CN103193701A - Functional ligand and preparation method thereof - Google Patents
Functional ligand and preparation method thereof Download PDFInfo
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- CN103193701A CN103193701A CN2013101045310A CN201310104531A CN103193701A CN 103193701 A CN103193701 A CN 103193701A CN 2013101045310 A CN2013101045310 A CN 2013101045310A CN 201310104531 A CN201310104531 A CN 201310104531A CN 103193701 A CN103193701 A CN 103193701A
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Abstract
The invention provides a functional ligand for preparing a coordination polymer. A functional ligand molecule comprises gemini quaternary ammonium salt, a bi(salicylaldehyde amino acid) Schiff base conjugate unit and a carboxylic acid group. The water solubility of the functional ligand is guaranteed through the gemini quaternary ammonium salt, the bi(salicylaldehyde amino acid) Schiff base conjugate unit provides conditions for developing or fluorescence color development of the coordination polymer, and the carboxylic acid group reacts with metal ions so as to prepare the center of the coordination polymer.
Description
Technical field
The present invention relates to a kind of organic ligand, the particularly functional ligand of gemini quaternary ammonium salt support two (salicylidene amino acid), (metal-organic frameworks MOFs), belongs to field of functional materials for the preparation of organo-metallic coordination polymkeric substance.
Technical background
Organo-metallic coordination polymkeric substance is also referred to as organic metal framework or metal organic coordination reticulated structure (metal-organic coordination network), refer to that with metal ion or metal cluster be node, be the bridging body with the organic ligand, utilize the coordination geometric configuration of metal ion and the variation of organic ligand structure, have the porous framework ligand polymer of periodic one-dimensional chain, two-dimensional layer or three-dimensional net structure by coordinate bond self-assembly formation.Metal ion for the preparation of ligand polymer refers to transition metal ion and rare earth ion more, the organic ligand that uses mainly is that polynary aromatic acid and azepine aromatic ring are (referring to Chem.Soc.Rev., 2012,41,1088-1110), because polynary aromatic acid and azepine aromatic ring all have the rigidity chemical structure, so the porous ligand polymer of studying so far is mostly as rigidity porous framework material.Some achievements in research show that flexible part also can be self-assembled into ligand polymer, and the flexibility of organic ligand is more good, the diversity of its configuration and uncertainty are just bigger, can synthesize the ligand polymer of different novel structures under different synthesis conditions, have widened the ligand polymer intension greatly.
People such as Filipe A.Almeida Paz have explained the application characteristic of the function organic ligand of azo aromatic acid part or conjugation aromatic acid part on " Chem.Soc.Rev., 2012,41,1088-1110 "; " self-assembly chemistry and the property research of the bending type organic ligand of two Schiffbase carboxylic acid parts and ehter bond bridging " Shandong Normal University of Xiao Jing master thesis in 2011 has been illustrated based on Schiff base carboxylic acid and has been made and character as the organic metal framework of organic ligand; Tian Chunyan " mixes the synthetic of bridge ligand polymer based on carboxyl one nitrine of two (carboxyl pyridine) part, structure and magnetic properties " East China Normal University's master thesis in 2010 disclosed quaternary ammonium salt and modified the cup aromatic acid to the influence of ligand polymer preparation, " the synthesizing of the ligand polymer that flexible bisbenzimidazole part is constructed of Jiang Yingyin, structure and property research " Northeast Normal University's master thesis in 2010 has reported flexible part because its character that can freely stretch, tend to construct the ligand polymer with IPN and spirane structure, if and carbochain is more long, the σ key that rotates freely is more many, then the flexibility of organic ligand is just more good, the diversity of its configuration and uncertainty are just bigger, can synthesize the ligand polymer of different novel structures under different synthesis conditions.
Above achievement in research has illustrated that organic ligand is carried out functional modification or organic ligand is carried out the snappiness transformation is the novel organic ligand of screening, expansion ligand polymer function, the main basis of development ligand polymer theory.Design, the organic ligand that the synthetic chemistry structure is special, function is clear and definite, ligancy is good just become ligand polymer preparation research, functional development, framework is various and the indispensable committed step of practical application.Yet the professional knows, the poorly water-soluble of existing aromatic acid part, the preparation ligand polymer is mostly carried out in the organic solvent, and desired temperature of reaction is also high, influence the self-assembly slow process between organic ligand and the metal ion, be difficult to turn out the very large crystalline material of ligand polymer or mould material.
Summary of the invention
The present invention is tridentate chelating ligand with salicylidene amino acid, azepine aromatic ring type gemini quaternary ammonium salt is as the amino acid whose junctor of described salicylidene, the functional ligand of a kind of gemini quaternary ammonium salt support two (salicylidene amino acid) is provided, has chemical structure shown in general formula (Ia) or the general formula (Ib):
Q in its formula of (Ia) or the general formula (Ib) is selected from a kind of in CHY, phenyl ring or the naphthalene nucleus, and described Y is selected from H or C
1～C
6A kind of in the alkyl, described Z is selected from: 0, O, S, C
1～C
6Alkyl,
Or
In a kind of, described n is selected from a kind of in 1,2 or 3.
The invention has the beneficial effects as follows that the double type quaternary ammonium salt unit in two (salicylidene amino acid) the functional ligand molecular structures of described gemini quaternary ammonium salt support has guaranteed the water-soluble of described functional ligand, Schiff base conjugate unit in two (salicylidene amino acid) the functional ligand molecular structures of described gemini quaternary ammonium salt support provides condition for colour developing or the fluorescence color development of ligand polymer, and the carboxylic acid group of containing in two (salicylidene amino acid) the functional ligand molecular structures of described gemini quaternary ammonium salt support is the center of reacting and then preparing ligand polymer with metal ion.
The functional ligand of a kind of gemini quaternary ammonium salt support of the present invention two (salicylidene amino acid), through and the alkali reagent effect, be easy to be converted into the inner salt carboxylic acid structure, referring to following structural formula:
Inner salt carboxylic acid part is compared with other carboxylic acid part to have coordination competition and releives, with the flexile characteristics of metal example coordination mode.
The concrete preparation method of two (salicylidene amino acid) functional ligands of general formula of the present invention (Ia) or general formula (Ib) gemini quaternary ammonium salt support realizes by two steps:
The preparation of step 1 double salicylaldehyde modification gemini quaternary ammonium salt
Take by weighing general formula (IIa) or general formula (IIb) polyamines and 5-chloromethyl salicylic aldehyde and be dissolved in respectively in the solvent, make general formula (IIa) or general formula (IIb) polyamines solution and 5-chloromethyl salicylic aldehyde solution; Control described logical
Formula (IIa) or general formula (IIb) polyamines solution temperature to 0～60 ℃, stir down and slowly in described general formula (IIa) or general formula (IIb) polyamines solution, add 5-chloromethyl salicylic aldehyde solution, reacted 2～6 hours, after this distillation eliminates the solvent residuum, with dehydrated alcohol described residue is dissolved recrystallize and purify, make the double salicylaldehyde modification gemini quaternary ammonium salt of structure shown in general formula (IIIa) or the general formula (IIIb).1. reaction formula has expressed the process of general formula (IIa) or general formula (IIb) polyamines and 5-chloromethyl salicylic aldehyde prepared in reaction double salicylaldehyde modification gemini quaternary ammonium salt:
Wherein the Z of reaction formula in 1. be selected from 0, O, S, C
1～C
6Alkyl,
Or
In a kind of, described n is selected from a kind of in 1,2 or 3.
Described solvent refers to acetone, butanone, 1,4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene, chlorobenzene, ethyl acetate, methyl acetate, butylacetate, chloroform, tetracol phenixin, 1,2-ethylene dichloride, methylcyclohexane, N, in dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or the acetonitrile one or more.
The molar weight ratio of described general formula (IIa) or general formula (IIb) polyamines and 5-chloromethyl salicylic aldehyde is 1: 2.2～2.5.
The consumption of described solvent is general formula (IIa) or general formula (IIb) and 5-chloromethyl salicylic aldehyde quality summation 2～5 times.
The preparation of two (salicylidene amino acid) functional ligands of step 2 gemini quaternary ammonium salt support
Take by weighing double salicylaldehyde modification gemini quaternary ammonium salt and the NH of structure shown in general formula (IIIa) or the general formula (IIIb) respectively
2QCOOH is dissolved in the organic solvent, Glacial acetic acid is as souring agent and catalyzer, after the back flow reaction 4～12 hours, steam organic solvent/water azeotrope, after thin layer chromatography detects the condensation reaction end, cooling reaction product system temperature filters to-15～15 ℃ of crystallizations, makes two (salicylidene amino acid) functional ligands of gemini quaternary ammonium salt support of structure shown in general formula (Ia) or the general formula (Ib).The double salicylaldehyde modification gemini quaternary ammonium salt that 2. reaction formula has expressed structure shown in general formula (IIIa) or the general formula (IIIb) respectively and NH
2QCOOH carries out condensation reaction, the process of two (salicylidene amino acid) functional ligands of the gemini quaternary ammonium salt support of structure shown in preparation general formula (Ia) or the general formula (Ib):
Wherein the Q of reaction formula in 2. is selected from a kind of in CHY, phenyl ring or the naphthalene nucleus, and described Y is selected from H or C
1～C
6A kind of in the alkyl, described Z is selected from: 0, O, S, C
1～C
6Alkyl,
Or
In a kind of, described n is selected from a kind of in 1,2 or 3.
Described organic solvent refers to methyl alcohol, ethanol, propyl alcohol, acetone, butanone, N, one or more in dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or the acetonitrile.
Double salicylaldehyde modification gemini quaternary ammonium salt and the NH of structure shown in described general formula (IIIa) or the general formula (IIIb)
2QCOOH molar weight ratio is 1: 2.2～2.5.
The consumption of described organic solvent is double salicylaldehyde modification gemini quaternary ammonium salt and the NH of structure shown in described general formula (IIIa) or the general formula (IIIb)
22～5 times of QCOOH quality summation.
Two (salicylidene amino acid) functional ligands of a kind of gemini quaternary ammonium salt support provided by the invention have following feature:
1. the method for preparing two (salicylidene amino acid) functional ligands of gemini quaternary ammonium salt support of the present invention is simple, and the starting material source is abundant, with low cost.
2. the good water solubility of two (salicylidene amino acid) functional ligands of gemini quaternary ammonium salt support of the present invention, can be under the normal temperature state in the aqueous solution with metal ion prepared in reaction ligand polymer, by water solvent slow vaporization process, cultivate the very large crystalline material of described ligand polymer accordingly.
3. the novel structure of two (salicylidene amino acid) functional ligands of gemini quaternary ammonium salt support of the present invention has symmetry, by regulating Z and Q base, can obtain the ligand polymer of skeleton construction novelty.
Specific embodiment
By following embodiment two (salicylidene amino acid) functional ligands of the Gemini quaternary ammonium salt support shown in the general formula provided by the invention (I) and preparation method are further specified, its purpose is to understand better content of the present invention.Therefore, two (salicylidene amino acid) functional ligand and the preparation methods of unlisted Gemini quaternary ammonium salt support should not be considered as limiting the scope of the invention among the embodiment.
The preparation of the preparation process 1 double salicylaldehyde modification gemini quaternary ammonium salt IIIa-1 of two (salicylidene amino acid) functional ligands (Ia-1) of embodiment 1 gemini quaternary ammonium salt support
In the four-hole boiling flask of agitator is housed, take by weighing 4,4 '-bipyridine, 32 grams are dissolved in 80 milliliters of acetonitriles, make 4, the acetonitrile solution of 4 '-bipyridine takes by weighing 5-chloromethyl salicylic aldehyde 70 grams again and is dissolved in 100 milliliters of acetonitriles, makes the acetonitrile solution of 5-chloromethyl salicylic aldehyde.Control the acetonitrile solution temperature of described 5-chloromethyl salicylic aldehyde between 8～15 ℃, stir down 4, the acetonitrile solution of 4 '-bipyridine slowly adds in the acetonitrile solution of described 5-chloromethyl salicylic aldehyde, react after 4 hours, the reaction mass temperature is brought up to 80～85 ℃, restir reaction 10 hours, the reaction product system temperature is down to 5～10 ℃, filter, filter cake uses acetonitrile washing 3～5 times, after the drying, makes 88.3 grammeter looks crystalline double salicylaldehyde modification gemini quaternary ammonium salts (IIIa-1), yield 88.4%, fusing point＞300 ℃; Ultimate analysis: C
26H
22Cl
2N
2O
4Measured value (calculated value) C62.38 (62.79), H4.43 (4.46), N5.61 (5.63), Cl14.18 (14.26); H
1-NMR (DMSO-d
6, 5): 2.63 (s, 4H), 5.41 (s, 2H), 6.81～9.47 (m, 14H), 10.26 (s, 2H).
The preparation of two (salicylidene amino acid) functional ligands (Ia-1) of step 2 gemini quaternary ammonium salt support
Taking by weighing 50 gram double salicylaldehyde modification gemini quaternary ammonium salts (IIIa-1) and 28 restrains anthranilic acids and is dissolved in 160 milliliters of ethanol, 2 milliliters of Glacial acetic acid are as souring agent and catalyzer, back flow reaction 8 hours, component distillation part ethanol promotes condensation reaction to carry through to the end.After reaction finishes, near the cooling reaction product system temperature to 0 ℃ about, filter, with acid dehydrated alcohol filter cake is carried out recrystallization, drying makes safran gemini quaternary ammonium salt support pair (salicylidene amino acid) functional ligands (Ia-1), fusing point＞300 ℃; Ultimate analysis: C
40H
32Cl
2N
4O
6Measured value (calculated value) C65.28 (65.31), H4.31 (4.38), N7.62 (7.62), Cl9.42 (9.64); H
1-NMR (DMSO-d
6): 2.62 (s, 4H), 5.17 (s, 2H), 6.74～9.45 (m, 24H), 11.01 (s, 2H).
The preparation that described (Ia-1) is used for ligand polymer is that 2 grams saffron (Ia-1) are dissolved in 20 milliliters of deionizations, regulate pH～8.5 with saturated aqueous sodium carbonate, slowly be added dropwise to copper chloride solution then, solution colour becomes green-yellow gradually by orange, separates out the light green crystal after a few days.
The preparation of two (salicylidene amino acid) functional ligands (Ia-2) of embodiment 2 gemini quaternary ammonium salt supports
According to method and the operation steps of embodiment 1, the anthranilic acid in embodiment 1 step 3 is changed to glycine, make flaxen Ia-2.
Faint yellow Ia-2 is dissolved in deionized water, regulates pH～8.5 with aqueous sodium carbonate, slowly be added dropwise to copper chloride solution, solution colour becomes mazarine gradually, separates out blue colored crystal after a few days.
The preparation of two (salicylidene amino acid) functional ligands (IIa-1) of embodiment 3 gemini quaternary ammonium salt supports
According to method and the operation steps of embodiment 1, with the N in embodiment 1 step 3, N, N ', N '-Tetramethyl Ethylene Diamine change 1,4-diimidazole butane, make the IIa-1 of orange.
The IIa-1 of orange is dissolved in deionized water, regulates pH～8.5 with aqueous sodium carbonate, slowly be added dropwise to solder(ing)acid, solution colour is deepened gradually, separates out red crystals after a few days.
The preparation of two (salicylidene amino acid) functional ligands (IIa-2) of embodiment 4 gemini quaternary ammonium salt supports
According to method and the operation steps of embodiment 1, with the N in embodiment 1 step 3, N, N ', N '-Tetramethyl Ethylene Diamine changes 2,2 '-(diimidazole) diethyl ether, makes flaxen IIa-2.
Flaxen IIa-2 is dissolved in deionized water, regulates pH～8.5 with aqueous sodium carbonate, slowly be added dropwise to chromium chloride solution, separate out the bluish voilet crystal after a few days.
Claims (2)
1. a functional ligand refers to the functional ligand of gemini quaternary ammonium salt support two (salicylidene amino acid), and its feature has chemical structure shown in general formula (Ia) or the general formula (Ib):
Q in its formula of (Ia) or the general formula (Ib) is selected from a kind of in CHY, phenyl ring or the naphthalene nucleus, and described Y is selected from H or C
1～C
6A kind of in the alkyl, described Z is selected from: 0, O, S, C
1～C
6Alkyl,
Or
In a kind of, described n is selected from a kind of in 1,2 or 3.
2. according to the preparation method of two (salicylidene amino acid) functional ligands of the described gemini quaternary ammonium salt support of claim 1, it is characterized in that being realizing according to following preparation process:
Step 1: the preparation of double salicylaldehyde modification gemini quaternary ammonium salt
Take by weighing general formula (IIa) or general formula (IIb) polyamines and 5-chloromethyl salicylic aldehyde and be dissolved in respectively in the solvent, make general formula (IIa) or general formula (IIb) polyamines solution and 5-chloromethyl salicylic aldehyde solution; Control described general formula (IIa) or general formula (IIb) polyamines solution temperature to 0～60 ℃, stir down and slowly in described general formula (IIa) or general formula (IIb) polyamines solution, add 5-chloromethyl salicylic aldehyde solution, reacted 2～6 hours, after this distill the desolventizing residuum, with dehydrated alcohol described residue being dissolved recrystallize purifies, make the double salicylaldehyde modification gemini quaternary ammonium salt of structure shown in general formula (IIIa) or the general formula (IIIb), 1. expressed by reaction formula:
Wherein the Z of reaction formula in 1. be selected from 0, O, S, C
1～C
6Alkyl,
Or
In a kind of, described n is selected from a kind of in 1,2 or 3;
Described solvent refers to acetone, butanone, 1,4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene, chlorobenzene, ethyl acetate, methyl acetate, butylacetate, chloroform, tetracol phenixin, 1,2-ethylene dichloride, methylcyclohexane, N, in dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or the acetonitrile one or more;
The molar weight ratio of described general formula (IIa) or general formula (IIb) polyamines and 5-chloromethyl salicylic aldehyde is 1: 2.2～2.5;
The consumption of described solvent is general formula (IIa) or general formula (IIb) polyamines and 5-chloromethyl salicylic aldehyde quality summation 2～5 times;
Step 2: the preparation of two (salicylidene amino acid) functional ligands of gemini quaternary ammonium salt support
Take by weighing double salicylaldehyde modification gemini quaternary ammonium salt and the NH of structure shown in general formula (IIIa) or the general formula (IIIb) respectively
2QCOOH is dissolved in the organic solvent, Glacial acetic acid is as souring agent and catalyzer, after the back flow reaction 4～12 hours, steam the azeotrope of organic solvent/water, after thin layer chromatography detected the condensation reaction end, cooling reaction product system temperature filtered to-15～15 ℃ of crystallizations, make two (salicylidene amino acid) functional ligands of gemini quaternary ammonium salt support of structure shown in general formula (Ia) or the general formula (Ib), 2. expressed by reaction formula:
Wherein the Q of reaction formula in 2. is selected from a kind of in CHY, phenyl ring or the naphthalene nucleus, and described Y is selected from H or C
1～C
6A kind of in the alkyl, described Z is selected from: 0, O, S, C
1～C
6Alkyl,
Or
In a kind of, described n is selected from a kind of in 1,2 or 3;
Described organic solvent refers to methyl alcohol, ethanol, propyl alcohol, acetone, butanone, N, one or more in dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or the acetonitrile;
Double salicylaldehyde modification gemini quaternary ammonium salt and the NH of structure shown in described general formula (IIIa) or the general formula (IIIb)
2QCOOH molar weight ratio is 1: 2.2～2.5;
The consumption of described organic solvent is double salicylaldehyde modification gemini quaternary ammonium salt and the NH of structure shown in described general formula (IIIa) or the general formula (IIIb)
22～5 times of QCOOH quality summation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114057628A (en) * | 2021-11-10 | 2022-02-18 | 河西学院 | Pyridine quaternary ammonium salt anion recognition receptor and preparation method and application thereof |
| CN117865802A (en) * | 2024-03-11 | 2024-04-12 | 山东顺成化学有限公司 | Preparation method of ethyl 4-bromobutyrate |
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