CN101870675B - Novel organogel compound and preparation method thereof - Google Patents
Novel organogel compound and preparation method thereof Download PDFInfo
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- CN101870675B CN101870675B CN2010101979228A CN201010197922A CN101870675B CN 101870675 B CN101870675 B CN 101870675B CN 2010101979228 A CN2010101979228 A CN 2010101979228A CN 201010197922 A CN201010197922 A CN 201010197922A CN 101870675 B CN101870675 B CN 101870675B
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- gel
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- polyamines
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Abstract
The invention belongs to the technical field of supramolecular chemistry, in particular relates to a novel organogel compound, a preparation method thereof and organogel prepared from the organogel compound. A structural formula of the organogel compound provided by the invention is 6-C6H5O-C12H5NO2-(CH2)10-COOH. The compound does no t have the characteristic of forming gel, and the gel can be formed by mixing the compound and diamine or polyamines, wherein anhydride naphthalene is excellent illuminophore, so that the photoinduced response is realized in the state of solution or the gel. The amine or an organic solvent for forming the gel has a certain regulating and control effect on various physical and chemical properties such as appearance, spectra of the gel and the like.
Description
Technical field
The invention belongs to the supramolecular chemistry technical field, be specifically related to a kind of novel organogel compound and preparation method thereof, and the organogel that obtains by such gelatinous cpd.
Background technology
Organogel (Organogel) is through the molecular interaction of the gel factor and wraps up the colloid that various organic solvents form.This organogel has thermal reversibility and to the sensitivity characteristic of outside environmental change, makes organogel at aspects such as preparation environment sensitive gel, new inorganic material template, phase-transfer catalysis organic reaction, medicament slow releases good using value arranged.In addition, the various nanofibrous structures that organogel forms through molecular interaction are for we design nano-scale device and novel material provides molecular model and theoretical foundation.Therefore, the novel organogel of design composite structure is having tempting application prospect aspect the performance development of molecule self-assembly novel material.
Summary of the invention
The object of the present invention is to provide a kind of novel organogel compound and preparation method thereof.
Organogel compound provided by the invention is a kind of organic fluorescent gel compound based on the naphthalene acid anhydride, it is characterized in that this compounds is is chromophoric alkane chain carboxylic acid 4-phenoxy-N-undeeanoic acid base-1 with the naphthalene acid anhydride, the 8-naphthalimide, and its structural formula is:
Molecular formula is: [6-C
6H
5O-C
12H
5NO
2-(CH
2)
10-COOH], this compound itself does not have into the characteristic of gel, and can form gel after diamines or polyamines mix.
Among the present invention, the preparation method of above-claimed cpd is following: aminoundecanoic acid methyl esters heating reflux reaction in toluene solution that will contain naphthalene acid anhydride and the quintuple of functional group generates the carboxylicesters of naphthalene acid anhydride, and taking off the carboxylic acid that obtains behind the ester is required compound.Wherein the naphthalene acid anhydride is good luminophor, can realize the photoinduction response under solution or the gel state.This compounds does not become gel separately in organic solvent or water, have into the gel ability and mix back gained material with diamines or polyamines.Different amine exerts an influence to various physics, chemical property such as gel pattern, spectrum.That is to say, can regulate the sympathesis of intermolecular ydrogen bonding effect and fluorophore through the type that changes ammonia, thereby reach regulation and control gelling properties.
Diamines described in the present invention or polyamines are preferably quadrol (EDA), hexanediamine (HDA), triethylamine (TEA), 4,5-dinitrobenzene-1,2-phenylenediamine (NBDA) and 1,2-diaminoanthraquinone--9,10-dioxy (DAOA).
Compound according to the invention with the concrete steps that diamines or polyamines form gel is: gelatinous cpd is dissolved in the organic solvent with 1: 1 equivalent by carboxy-containing acid group of institute and primary amine group respectively with organic amine mixes; Revolve then to steam and obtain pressed powder; Again with about this pressed powder heated sealed to solvent boiling point; Make the dissolving as far as possible of gel factor pressed powder, leave standstill cooling then and promptly form gel.
According to the one-tenth glue of organogel mechanism, we can infer, suitable extension or shorten the chain length of long alkyl chain in the compound molecule and do not influence its intermolecular stacked structure also can form new gelatinous cpd.
Description of drawings
Fig. 1: made gel photograph; L+EDA is in toluene (a), octanol (b); L+HDA is in methyl alcohol (c), hexanaphthene (d), octanol (e), and L+NBDA (f), L+DAOA (g) become the photo of gel (25mg/ml) under natural lighting (left side) and uv-radiation (right side) condition in acetonitrile.
Fig. 2: (a) (concentration is 10 to gelatinous cpd (mixture of compound L and HDA) in ethanol, octanol, acetonitrile solution respectively
-4Mol) absorption spectrum.(b) gelatinous cpd (mixture of compound L and the HDA) solution in hexanaphthene, ethanol, octanol, acetonitrile (10 respectively
-4Mol) and the fluorescence spectrum (Fig. 1 b) of gel (25 mg/ml), dotted line is a solution fluorescence, and solid line is a gel fluorescence.
Fig. 3: gelatinous cpd becomes the sem photograph of xerogel in various organic solvents; A:L+EDA, scale 20 μ m; B:L+HDA, scale 20 μ m; C:L+TEA, scale 20 μ m, d:L+NBDA, scale 20 μ m, e:L+DAOA, scale 50 μ m form the SEM figure of xerogel in ethanol.
Fig. 4: compound L
1The HNMR spectrogram.
Embodiment
Further specify the preparation method of gelatinous cpd below with instance.Following all raw materials can be self-controls or commercially available.
Aminoundecanoic acid methyl esters [NH
2-(CH
2)
10-COOCH
3]:
Aminoundecanoic acid 8.05g (0.04mol) is dissolved in the 50mL anhydrous methanol, stirs and slowly splash into 98% sulfuric acid, heating reflux reaction 8 hours down.After reaction is accomplished, reaction solution revolved to steam obtain white powder, with ETHYLE ACETATE wash the aminoundecanoic acid methyl esters.
4-bromo-N-methyl undecylate-1,8-naphthalimide [4-Br-C
12H
5NO
2-(CH
2)
10-COOCH
3]:
4-bromo-1, (5.54g, 0.02mol) (5.17g 0.024mol) is dissolved in 100ml toluene to 8-naphthalene acid anhydride, and stirring heating refluxed 12 hours with the aminoundecanoic acid methyl esters.Reaction finishes the back vacuum rotary steam, and the thick product of gained carries out column chromatography with ETHYLE ACETATE, uses ethanol and water 4: 1 (v/v) recrystallization then, and productive rate is 83%; Fusing point is 61-63 ℃;
1H NMR (400MHz, CDCl
3): δ 8.66 (d, 1H, J=12Hz), 8.57 (d, 1H, J=12Hz), 8.41 (d, 1H, J=12Hz); 8.04 (d, 1H, J=12Hz), 7.85 (t, 1H, J=16Hz), 4.15 (t, 2H); 3.66 (s, 3H), 2.29 (t, 2H), 1.75-1.68 (m, 2H), 1.41-1.27 (m, 16H);
13C NMR (100MHz, CDCl
3): δ 174.6,163.8, and 163.7,133.4,132.2,131.4,131.3,130.7,130.4,129.1,128.3,123.3,122.4,51.7,40.8,34.3,29.7,29.6,29.5,29.4,28.3,27.3,25.2.
4-phenoxy-N-methyl undecylate-1,8-naphthalimide [4-C
6H
5O-C
12H
5NO
2-(CH
2)
10-COOCH
3]:
The 4-bromine is to phenylene-N-methyl undecylate-1, and the 8-naphthalimide (2.0g, 5.31mmol), phenol (1.1g, 11.69mmol) and K
2CO
3(2.2g, 15.94mmol) mixing is dissolved in DMF (40mL), N
2Be heated to 100 ℃ of stirring reactions 8 hours under the protection.Reaction finishes the back underpressure distillation, and the thick product of gained carries out column chromatography, and (methylene dichloride/sherwood oil=1/1 v/v) obtains white powder.Productive rate is 71%; Fusing point is 72-74 ℃.
1H NMR (400MHz, CDCl
3): δ 8.68 (q, 2H), 8.45 (d, 1H, J=8Hz), 7.78 (t, 1H, J=16Hz); 7.49 (t, 2H, J=16Hz), 7.31 (t, 1H, J=12Hz), 7.19 (d, 2H; J=8Hz), 6.91 (d, 1H, J=8Hz), 4.16 (t, 2H), 3.66 (s; 3H), 2.30 (t, 2H), 1.76-1.69 (m, 2H), 1.42-1.280 (m, 16H);
13C NMR (100MHz, CDCl
3): δ 174.6,164.6, and 164.0,160.1,155.0,133.0,132.1,130.6,129.9,128.7; 126.7,125.8,124.1,122.9,121.0,116.8,110.8,51.7,40.6; 34.4,29.7,29.6,29.6,29.5,29.4,28.4,27.4,25.2.MS (EI): C
30H
33NO
5M/z, 488.3; C
30H
33NO
5Ultimate analysis: C, 73.90; H, 6.82; N, 2.87.Found:C, 74.09; H, 6.82; N, 2.80.
4-phenoxy-N-undeeanoic acid base-1,8-naphthalimide [4-C
6H
5O-C
12H
5NO
2-(CH
2)
10-COOH]:
The 4-phenoxy is to phenylene-N-methyl undecylate-1, and (4.5g 9.23mmol) is dissolved among the THF (40mL) the 8-naphthalimide, and (reaction was stirred 3 days for 6.6g, the 276.87mmol) aqueous solution (40mL) to add LiOH.Reaction finishes the back and uses organic solvent extraction, and water has deposition to generate with HCl adjustment PH to 2-3, filters back gained solid and product.With obtaining white powder compound 1 after the ether washing, productive rate is 83%.Fusing point is 110-112 ℃.
1H NMR (400MHz, CDCl
3) shown in accompanying drawing 4.
Technique effect of the present invention:
1. the gellifying property of gained gelatinous cpd test: at first compound (being labeled as L) is mixed to be dissolved in the chloroform with the primary amine groups equivalent with the carboxylic acid group with organic amine and stir; Revolve then to steam and obtain pressed powder; For example; 0.1g (0.21mmol) L mixed with 7.35 μ l (0.11mmol) quadrols be dissolved in the chloroform, remove chloroform then and obtain white powder L+EDA.Obtain the five kinds of gel factor: L+EDA (white), L+HDA (white), L+TEA (white), L+NBDA (brown), L+DAOA (dark red brown).Take by weighing the 5mg gel factor in sealed vial, add 200 μ l organic solvents, about heated sealed to solvent boiling point, make the dissolving as far as possible of the gel factor, leave standstill cooling then, observe its one-tenth gel ability in different solvents.Gel all is the thermodynamics reversible, becomes flowable colloidal sol after the heating.Concrete gellifying property is seen table 1.
The one-tenth gel capabilities list of table 1:L+ amine
Wherein, G representes gel, and PG representes partial gel, and P representes to dissolve postprecipitation, and S representes dissolving, and PS representes to be partly dissolved, and I representes insoluble; In the bracket minimum one-tenth gum concentration, the mg/ml of unit.
2. gelatinous cpd (mixture of L and HDA) is in the uv-absorbing behavior of solution state.
Compound L is at nonpolar acetonitrile solution (10
-4Mol) maximum absorption band is at 359nm in, and in polar ethanol, octanol solution (10
-4Mol) maximum absorption band is at 362nm.(Fig. 2 a) to show the faint red shift phenomenon of spectrum that increases along with solvent polarity.In addition, add before and after the HDA, absorption spectrum does not have any variation.
3. the fluorescence spectrum behavior of gelatinous cpd (mixture of compound L and HDA).
We adopt the excitation light source of wavelength 340nm, have tested the solution (10 of above-mentioned gelatinous cpd in hexanaphthene, ethanol, octanol, acetonitrile respectively
-4Mol) and the fluorescence spectrum (Fig. 2 b) of gel (25 mg/ml), dotted line is a solution fluorescence, and solid line is a gel fluorescence.Gel is that the maximum emission peak wavelength of solvent is respectively 451nm, 475nm, 433nm and 505nm with hexanaphthene, ethanol, octanol, acetonitrile, and fluorescence is with the just big displacement of change of solvent, and tangible red shift has all taken place from solution to the gel.
4. the ESEM (SEM) of gelatinous cpd (mixtures of compound L and various amine) is schemed.
In order to obtain the accumulation mode of gelatinous cpd, we carry out the detection of sem (SEM) respectively with xerogel that various amine becomes to compound L.The structure of these gels has nothing in common with each other, and is widely different.For compound L (a-e), be solvent equally with ethanol, it is acicular structure that itself and EDA form micella, with HDA be laminar, with TEA be the fold lamelliform, NBDA and DAOA are sheet.
Claims (3)
1. organogel compound is characterized in that: this compound is to be chromophoric alkane chain carboxylic acid with naphthalimide: 4-phenoxy-N-undeeanoic acid base-1, and the 8-naphthalimide, its structural formula is:
This compound itself does not have into the characteristic of gel, and itself and the mixed mixture of polyamines have gelling properties.
2. organogel compound according to claim 1 is characterized in that polyamines is selected from quadrol, hexanediamine, triethylamine, 4,5-dinitrobenzene-1,2-phenylenediamine and 1,2-diaminoanthraquinone--9,10-dioxy.
3. organogel compound as claimed in claim 1 and polyamines form the method for gel; It is characterized in that concrete steps are: gelatinous cpd is mixed with 1: 1 equivalent by carboxy-containing acid group of institute and primary amine group respectively with polyamines; In organic solvent, be heated to dissolved state, form gel after being cooled to room temperature.
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| CN102924397A (en) * | 2012-09-27 | 2013-02-13 | 西南石油大学 | Dual-component micromolecular organic gel |
| CN103992271B (en) * | 2014-05-30 | 2016-07-06 | 信阳师范学院 | A kind of organic fluorescent gel compound based on naphthalimide and preparation method thereof and application |
| CN106349219B (en) * | 2016-08-24 | 2019-03-01 | 信阳师范学院 | A kind of organogel compound of naphthalimide and preparation method thereof, gel and application |
| CN112316861A (en) * | 2020-10-30 | 2021-02-05 | 中北大学 | Double-component organic gel composition and application thereof |
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| Title |
|---|
| 疏天民.功能化有机小分子凝胶的合成与性质研究.《中国优秀硕士学位论文全文数据库工程科技I辑》.2009,(第4期), * |
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