CN101348445A - Preparation of carboxylazocalix [4] arene derivatives - Google Patents
Preparation of carboxylazocalix [4] arene derivatives Download PDFInfo
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- CN101348445A CN101348445A CNA2008101958582A CN200810195858A CN101348445A CN 101348445 A CN101348445 A CN 101348445A CN A2008101958582 A CNA2008101958582 A CN A2008101958582A CN 200810195858 A CN200810195858 A CN 200810195858A CN 101348445 A CN101348445 A CN 101348445A
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Abstract
The invention discloses a preparation method for a phenylazocalix [4] arene derivative. The preparation method comprises the following steps that azobenzene chloride and calix [4] arene are taken as reactants, a mixed solution of N, N'-dimethyl formamide and methanol as solvent and sodium acetate as an initiator so as to prepare the phenylazocalix [4] arene derivative; and products include 5-azobenzol-25, 26, 27, 28-tetrahydroxycalix [4] arene, 5, 11-biazobenzol-25, 26, 27, 28-tetrahydroxycalix [4] arene, 5, 11, 17-triazobenzol-25, 26, 27, 28-tetrahydroxycalix [4] arene and 5, 11, 17, 23-tetraazobenzol-25, 26, 27, 28-tetrahydroxycalix [4] arene. Moreover, because the adopted initiator is sodium acetate, the preparation method does not adopt pyridine with heavier smell and more toxicity; moreover, the method can adjust the relative proportion of four reactants through controlling reaction time.
Description
Technical field
The present invention relates to a kind of preparation method of Calixarene Derivatives, be specifically related to the preparation method of carboxylazocalix [4] arene derivatives.
Background technology
Calixarene is the cyclic oligomer that is linked to each other by methylene radical by phenol units, and having cavity can regulate, and conformation is convertible, and is easy to characteristics such as chemical modification and modification.
Suitable functional group all can be introduced by chemical reaction in upper edge and lower edge at calixarene, and the calixarene that passes through chemically modified like this has potential and great application prospect as host molecule at identification organic molecule and conveying cationic side mask.The functionalization group of calixarene both can be incorporated into the upper edge, also can enter into the lower edge.The modification of calixarene upper edge is normally earlier sloughed the tertiary butyl with it and is carried out derivative reaction again, utilize the adjacency pair position sucting electronic effect of phenolic hydroxyl group often, electrophilic substitution reaction is carried out in contraposition at phenolic hydroxyl group, and its purpose one is to introduce various functional groups, improves the performance of calixarene; The 2nd, enlarge or deepen the hole.Common derivatize has sulfonation, nitrated, chlorine alkylation, azoization etc.
Because azo group has characteristics such as fluorescence, ultraviolet, cis-trans isomerism preferably, therefore the upper edge of azo group introducing calixarene had been caused extensive concern in recent years, for example: utilize the color, ultraviolet, fluorescence etc. of azo calixarene to change detection (referring to Chem.Eur.J. to metal ion, 2001,7,4878-4886; New J.Chem., 2004,28,1575-1578).
At present, azo-group cup [4] aromatic hydrocarbons that has been in the news comprises: carboxylazocalix [4] aromatic hydrocarbons, carboxyl benzene-azo-benzene cup [4] aromatic hydrocarbons, pyridylazo base cup [4] aromatic hydrocarbons etc.; About carboxylazocalix [4] aromatic hydrocarbons, people such as SeijiShinkai are published in J.CHEM.SOC.PERKIN TRANS.1,1990, the preparation method of a kind of carboxylazocalix [4] arene derivatives reported in article on the 3333-3337, its process comprises: get cup [4] aromatic hydrocarbons of 1.1mmol and the tetrafluoro boronation nitrogen benzide of 5.5mmol and be dissolved in the 20ml tetrahydrofuran (THF), under 0 degree centigrade, pyridine with 1ml causes this reaction, after 3 hours, obtain the orange product, washing, separate, dry, obtain carboxylazocalix [4] aromatic hydrocarbons 1 (5-azobenzene-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons), carboxylazocalix [4] aromatic hydrocarbons 2 (5,11-two azobenzenes-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons), carboxylazocalix [4] aromatic hydrocarbons 3 (5,11,17-trisazo-phenyl-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons), carboxylazocalix [4] aromatic hydrocarbons 4 (5,11,17,23-four azobenzenes-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons), because the selection of above-mentioned reactant ratio (the tetrafluoro boronation nitrogen benzide of the cup of 1.1mmol [4] aromatic hydrocarbons and 5.5mmol), the ratio of carboxylazocalix in the product that above-mentioned reaction obtains [4] aromatic hydrocarbons 4 in four kinds of carboxylazocalixes [4] aromatic hydrocarbons reached 89%, and the productive rate of carboxylazocalix [4] aromatic hydrocarbons 4 has reached 43%; Its reaction process can be expressed as follows:
Described carboxylazocalix [4] aromatic hydrocarbons 1 is 5-azobenzene-25,26,27, and the chemical formula of 28-tetrahydroxy cup [4] aromatic hydrocarbons is:
Described carboxylazocalix [4] aromatic hydrocarbons 2 is 5,11-two azobenzenes-25,26,27, and the chemical formula of 28-tetrahydroxy cup [4] aromatic hydrocarbons is:
Described carboxylazocalix [4] aromatic hydrocarbons 3 is 5,11,17-trisazo-phenyl-25,26,27, and the chemical formula of 28-tetrahydroxy cup [4] aromatic hydrocarbons is:
Described carboxylazocalix [4] aromatic hydrocarbons 4 is 5,11,17,23-four azobenzenes-25,26,27, and the chemical formula of 28-tetrahydroxy cup [4] aromatic hydrocarbons is:
Yet, inflammable, the poisonous and breath malodor of initiator pyridine that above-mentioned preparation method uses.
Summary of the invention
The object of the invention provides a kind of method for preparing carboxylazocalix [4] aromatic hydrocarbons, to overcome the shortcoming of prior art, reduces the pollution of reaction pair environment.
For achieving the above object, the concrete technical scheme of the present invention is the preparation method of a kind of carboxylazocalix [4] arene derivatives, with chlorination nitrogen benzide and cup [4] aromatic hydrocarbons is reactant, and N, the mixing solutions of N '-dimethyl formamide and methyl alcohol are solvent, sodium-acetate is an initiator, carries out the mixture of 4 kinds of carboxylazocalixes of prepared in reaction [4] aromatic hydrocarbons, filters then, washing, drying is separated through silica gel column chromatography, obtain 5-azobenzene-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons, 5,11-two azobenzenes-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons, 5,11,17-trisazo-phenyl-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons and 5,11,17,23-four azobenzenes-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons;
Wherein, described reaction may further comprise the steps:
(1) the chlorination nitrogen benzide is added the N that is dissolved with cup [4] aromatic hydrocarbons and sodium-acetate, in the mixing solutions of N '-dimethyl formamide and methyl alcohol;
(2) in 0～5 ℃ temperature, reaction obtained the mixture of 4 kinds of carboxylazocalixes [4] aromatic hydrocarbons more than 2 hours.
Above-mentioned reaction process can be expressed as follows:
In the technique scheme, can regulate and control the productive rate of each target product according to the different reaction times: when the reaction times was 2～3 hours, the product that obtains was based on carboxylazocalix [4] aromatic hydrocarbons 1 and carboxylazocalix [4] aromatic hydrocarbons 2; When the reaction times was 4～5 hours, the product that obtains was based on carboxylazocalix [4] aromatic hydrocarbons 3 and carboxylazocalix [4] aromatic hydrocarbons 4; When the reaction times reached more than 6 hours, the product that obtains was based on carboxylazocalix [4] aromatic hydrocarbons 4.
Because serial carboxylazocalix of the present invention [4] aromatic hydrocarbons can be used to discern metal ion, the particularly identification of basic metal and alkaline-earth metal, principle that in addition can also its color changes according to the pH value is different is used to do novel acid base indicator, so it is significant and be worth to adjust the relative proportion of four kinds of products according to the reaction times.
In technique scheme, owing to can react by generation self azo between the diazo salt, produce oily mater, therefore after washing, can remove the part oily mater stirring in the mixed solvent of target product adding hexanaphthene and ether again.
Further in the technical scheme, after the silica gel column chromatography separation obtains carboxylazocalix [4] aromatic hydrocarbons series compound, again it is carried out recrystallization respectively, to adapt to higher level needs.Described purge process is that above-mentioned target product 1,2,3,4 is dissolved in trichloromethane: in the mixed solvent of normal hexane=3: 1 (volume ratio), recrystallization is separated out crystal.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the present invention adopts the chlorination nitrogen benzide as reactant, cooperates with it to adopt sodium-acetate as initiator, thereby has avoided the application that big smell and toxic pyridine are arranged of bibliographical information.
2. the present invention can adjust the relative proportion of four kinds of reactants according to the regulation and control reaction times.
3. the reaction conditions gentleness of the inventive method is simple to operate, and the overall yield of four kinds of carboxylazocalixes [4] aromatic hydrocarbons is more than 80%.
Description of drawings
Accompanying drawing 1 is the ultraviolet spectrogram of four products obtaining among the embodiment one and two;
Accompanying drawing 2 is the space structure synoptic diagram of carboxylazocalix [4] aromatic hydrocarbons 1 that obtains among the embodiment one and two;
Accompanying drawing 4 is the space structure synoptic diagram of carboxylazocalix [4] aromatic hydrocarbons 4 that obtains among the embodiment one and two.
Wherein 1 is 5-azobenzene-25,26,27, the ultraviolet spectrogram of 28-tetrahydroxy cup [4] aromatic hydrocarbons; 2 is 5,11-two azobenzenes-25,26,27, the ultraviolet spectrogram of 28-tetrahydroxy cup [4] aromatic hydrocarbons; 3 is 5,11,17-trisazo-phenyl-25,26,27, the ultraviolet spectrogram of 28-tetrahydroxy cup [4] aromatic hydrocarbons; 4 is 5,11,17,23-four azobenzenes-25,26,27, the spectrogram of 28-tetrahydroxy cup [4] aromatic hydrocarbons.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one
Because aniline can be rotten after placing for some time, so the aniline in this present embodiment must be to obtain with nitrogen protection distillation after the molecular sieve drying.
Sodium Nitrite 0.69g (10mmol) is dissolved in the water of 5mL, under agitation slowly be added drop-wise to then and contain the concentrated hydrochloric acid that 0.91mL (10mmol) newly steams aniline: water=3: 7 (volume ratios, wherein concentrated hydrochloric acid is 3mL) solution in, make it temperature and remain on 0～5 ℃, dropwised back and restir 30 minutes.
Because diazo salt is unstable at normal temperatures, and the preparation diazo salt is thermopositive reaction, so temperature of reaction should remain at 0～5 ℃.
Then above-mentioned diazo salt solution slowly is added drop-wise to the 26mLN that is mixed with 1g (2.36mmol) cup [4] aromatic hydrocarbons and 4.08g (30mmol) sodium-acetate that is stirring, (N in the mixing solutions of N '-dimethyl formamide and methyl alcohol, the volume ratio of N '-dimethyl formamide and methyl alcohol is 8: 5), there is red precipitate to produce gradually, temperature still makes it to remain on 0～5 ℃, leaves standstill after dripping about 2.5 hours.
After question response is complete, the adding massfraction is 0.25% 150mL dilute hydrochloric acid, be heated to 60 ℃ then, stirred about 30 minutes, have a large amount of cotton-shaped red precipitates to produce, suction filtration, be washed with water to neutrality, use methanol wash afterwards, afterwards precipitation is joined middle the stirring 3 hours of mixed solvent (wherein the volume ratio of hexanaphthene and ether is 1: 1) of 150mL hexanaphthene and ether, filter the back precipitation is dissolved in the 40mL trichloromethane, and carry out dried overnight with anhydrous sodium sulphate.
Products therefrom is carried out silica gel column chromatography to be separated, eluent is a methylene dichloride: sherwood oil (60-90 ℃)=2: 1 (volume ratio), obtain target product carboxylazocalix [4] aromatic hydrocarbons 1 (pale yellow), carboxylazocalix [4] aromatic hydrocarbons 2 (yellow), carboxylazocalix [4] aromatic hydrocarbons 3 (orange), carboxylazocalix [4] aromatic hydrocarbons 4 (redness) successively according to its polarity difference, the productive rate that obtains product is respectively 27% carboxylazocalix [4] aromatic hydrocarbons 1,51% carboxylazocalix [4] aromatic hydrocarbons 2,13% carboxylazocalix [4] aromatic hydrocarbons 3,5% carboxylazocalix [4] aromatic hydrocarbons 4; The overall yield of four kinds of products reaches 95%.
Embodiment two:
Because aniline can be rotten after placing for some time, so the aniline in this present embodiment must be to obtain with nitrogen protection distillation after the molecular sieve drying.
Sodium Nitrite 0.69g (10mmol) is dissolved in the water of 5mL, under agitation slowly be added drop-wise to then and contain the concentrated hydrochloric acid that 0.91mL (10mmol) newly steams aniline: water=3: 7 (volume ratios, wherein concentrated hydrochloric acid is 3mL) solution in, make it temperature and remain on 0～5 ℃, dropwised back and restir 30 minutes.
Because diazo salt is unstable at normal temperatures, and the preparation diazo salt is thermopositive reaction, so temperature of reaction should remain at 0～5 ℃.
Then above-mentioned diazo salt solution slowly is added drop-wise to the 26mLN that is mixed with 1g (2.36mmol) cup [4] aromatic hydrocarbons and 4.08g (30mmol) sodium-acetate that is stirring, (N in the mixing solutions of N '-dimethyl formamide and methyl alcohol, the volume ratio of N '-dimethyl formamide and methyl alcohol is 8: 5), there is red precipitate to produce gradually, temperature still makes it to remain on 0～5 ℃, leaves standstill after dripping about 4.5 hours.
After question response is complete, the adding massfraction is 0.25% 150mL dilute hydrochloric acid, be heated to 60 ℃ then, stirred about 30 minutes, have a large amount of cotton-shaped red precipitates to produce, suction filtration, be washed with water to neutrality, use methanol wash afterwards, afterwards precipitation is joined the 150mL hexanaphthene: stirred 3 hours in the mixed solvent of ether=1: 1 (volume ratio), filter the back precipitation is dissolved in the 40mL trichloromethane, and carry out dried overnight with anhydrous sodium sulphate.
Products therefrom is carried out silica gel column chromatography to be separated, eluent is a methylene dichloride: sherwood oil (60-90 ℃)=2: 1 (volume ratio), obtain target product carboxylazocalix [4] aromatic hydrocarbons 1 (pale yellow), carboxylazocalix [4] aromatic hydrocarbons 2 (yellow), carboxylazocalix [4] aromatic hydrocarbons 3 (orange), carboxylazocalix [4] aromatic hydrocarbons 4 (redness) successively according to its polarity difference, the productive rate that obtains product is respectively 5% carboxylazocalix [4] aromatic hydrocarbons 1,13% carboxylazocalix [4] aromatic hydrocarbons 2,50% carboxylazocalix [4] aromatic hydrocarbons 3,23% carboxylazocalix [4] aromatic hydrocarbons 4; The overall yield of four kinds of products reaches 91%.
Embodiment three:
Because aniline can be rotten after placing for some time, so the aniline in this present embodiment must be to obtain with nitrogen protection distillation after the molecular sieve drying.
Sodium Nitrite 0.69g (10mmol) is dissolved in the water of 5mL, under agitation slowly be added drop-wise to then and contain the concentrated hydrochloric acid that 0.91mL (10mmol) newly steams aniline: water=3: 7 (volume ratios, wherein concentrated hydrochloric acid is 3mL) solution in, make it temperature and remain on 0～5 ℃, dropwised back and restir 30 minutes.
Because diazo salt is unstable at normal temperatures, and the preparation diazo salt is thermopositive reaction, so temperature of reaction should remain at 0～5 ℃.
Then above-mentioned diazo salt solution slowly is added drop-wise to the 26mLN that is mixed with 1g (2.36mmol) cup [4] aromatic hydrocarbons and 4.08g (30mmol) sodium-acetate that is stirring, (N in the mixing solutions of N '-dimethyl formamide and methyl alcohol, the volume ratio of N '-dimethyl formamide and methyl alcohol is 8: 5), there is red precipitate to produce gradually, temperature still makes it to remain on 0～5 ℃, leaves standstill after dripping about 7 hours.
After question response is complete, the adding massfraction is 0.25% 150mL dilute hydrochloric acid, be heated to 60 ℃ then, stirred about 30 minutes, have a large amount of cotton-shaped red precipitates to produce, suction filtration, be washed with water to neutrality, use methanol wash afterwards, afterwards precipitation is joined middle the stirring 3 hours of mixed solvent (wherein the volume ratio of hexanaphthene and ether is 1: 1) of 150mL hexanaphthene and ether, filter the back precipitation is dissolved in the 40mL trichloromethane, and carry out dried overnight with anhydrous sodium sulphate.
Products therefrom is carried out silica gel column chromatography to be separated, eluent is a methylene dichloride: sherwood oil (60-90 ℃)=2: 1 (volume ratio), obtain target product carboxylazocalix [4] aromatic hydrocarbons 3 (orange), carboxylazocalix [4] aromatic hydrocarbons 4 (redness) successively according to its polarity difference, the productive rate that obtains product is respectively 3% carboxylazocalix [4] aromatic hydrocarbons 2,30% carboxylazocalix [4] aromatic hydrocarbons 3,53% carboxylazocalix [4] aromatic hydrocarbons 4; The overall yield of three kinds of products reaches 86%.
Embodiment four:
The target product 1,2,3,4 that embodiment one and two is obtained is dissolved in trichloromethane: in the mixed solvent of normal hexane=3: 1 (volume ratio), recrystallization is separated out crystal, carries out infrared, hydrogen spectrum, carbon spectrum, elemental analysis then, and concrete outcome is as follows:
Carboxylazocalix [4] aromatic hydrocarbons 1:
IR：v(KBr)/cm
-11595(N＝N)；
1H?NMR(400Hz，CDCl
3)：3.46，3.57(’q’，AB，8H，Ar-CH
2-Ar)；6.61-6.68(m，3H，H-Ar)；6.95-6.99(t，4H，H-Ar)；7.05-7.07(d，2H，H-Ar)；7.29-7.39(m，3H，H-Ar)；7.61(s，1H，H-Ar)；7.72-7.74(d，2H，H-Ar)；10.13(s，4H，OH)；
13CNMR(300Hz，CDCl
3)：153.02，152.04，148.92，147.70，130.67，129.48，129.27，129.18，128.60，128.34，127.91，124.29，122.76，122.71，122.64，32.04，31.92；
Ultimate analysis: theoretical value (%): C, 77.25; H, 5.34; N, 5.30;
Measured value (%): C, 76.84; H, 5.36; N, 5.22.
Carboxylazocalix [4] aromatic hydrocarbons 2:
IR：v(KBr)/cm
-11589(N＝N)；
1HNMR(400Hz，CDCl
3)：3.71，4.32(’q’，AB，8H，Ar-CH
2-Ar)；6.75-6.83(m，2H，H-Ar)；7.07-7.20(m，4H，H-Ar)；7.40-7.50(m，6H，H-Ar)；7.70-7.72(t，3H，H-Ar)；7.78-7.83(m，5H，H-Ar)；10.24(s，4H，OH)；
13CNMR(300Hz，CDCl
3)：152.96，151.71，148.70，147.96，147.66，130.79，130.74，129.76，129.25，128.64，128.38，127.83，125.17，124.60，123.78，123.00，122.86，122.80，32.10，31.95；
Ultimate analysis: theoretical value (%): C, 75.93; H, 5.10; N, 8.86;
Measured value (%): C, 75.50; H, 5.02; N, 9.02.
Carboxylazocalix [4] aromatic hydrocarbons 3:
IR：v(KBr)/cm
-11573(N＝N)；
1HNMR(400Hz，CDCl
3)：3.69，4.34(’q’，AB，8H，Ar-CH
2-Ar)；6.81-6.83(t，1H，H-Ar)；7.16-7.19(d，2H，H-Ar)；7.37-7.48(m，9H，H-Ar)；7.71-7.70(d，2H，H-Ar)；7.79-7.85(m，10H，H-Ar)；10.24(s，4H，OH)；
13CNMR(300Hz，CDCl
3)：153.15，151.90，151.85，130.99，130.93，129.95，129.44，129.35，128.83，128.56，128.01，125.36，124.79，123.97，123.19，123.06，122.99，32.29，32.14；
Ultimate analysis: theoretical value (%): C, 74.98; H, 4.92; N, 11.41;
Measured value (%): C, 74.52; H, 5.10; N, 10.93.
Carboxylazocalix [4] aromatic hydrocarbons 4
IR：v(KBr)/cm
-11563(N＝N)；
1HNMR(400Hz，CDCl
3)：3.85，4.38(’q’，AB，8H，Ar-CH
2-Ar)；7.38-7.47(m，13H，H-Ar)；7.81-7.83(d，15H，H-Ar)；10.26(s，4H，OH)；
13CNMR(300Hz，CDCl
3)：153.11，151.72，148.17，130.97，129.42，128.67，124.82，123.02，32.25；
Ultimate analysis: theoretical value (%): C, 74.27; H, 4.79; N, 13.33;
Measured value (%): C, 74.32; H, 4.87; N, 12.89.
Table 1, table 2, table 3 have been listed the crystallographic parameter of carboxylazocalix [4] aromatic hydrocarbons 1,2,4 respectively.
The crystallographic parameter of table 1. carboxylazocalix [4] aromatic hydrocarbons 1
The crystallographic parameter of table 2. carboxylazocalix [4] aromatic hydrocarbons 2
The crystallographic parameter of table 3. carboxylazocalix [4] aromatic hydrocarbons 4
The present invention has also carried out ultraviolet research to four kinds of products, (solvent is N to their uv-absorbing λ max, N '-dimethyl formamide) is respectively carboxylazocalix [4] aromatic hydrocarbons 1 (620nm), carboxylazocalix [4] aromatic hydrocarbons 2 (568nm), carboxylazocalix [4] aromatic hydrocarbons 3 (566nm), carboxylazocalix [4] aromatic hydrocarbons 4 (563nm), discovery has less blue shift along with 1,2,3,4, and this absorption peak is the charateristic avsorption band of azo-group.Concrete collection of illustrative plates can be referring to Fig. 1.
Claims (3)
1. the preparation method of a carboxylazocalix [4] arene derivatives is characterized in that: with chlorination nitrogen benzide and cup [4] aromatic hydrocarbons is reactant, N, the mixing solutions of N '-dimethyl formamide and methyl alcohol is a solvent, and sodium-acetate is an initiator, carries out the mixture of 4 kinds of carboxylazocalixes of prepared in reaction [4] aromatic hydrocarbons, filter washing, drying then, separate through silica gel column chromatography, obtain 5-azobenzene-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons, 5,11-two azobenzenes-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons, 5,11,17-trisazo-phenyl-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons and 5,11,17,23-four azobenzenes-25,26,27,28-tetrahydroxy cup [4] aromatic hydrocarbons;
Wherein, described reaction may further comprise the steps:
(1) the chlorination nitrogen benzide is added the N that is dissolved with cup [4] aromatic hydrocarbons and sodium-acetate, in the mixing solutions of N '-dimethyl formamide and methyl alcohol;
(2) in 0～5 ℃ temperature, reaction obtained the mixture of 4 kinds of carboxylazocalixes [4] aromatic hydrocarbons more than 2 hours.
2. the preparation method of carboxylazocalix according to claim 1 [4] arene derivatives is characterized in that: the reaction times of described step (2) is 2～3 hours.
3. the preparation method of carboxylazocalix according to claim 1 [4] arene derivatives is characterized in that: the reaction times of described step (2) is 4～5 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130158A (en) * | 2014-07-25 | 2014-11-05 | 辽宁大学 | Novel calix[4]arene derivative of which lower edge simultaneously containing azo and schiff base groups and its synthesis method and use |
| CN104844473A (en) * | 2014-04-10 | 2015-08-19 | 刘雷雷 | 2,4,6-Tri(4-carboxylazophenyl)-1,3,5-trihydroxybenzene and preparation method thereof |
| CN114479102A (en) * | 2022-01-24 | 2022-05-13 | 中国科学院兰州化学物理研究所 | Azo reductase and glutathione double-response type supramolecular fluorescent probe as well as preparation and application thereof |
-
2008
- 2008-09-05 CN CNA2008101958582A patent/CN101348445A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844473A (en) * | 2014-04-10 | 2015-08-19 | 刘雷雷 | 2,4,6-Tri(4-carboxylazophenyl)-1,3,5-trihydroxybenzene and preparation method thereof |
| CN104130158A (en) * | 2014-07-25 | 2014-11-05 | 辽宁大学 | Novel calix[4]arene derivative of which lower edge simultaneously containing azo and schiff base groups and its synthesis method and use |
| CN104130158B (en) * | 2014-07-25 | 2015-10-28 | 辽宁大学 | Cup [4] arene derivatives of a kind of lower edge simultaneously containing azo and schiff bases group and synthetic method thereof and application |
| CN114479102A (en) * | 2022-01-24 | 2022-05-13 | 中国科学院兰州化学物理研究所 | Azo reductase and glutathione double-response type supramolecular fluorescent probe as well as preparation and application thereof |
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