CN105080423A - Quaternary ammonium salt type Gemini surfactant and preparation method therefor - Google Patents
Quaternary ammonium salt type Gemini surfactant and preparation method therefor Download PDFInfo
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- CN105080423A CN105080423A CN201410191043.2A CN201410191043A CN105080423A CN 105080423 A CN105080423 A CN 105080423A CN 201410191043 A CN201410191043 A CN 201410191043A CN 105080423 A CN105080423 A CN 105080423A
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- quaternary ammonium
- porphyrin
- gemini surfactants
- ammonium gemini
- bromomethyl
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Abstract
The invention provides a quaternary ammonium salt type Gemini surfactant shown in a formula I. According to the quaternary ammonium salt type Gemini surfactant, a conjugated system is introduced into a linking group and a tail chain of the Gemini surfactant, so that the quaternary ammonium salt type Gemini surfactant with better spectral characteristic and phi-phi bulk property is obtained, and therefore, an aggregation structure and changes thereof of surfactant molecules are researched in a facilitated mode, and guidance is provided for developing a functional material of a new Gemini surfactant; and the conjugated system can be a benzene ring, biphenyl, a condensed ring, porphin and the like.
Description
Technical field
The present invention relates to a kind of Gemini surface active, specifically a kind of Quaternary Ammonium Gemini Surfactants and preparation method thereof.
Background technology
Microstructure, the pattern and adhesion strength etc. at interface have significant impact to the performance of material.The ordered arrangement of understanding and control inerface molecule and self assembling process, have important directive significance for designing and preparing the functional materials such as microstructure controlled thin layer, nano-patterning, biology sensor and photoelectric device.The crystallization of gas-liquid interface, comprises the nucleation of crystal, growth and Morphological control etc., is the research arrangement of interfacial molecular and the ideal model system of process of self-organization.
Crystalline polamer on gas-liquid interface can for illustrating molecular self-assembling process, disclose the research of the aspect such as origin of life and development of new functional material desirable model system be provided.
Soluble surfactant is a kind of new interfacial phenomenon in the crystallization of gas-liquid interface, its molecular structure with surfactant and intermolecular special interaction relevant, particularly closely related in the self assembly behavior of boundary zone with surfactant, new information can being provided for understanding surfactant in depth in the self assembly behavior of gas-liquid interface to the research of its crystallization mechanism and crystal structure, providing basis for exploring biomineralization process further.For this reason, we need a kind of Gemini surface active containing rigid radical to be object, further investigate in the mechanism two of the usefulness of weak interaction in regulation and control Gemini surface active interfacial crystallization and Gemini surface active interfacial crystallization.
But current Gemini surface active cannot meet the requirement of above-mentioned research.Therefore, we need a kind of new Gemini surface active, clear and definite Gemini intermolecular weak interaction can be carried out on the impact of interfacial crystallization performance by this Gemini surface active, disclose the assembling process of Gibbs monomolecular film induction interfacial crystallization, illustrate the interfacial crystallization mechanism of Gemini surface active; The structure-activity relationship of Gemini surface active in interfacial crystallization can also be grasped, for the functional material of development of new Gemini surface active provides guidance simultaneously.
Summary of the invention
For solving the deficiencies in the prior art, the present invention proposes a kind of Quaternary Ammonium Gemini Surfactants, at linking group and the tail chain place introducing conjugated system of Gemini surface active, described conjugated system can be phenyl ring, connect benzene, condensed ring and porphines etc., thus obtain a kind of Quaternary Ammonium Gemini Surfactants with better spectral characteristic and pi-pi accumulation performance, and then contribute to aggregated structure and the change thereof of studying surfactant molecule, for the functional material of development of new Gemini surface active provides guidance.
In order to achieve the above object, the invention provides a kind of Quaternary Ammonium Gemini Surfactants, represent with following general formula I:
Wherein, R
1and R
2be identical or different group, be selected from-H respectively, C
1~ C
15straight or branched alkyl.
In an embodiment of the present invention, described R
2for-H, R
1be selected from C
10~ C
15straight or branched alkyl; Preferably, described R
2for-H, R
1for C
12linear paraffin base.
In the present invention one preferred embodiment, described Quaternary Ammonium Gemini Surfactants represents with chemical formula i:
The present invention also provides the preparation method of above-mentioned Quaternary Ammonium Gemini Surfactants, and with porphyrin and alkylamine for reactant, heating reflux reaction 8 ~ 16 hours, obtains target product after purifying.
In an embodiment of the present invention, described preparation method specifically comprises following steps:
(1) replacing dipyrrylmethanes or dipyrromethane for raw material with 5-, obtaining porphyrin through reacting under trifluoroacetic acid condition with 4-bromomethyl benzaldehyde; (2) porphyrin obtained with step (1) and alkylamine are for reactant, and heating reflux reaction 8 ~ 16 hours, obtains target product after purifying; Preparation path is as follows:
(1)
(2)
In a preferred embodiment of the present invention, the concrete preparation method such as formula the Quaternary Ammonium Gemini Surfactants shown in i is provided, said method comprising the steps of:
(1) dipyrrylmethanes is prepared
Under argon shield, make pyrroles, paraformaldehyde room temperature reaction 20 hours under sour environment, purified rear acquisition dipyrrylmethanes; Described pyrroles is 40:1 with the molal weight ratio of paraformaldehyde;
(2) 5,15-bis-(4-bromomethyl) phenyl porphyrin is prepared
Under argon shield, make dipyrrylmethanes and 4-bromomethyl dissolution of benzaldehyde in dichloromethane solvent, after adding trifluoroacetic acid, under room temperature, reaction is spent the night, then add dichloro-dimethyl benzoquinones (DDQ) and continue reaction 30 minutes, 5,15-bis-(4-bromomethyl) phenyl porphyrin is obtained after purifying; The mass ratio of described dipyrrylmethanes and 4-bromomethyl benzaldehyde is (0.70 ~ 0.75): 1;
(3) target product is prepared, the Quaternary Ammonium Gemini Surfactants shown in formula i
The porphyrin that step (2) is obtained, lauryl amine are dissolved in oxolane, heating reflux reaction 12 hours, purified rear acquisition target product; Described porphyrin is 1:0.4 with the molal weight ratio of lauryl amine.
It should be noted that, the reagent described in the present invention is all have commercially available product.
Quaternary Ammonium Gemini Surfactants of the present invention introduces as phenyl ring at the linking group of Gemini surface active and tail chain place, connect the large conjugation group such as benzene, condensed ring or porphines first, obtains a kind of Quaternary Ammonium Gemini Surfactants with better spectral characteristic and pi-pi accumulation performance.Quaternary Ammonium Gemini Surfactants of the present invention can form interfacial crystallization, and has better spectral characteristic and pi-pi accumulation performance.Therefore, by the research to Quaternary Ammonium Gemini Surfactants of the present invention, researcher can be helped to understand aggregated structure and the change thereof of surfactant molecule, for the functional material of development of new Gemini surface active provides guidance, containing porphyrin ring in this Gemini surface active, therefore new photoelectric material can be developed as, can harmful ion in enrichment water.
Accompanying drawing explanation
Fig. 1 is the nuclear-magnetism figure of the target product of embodiment 1;
Fig. 2 is the infrared spectrum of the target product of embodiment 1;
Fig. 3 is the surface pressing-molecular area isothermal curve of the target product of embodiment 1;
Fig. 4 is the uv atlas of the target product of embodiment 1.
Detailed description of the invention
Be described in detail the present invention below in conjunction with embodiment, embodiment is intended to explain and non-limiting technical scheme of the present invention.
Quaternary Ammonium Gemini Surfactants shown in embodiment 1. formula i and preparation thereof
In the present embodiment, provide such as formula the Quaternary Ammonium Gemini Surfactants shown in i and preparation thereof,
Concrete preparation method is as follows.
(1) dipyrrylmethanes is prepared
The pyrroles of 30ml (432mmol), the paraformaldehyde of 324mg (10.8mmol) and the acetic acid of 45ml is added in the three-neck flask of 100ml.Pass into argon shield, magnetic agitation, at room temperature react 20 hours.After reacting completely, the carrene adding 150ml dilutes, and the distilled water adding 90ml washes 2 times, and then the KOH solution of the 0.1mol adding 90ml neutralizes, and adds excessive anhydrous sodium sulfate drying, hold over night.
Second day, by filtering, anhydrous sodium sulfate being removed, revolving to boil off and desolventize, repeatedly carrying out decompression distillation to revolving the solution after steaming, pyrroles complete for high boiling unreacted is got rid of.By column chromatography, eluant, eluent CH
2cL
2be 2:1 with benzinum ratio, obtain pure white solid product.Productive rate: 596mg, 42%.1H-NMR(400Hz,CDCL3)：3.97(s,2H)，6.03(m,2H),6.14-6.16(m,2H),6.64-6.66(m,2H),7.83(br,2H,pyrroleNH)。
(2) 5,15-bis-(4-bromomethyl) phenyl porphyrin is prepared
In the three-neck flask of the 500ml of drying, add the dipyrrylmethanes of 367.23mg, the 4-bromomethyl benzaldehyde of 500mg and the carrene of 250ml, pass into argon gas, repeatedly to replace in bottle air three times.Add the trifluoroacetic acid of 0.1ml, solution becomes faint yellow, magnetic agitation, and reaction is spent the night.
Second day, join in reactant liquor by the DDQ of 0.768g, solution colour continues to react half an hour, then adds the triethylamine quencher reactant liquor of 2ml.Revolve and steam except desolventizing.By column chromatography, add eluant, eluent CH
2cL
2be 6:1 with benzinum ratio, obtain pure product: 368mg, productive rate 44.7%.1H-NMR
(3) target product is prepared, the Quaternary Ammonium Gemini Surfactants 12-{5 shown in formula i, 15-bis-(4-bromomethyl) phenyl porphyrin }-12Gemini quaternary ammonium salt
In the round-bottomed flask of the 50ml of drying, add the oxolane of the porphyrin of 63mg (0.097mmol), 0.052g (0.243mmol) lauryl amine and 15ml, magnetic agitation, be heated to backflow, after reaction 12h, after being cooled to room temperature, stop reaction.Steaming except after desolventizing by revolving, obtaining clean product by recrystallization method and being target product.
The nuclear-magnetism figure of the Quaternary Ammonium Gemini Surfactants shown in embodiment 2. formula i
Fig. 1 is the nuclear-magnetism figure of the Quaternary Ammonium Gemini Surfactants shown in formula i, and wherein solvent is DMSO.Analysis can obtain, and has 2 hydrogen in the porphin ring of porphyrin, and with shielding action in ring, for High-Field has very low chemical shift, nuclear-magnetism figure is negative peak, this is its characteristic peak.2 hydrogen so comparatively speaking outside large porphyrin ring receive the effect of deshielding, and belong to the high chemical shift in low field, so be in the peak of 10.70.2 hydrogen on phenyl ring receive because be in outside large porphyrin ring the effect of deshielding, chemical shift is from the closer hydrogen of porphyrin ring compared with higher position, so e-8.05, f-8.43, g and h is the H on pyrrole ring, because effect each other, to split point so carry out coupling, become double peak, be respectively the peak of 9.15 and 9.72.D above lauryl amine is a methylene, and namely it receive the effect of deshielding of phenyl ring, receives again the inducing action of N, and institute thinks unimodal, is in the position of 4.93.Next just judge according to the number of hydrogen, k 3.35 has 12 hydrogen, and c is the peak of 3.57, and have 4 hydrogen, b is the peak of 1.17 to 1.46, and have 40 hydrogen, a is the peak of 0.78, has 6 hydrogen.By above analysis, the structure of target product is in the main true.
The infrared spectrum of the Quaternary Ammonium Gemini Surfactants shown in embodiment 3. formula i
Fig. 2 is the infrared spectrum of the Quaternary Ammonium Gemini Surfactants shown in formula i.Fig. 2 is obtained, at 2920cm by KBr pressed disc method
-1and 2850cm
-1neighbouring peak is the C-H stretching vibration absworption peak of methylene on alkyl chain.1612cm
-1, 1492cm
-1for the stretching vibration peak of the C=C key on phenyl ring.At 1358cm
-1for-CH
3the stretching vibration absworption peak of base.3465cm
﹣ 1and 3295cm
﹣ 1having two peaks, is the absworption peak of amino N-H key stretching vibration on porphyrin ring, 855cm
-1for the absworption peak of methylene be connected with phenyl ring, 728cm
-1for (-(CH
2)
n-, n>=4) rocking vibration peak.
The position of absworption peak meets all very much, tentatively can be judged as target product.
Surface pressing-molecular area the isothermal curve of the Quaternary Ammonium Gemini Surfactants shown in embodiment 4. formula i
Fig. 3 is the surface pressing-molecular area isothermal curve of the Quaternary Ammonium Gemini Surfactants shown in formula i.Quaternary Ammonium Gemini Surfactants of the present invention defines stable monomolecular film on aqueous phase surface, and when surface pressing is 0mN/m, the mean molecular cross section of the Quaternary Ammonium Gemini Surfactants shown in formula i amasss as 2.6nm
2, As time goes on, surface pressing increases gradually, and porphyrin ring is holded up gradually on the water surface, and along with the reduction of molecular area, until 29mN/m place, molecular film collapses.This illustrates 12-{5,15-bis-(4-bromomethyl) phenyl porphyrin }-12Gemini quaternary ammonium salt molecular film has certain Collapse Pressure.
By 12-{5,15-bis-(4-bromomethyl) phenyl porphyrin under 5mN, 15mN, 25mN/m }-12Gemini quaternary ammonium salt unimolecule transfers to quartz plate from gas-liquid interface, obtained LB film.
The uv atlas of the Quaternary Ammonium Gemini Surfactants shown in embodiment 5. formula i
Fig. 4 is the uv atlas of the Quaternary Ammonium Gemini Surfactants shown in formula i.As seen from Figure 4, the maximum absorption wavelength of the peak value of the Soret band of the Quaternary Ammonium Gemini Surfactants shown in formula i in chloroformic solution is 408nm, and be with absworption peaks to be the Absorption Characteristics of porphyrin monomer at four Q of 502nm, 538nm, 575nm, 629nm, this just demonstrates the correctness of porphyrin structure further.The peak value maximum absorption wavelength of the Soret band of 12-porphyrin on LB film is 412nm, and compared with the peak value of 12-porphyrin in chloroformic solution, there occurs red shift, and absorption band broadens, four Q corresponded are with absorbing wavelength also to there occurs a small amount of red shift.Feature on these uv atlas shows, at the ordered arrangement of gas-liquid interface amphiphillic surfactant by molecular self-assembling, aggregation extent increases gradually, strengthens interaction, defines LB film, also illustrates really there is certain pi-pi accumulation effect.
Quaternary Ammonium Gemini Surfactants of the present invention introduces as phenyl ring at the linking group of Gemini surface active and tail chain place, connect the large conjugation group such as benzene, condensed ring or porphines first, obtains a kind of Quaternary Ammonium Gemini Surfactants with better spectral characteristic and pi-pi accumulation performance.Quaternary Ammonium Gemini Surfactants of the present invention can form interfacial crystallization, and has better spectral characteristic and pi-pi accumulation performance.Therefore, by the research to Quaternary Ammonium Gemini Surfactants of the present invention, researcher can be helped to understand aggregated structure and the change thereof of surfactant molecule, for the functional material of development of new Gemini surface active provides guidance.
The present invention is described by above-mentioned related embodiment, but above-described embodiment is only enforcement example of the present invention.Must it is noted that published embodiment limit the scope of the invention.On the contrary, be contained in the spirit of claims and the amendment of scope and impartial setting to be included in scope of the present invention.
Claims (6)
1. a Quaternary Ammonium Gemini Surfactants, represents with following general formula I:
Wherein, R
1and R
2be identical or different group, be selected from-H respectively, C
1~ C
15straight or branched alkyl.
2. Quaternary Ammonium Gemini Surfactants as claimed in claim 1, is characterized in that, described R
2for-H, R
1be selected from C
10~ C
15straight or branched alkyl.
3. Quaternary Ammonium Gemini Surfactants as claimed in claim 1, it is characterized in that, described Quaternary Ammonium Gemini Surfactants represents with chemical formula i:
4. a preparation method for Quaternary Ammonium Gemini Surfactants as claimed in claim 1, with porphyrin and alkylamine for reactant, heating reflux reaction 8 ~ 16 hours, obtains target product after purifying.
5. the preparation method of Quaternary Ammonium Gemini Surfactants as claimed in claim 4, it is characterized in that, described preparation method specifically comprises following steps:
(1) replacing dipyrrylmethanes or dipyrromethane for raw material with 5-, obtaining porphyrin through reacting under trifluoroacetic acid condition with 4-bromomethyl benzaldehyde; (2) porphyrin obtained with step (1) and alkylamine are for reactant, and heating reflux reaction 8 ~ 16 hours, obtains target product after purifying.
6. a concrete preparation method for Quaternary Ammonium Gemini Surfactants as claimed in claim 3, comprises the following steps:
(1) dipyrrylmethanes is prepared
Under argon shield, make pyrroles, paraformaldehyde room temperature reaction 20 hours under sour environment, purified rear acquisition dipyrrylmethanes; Described pyrroles is 40:1 with the molal weight ratio of paraformaldehyde;
(2) 5,15-bis-(4-bromomethyl) phenyl porphyrin is prepared
Under argon shield, make dipyrrylmethanes and 4-bromomethyl dissolution of benzaldehyde in dichloromethane solvent, after adding trifluoroacetic acid, under room temperature, reaction is spent the night, and then adds dichloro-dimethyl benzoquinones and continues reaction 30 minutes, 5,15-bis-(4-bromomethyl) phenyl porphyrin is obtained after purifying; The mass ratio of described dipyrrylmethanes and 4-bromomethyl benzaldehyde is (0.70 ~ 0.75): 1;
(3) prepare target product, the porphyrin that the Quaternary Ammonium Gemini Surfactants shown in formula i makes step (2) obtain, lauryl amine are dissolved in oxolane, heating reflux reaction 12 hours, purified rear acquisition target product; Described porphyrin is 1:0.4 with the molal weight ratio of lauryl amine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110914269A (en) * | 2017-07-31 | 2020-03-24 | 住友化学株式会社 | Process for producing macrocyclic compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020107148A1 (en) * | 2000-12-05 | 2002-08-08 | Crosby Kevin E. | Herbicidal composition |
| CN1403460A (en) * | 2002-10-08 | 2003-03-19 | 清华大学 | Synthesis of monocrystal porphyrin |
| CN101389631A (en) * | 2005-12-24 | 2009-03-18 | 命运之神药品有限公司 | Process for the preparation of porphyrin derivatives as antimicrobial agents by photodynamic therapy (PDT) |
-
2014
- 2014-05-07 CN CN201410191043.2A patent/CN105080423A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020107148A1 (en) * | 2000-12-05 | 2002-08-08 | Crosby Kevin E. | Herbicidal composition |
| CN1403460A (en) * | 2002-10-08 | 2003-03-19 | 清华大学 | Synthesis of monocrystal porphyrin |
| CN101389631A (en) * | 2005-12-24 | 2009-03-18 | 命运之神药品有限公司 | Process for the preparation of porphyrin derivatives as antimicrobial agents by photodynamic therapy (PDT) |
Non-Patent Citations (1)
| Title |
|---|
| VLADIMÍR KRÁL ET AL.: "New chiral porphyrin–brucine gelator characterized by methods of circular dichroism", 《TETRAHEDRON》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110914269A (en) * | 2017-07-31 | 2020-03-24 | 住友化学株式会社 | Process for producing macrocyclic compound |
| CN110914269B (en) * | 2017-07-31 | 2022-07-29 | 住友化学株式会社 | Process for producing macrocyclic compound |
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