stirred, following cyclization, cyclization target product external standard 31.9g, yield 76.7% are completed.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of Salen-Rh (II) coordination polymer, which is characterized in that the structure of Salen-Rh (II) coordination polymer
As shown in formula (i) or formula (ii)：
Wherein, R1For H ,-CH3Or-C (CH3)3。
2. a kind of preparation method of Salen-Rh as described in claim 1 (II) coordination polymer, which is characterized in that described
The preparation method of Salen-Rh (II) coordination polymer includes the following steps：
Step a：Prepare Salen ligands, salicylaldehyde derivatives are dissolved in methanol, mixed solution is obtained, by the mixed solution by
It is added dropwise in the methanol solution of (1R, 2R)-cyclohexanediamine, is stirred to react under the conditions of 15~25 DEG C to get shown in such as formula (III)
Salen ligands：
Wherein, the structural formula of salicylaldehyde derivatives is：
R1For H ,-CH3Or-C (CH3)3；R2For-COOH or
Step b：Salen-Rh (II) organometallic complex is prepared, the Salen ligands are dissolved in alcohol solvent, second is added
Sour rhodium is stirred at reflux reaction, is subsequently cooled to -5~-10 DEG C, and insulated and stirred 1~2 hour filters, and air blast drying obtains formula (IV)
Shown in Salen-Rh (II) organometallic complex；
R1For H ,-CH3Or-C (CH3)3；R2For-COOH or
Step c：Prepare Salen-Rh (II) coordination polymer：
(1) work as R2ForWhen, the Salen-Rh (II) organometallic complex is dissolved in dimethylformamide and first
In mixed alkoxide solution, terephthalic acid (TPA) is added, fully after dissolving, cadmium nitrate is added, agitating and heating reaction is subsequently cooled to -5
~-10 DEG C, insulated and stirred 1~2 hour filters drying, obtains Salen-Rh (I) coordination polymer shown in formula (II).
(2) work as R2For-COOH when, the Salen-Rh (II) organometallic complex is dissolved in dimethylformamide and hydrogen-oxygen
Change in aqueous solutions of potassium, 4,4'-Bipyridine is added after mixing, the dimethyl sulphoxide solution of cadmium nitrate is added, agitating and heating is anti-
It answers, is subsequently cooled to -5~-10 DEG C, insulated and stirred 1~2 hour filters drying, obtains Salen-Rh (II) shown in formula (II) and match
Position polymer.
3. the preparation method of Salen-Rh (II) coordination polymer as claimed in claim 2, which is characterized in that the step a
The molar ratio of middle salicylaldehyde derivatives and (1R, 2R)-cyclohexanediamine is 1~3:1.
4. the preparation method of Salen-Rh (II) coordination polymer as claimed in claim 2, which is characterized in that institute in step b
State the mass ratio 1 of Salen ligands and the alcohol solvent:10~30, the molar ratio 1 of the Salen ligands and the rhodium acetate:
0.5~1, the time of back flow reaction is 4~12h.
5. the preparation method of Salen-Rh (II) coordination polymer as claimed in claim 2, which is characterized in that work as R in step c2
For-COOH when, Salen-Rh (II) organometallic complexs and the potassium hydroxide molar ratio 1:2~3, the Salen-
Rh (II) organometallic complexs and the dimethylformamide mass ratio 1:100~150, the water and the dimethyl formyl
Amine volume ratio is 1:4~8, Salen-Rh (II) organometallic complexs and the 4,4'-Bipyridine molar ratio 1:1~4,
Salen-Rh (II) organometallic complexs and the cadmium nitrate molar ratio 1:2~4, it is 2~3h, temperature to be stirred to react the time
Degree is 30~60 DEG C.
6. the preparation method of Salen-Rh (II) coordination polymer as claimed in claim 2, which is characterized in that work as R in step c2
ForWhen, Salen-Rh (II) organometallic complexs and the terephthalic acid (TPA) molar ratio 1:0.5~2, it is described
Salen-Rh (II) organometallic complexs and the dimethylformamide mass ratio 1:15~30, the methanol and the diformazan
Base formamide volume ratio 1:8~12, Salen-Rh (II) organometallic complexs and the cadmium nitrate molar ratio 1:1~4,
It is 2~3h to be stirred to react the time, and temperature is 30~60 DEG C.
7. application of Salen-Rh (II) coordination polymers as described in claim 1 in catalytic decomposition diazonium compound reaction.
8. application of Salen-Rh (II) coordination polymers as claimed in claim 7 in catalytic decomposition diazonium compound reaction,
It is characterized in that, its reaction includes the following steps：
It using diazotate a as reaction substrate, is dissolved in dichloromethane, after dissolving fully, stops stirring, the Salen- is added
Rh (II) coordination polymer, agitating and heating back flow reaction 4h, through the dichloromethane solution that cyclization target product b is obtained by filtration.Its
Reaction equation is：
9. application of Salen-Rh (II) coordination polymers as claimed in claim 8 in catalytic decomposition diazonium compound reaction,
It is characterized in that, the diazotate a and the Salen-Rh (II) coordination polymers molar ratio 1:0.0005~0.0025, weight
The mass ratio of nitronate a and dichloromethane is 1:3~5.
10. application of Salen-Rh (II) coordination polymers as claimed in claim 8 in catalytic decomposition diazonium compound reaction,
It is characterized in that, filtration temperature is 25~35 DEG C.
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| CN111690145A (en) * | 2020-05-14 | 2020-09-22 | 遵义医科大学 | Pyridine type chiral Cu (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof |
| CN116726994A (en) * | 2023-06-02 | 2023-09-12 | 昆明理工大学 | Preparation method and application of Salen (M) porous ionic polymer heterogeneous catalyst |
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| CN102304062A (en) * | 2011-06-09 | 2012-01-04 | 山东省化工研究院 | Method for preparing Salen Ni |
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| CN102304062A (en) * | 2011-06-09 | 2012-01-04 | 山东省化工研究院 | Method for preparing Salen Ni |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111690145A (en) * | 2020-05-14 | 2020-09-22 | 遵义医科大学 | Pyridine type chiral Cu (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof |
| CN116726994A (en) * | 2023-06-02 | 2023-09-12 | 昆明理工大学 | Preparation method and application of Salen (M) porous ionic polymer heterogeneous catalyst |
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