CN103406065A - Novel amido-linkage imidazolium salt gemini surfactant and preparation method thereof - Google Patents
Novel amido-linkage imidazolium salt gemini surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a novel amido-linkage imidazolium salt gemini surfactant and a preparation method thereof, and the preparation method can be used for solving the problems that the existing preparation method of the amido-linkage heterocyclic gemini surfactant is complicated to operate, high in cost and reaction temperature, long in reaction time, and large in solvent toxicity. The preparation method comprises the following steps of: I, N-alkylation; II, amidation; III, quaternization to obtain the product amido-linkage imidazolium salt gemini surfactant. The preparation method is simple for three-step reaction operations, capable of shortening the reaction time, and mild in reaction conditions, the solvent toxicity is small, the raw material cost is low, the hydrophilic property of the novel amido-linkage imidazolium salt gemini surfactant can be greatly improved through introducing strong-polarity amido linkage and two positive nitrogen ion heads, the novel amido-linkage imidazolium salt gemini surfactant has good biodegradability through introducing nitrogen heterocyclic ring and amido linkage, and the environmentally-friendly gemini surfactant can be used in multiple fields of cleaning, sterilization, restraint of metal corrosion, sewage treatment and the like.
Description
Technical field
The present invention relates to a kind of novel gemini surfactants and preparation method thereof.
Background technology
The appearance of novel amphiphilic molecule, attracted much industry and academic research group to carry out a large amount of scientific researches.The amphipathic molecule of these types is surfactants of Shuangzi or dimerization, and they normally are linked together by a rigidity or flexible spacer by two hydrocarbon chains and two stature bases.These surfactants are compared with traditional single linked list surface-active agent has physicochemical property preferably as: lower critical micelle concentration (cmc), higher dissolubility, wetability and foaminess preferably.
In recent years, many emerging cation Gemini surfactants are synthesized out, as contain the cation Gemini surfactant of the heterocycles such as imidazoles, pyridine, triazine, nafoxidine, six hydrogen piperidines and triazole.Nitrogen-containing heterocycle compound has unique biologically active, and toxicity is low, and interior absorption is high, is often used as medicine and the structure component units of agricultural chemicals, plays an important role aspect synthesizing at medicine and agricultural chemicals.At present, synthetic and the performance study of the Gemini surface active agent of new construction constantly launch, but report mostly is two long linear quaternary ammonium types, the biological degradability of this class surfactant is poor, to environment, can cause adverse effect. along with the enhancing of people's environmental consciousness, synthesizing efficient, eco-friendly novel gemini surfactants have become this field problem demanding prompt solution.
Research shows, the compound that contains ester group or amido link in molecular structure has good biological degradability.To sum up amido link is incorporated in different heterocycle structures, can produces a series of Gemini surface active agents that broad-spectrum biological activity has again biological degradability that namely have by structural modification, but the research of this class surfactant and report are very few.
The patent No. of authorizing in 2008 is ZL200510110586.8, name is called and in the Chinese invention patent of " a kind of Gemini surfactant ", discloses a kind of 4-of take picoline and be raw material, obtains a kind of cation Gemini surfactant that contains pyridine through alkylation, amination, amidatioon connection and salify four-step reaction.This patent has following deficiency: (1), four-step reaction complex operation; (2), alkylated reaction temperature-10～50 ℃, reaction time is 1h～10h, the ammoxidation temperature is 100～180 ℃, and the reaction time is 2h～10h, and the amidation process temperature is 50～180 ℃, reaction time is 10h～60h, the salt-forming reaction temperature is 0～40 ℃, and the reaction time is 0.5h～5h, amination and amidatioon, reaction temperature is high and the reaction time is long, and post processing is loaded down with trivial details; (3) use mesitylene and ether etc. as in reaction or the solvent during post processing, toxicity is larger; (4), the price such as reaction raw materials lithium diisopropyl amido, butyl lithium, sodium hydride, oxalyl chloride, mesitylene, cost is high; (5), compound is to take amido link to be spacer group, but is not to connect with nitrogen ion head, but is connected on the ortho position carbon atom of nitrogen ion head, with nitrogen ion head, do not connect, bactericidal properties is not high.
Summary of the invention
Of the present invention is the problem that complicated operation, cost are high, reaction temperature is high, the reaction time is long, solvent for use toxicity is large existed in the preparation method who solves existing amide bond heterocycle Gemini surface active agent, and provides a kind of novel amido link to connect imidazoles alkali Gemini surface active agent and preparation method thereof.
The general structure of novel amido link connection imidazoles alkali Gemini surface active agent of the present invention is as follows:
R=C wherein
nH
2n+1, n=6,8,10,12,14,16,18.
The method for preparing above-mentioned novel amido link connection imidazoles alkali Gemini surface active agent is carried out according to the following steps:
One, ethylenediamine and 1-brominated alkanes are joined in solvent dimethylformamide, then add NaOH, in room temperature and mixing speed, be under the condition of 800r/pm～1200r/pm, reaction 26h～30h, reacted rear filtration, obtain white solid, with mass fraction, be 50%～70% NaOH solution washing white solid 3～5 times, then with ethanol water, be recrystallized, by crystal, be 0.09MPa～0.1MPa in vacuum, temperature is dry 5h～6h under the condition of 30～35 ℃, obtains N, the N'-Dialkylaminoethylamine; Wherein said and 1-brominated alkanes chemical formula is C
nH
2n+1Br, n=6,8,10,12,14,16,18, described ethylenediamine is 1:(2～3 with the ratio of the amount of substance of 1-brominated alkanes), the volume of described dimethyl formamide is 20mL:(0.02～0.03 with the ratio of amount of substance with the 1-brominated alkanes) mol, the quality of described NaOH is (0.1～0.2) g:0.01mol with the ratio of the amount of substance of ethylenediamine, described ethanol water is mixed by the second alcohol and water, wherein the volume ratio of ethanol and water (4～6): 1;
Two, the N that step 1 is obtained, N'-Dialkylaminoethylamine and triethylamine are dissolved in the reaction vessel that carrene is housed, then reaction vessel is placed in to ice-water bath, low whipping speed is under the condition of 800r/pm～1200r/pm, the constant rate of addition of take is 3mL/min～5mL/min, in reaction vessel, drip chloracetyl chloride, dropwising rear continuation take mixing speed and reacts 4h～6h as 800r/pm～1200r/pm, after finishing, reaction obtains pressed powder except desolventizing, after being washed to 3～5 times with distilled water, the pressed powder obtained is recrystallized at ambient temperature with ethanol, obtain N, N'-(ethane-1, 2-bis-bases) two (N-alkyl-2-chloroacetamides), wherein said N, the N'-Dialkylaminoethylamine is 1:(3～5 with the ratio of the amount of substance of triethylamine), the amount of substance of described triethylamine is 2mmol:(4～6 with the ratio of the volume of carrene) mL, described chloracetyl chloride is 1:(0.5～1.5 with the ratio of the amount of substance of triethylamine),
Three, N step 2 obtained, N'-(ethane-1,2-bis-bases) after two (N-alkyl-2-chloroacetamides), N-methylimidazole and acetonitrile mix, in temperature, be that 50～70 ℃ and supersonic frequency are ultrasonic reaction 6h～8h under the condition of 30KHz～50KHz, except after desolventizing, washing 3～5 times with acetone, then in temperature, be dry 5h～6h under the condition of 50～70 ℃, obtain amido link and connect imidazoles alkali Gemini surface active agent; Wherein said N, N'-(ethane-1,2-bis-bases) two (N-alkyl-2-chloroacetamides) are 1:(3～5 with the ratio of the amount of substance of N-methylimidazole), the amount of substance of described N-methylimidazole is (4～6) mmol:2mL with the ratio of the volume of acetonitrile.
The present invention's design, the synthetic Gemini surface active agent two imidazoles alkali are connected into two amido links, this compounds makes through N-alkylation, amidatioon and quaternized three-step reaction, and preparation method of the present invention has following advantage: (1), three-step reaction are simple to operate, (2), N-alkylated reaction temperature is 30～35 ℃, reaction time is 5h～6h, alkylated reaction temperature-10～50 ℃ than a kind of Gemini surfactant in background technology, reaction time is 1h～10h, the ammoxidation temperature is 100～180 ℃, reaction time is 2h～10h, method reaction condition milder of the present invention, reaction time is shorter, the amidation process temperature is the ice-water bath temperature, reaction time is 4h～6h, than 50～180 ℃ of the amidation process temperature of a kind of Gemini surfactant in background technology, reaction time is 10h～60h, method reaction temperature of the present invention is low, reaction time short 4h～56h, although quaterisation temperature of the present invention is slightly high than the salify temperature of a kind of Gemini surfactant in background technology, time is slightly long, but from reacting whole process, method temperature milder of the present invention, easily reach, and shortened the reaction time, (3), solvent for use toxicity of the present invention is less, (4), the present invention is raw materials used cheap and easy to get, 5), introducing and two nitrogen cation heads of strong polarity amido link make it water-soluble better in its molecular structure of surfactant of the present invention, the introducing of nitrogen heterocyclic ring and amido link simultaneously makes it have good biological degradability, and bactericidal activity is stronger.
The Gemini surface active agent of imidazoles alkali is because containing imidazoles head base simultaneously, so have in stronger self aggregation tendency, reverse micelle to endorse to hold between more solute, heterocycle head base and cosurfactant and have stronger sucking action, and the secondary structure that more easily makes protein destroyed and sex change occurs, therefore can be used as bactericide.Imidazoles alkali in molecule and the activity of long alkyl chain are stronger; molecule more easily forms diaphragm at the steel surface close-packed arrays; thereby make it high and consumption is low to the inhibition efficiency of carbon steel in hydrochloric acid, so this class Gemini surface active agent can be used for suppressing metal erosion.Such surfactant is expected to be widely used in a plurality of fields such as cleaning, sterilization, inhibition metal erosion and sewage disposals in sum.
The accompanying drawing explanation
The N that Fig. 1 obtains for step 1 in test one, the infrared spectrum spectrogram of N'-bis-(dodecyl) ethylenediamine;
The N that Fig. 2 obtains for step 1 in test one, the proton nmr spectra of N'-bis-(dodecyl) ethylenediamine (
1HNMR);
The N that Fig. 3 obtains for step 2 in test one, the infrared spectrum spectrogram of N'-(ethane-1,2-bis-bases) two (N-dodecyl-2-chloroacetamides);
The N that Fig. 4 obtains for step 2 in test one, the proton nmr spectra of N'-(ethane-1,2-bis-bases) two (N-dodecyl-2-chloroacetamides) (
1HNMR);
The amido link that Fig. 5 obtains for step 3 in test one connects the infrared spectrum spectrogram of imidazoles alkali Gemini surface active agent;
Fig. 6 for the amido link that obtains of step 3 in test one connect the proton nmr spectra of imidazoles alkali Gemini surface active agent (
1HNMR).
The specific embodiment
The specific embodiment one: the general structure of the novel amido link connection imidazoles alkali Gemini surface active agent of present embodiment is as follows:
R=C wherein
nH
2n+1, n=6,8,10,12,14,16,18.
The specific embodiment two: the preparation method that the novel amido link of present embodiment connects imidazoles alkali Gemini surface active agent carries out according to the following steps:
One, ethylenediamine and 1-brominated alkanes are joined in solvent dimethylformamide, then add NaOH, in room temperature and mixing speed, be under the condition of 800r/pm～1200r/pm, reaction 26h～30h, reacted rear filtration, obtain white solid, with mass fraction, be 50%～70% NaOH solution washing white solid 3～5 times, then with ethanol water, be recrystallized, by crystal, be 0.09MPa～0.1MPa in vacuum, temperature is dry 5h～6h under the condition of 30～35 ℃, obtains N, the N'-Dialkylaminoethylamine; Wherein said and 1-brominated alkanes chemical formula is C
nH
2n+1Br, n=6,8,10,12,14,16,18, described ethylenediamine is 1:(2～3 with the ratio of the amount of substance of 1-brominated alkanes), the volume of described dimethyl formamide is 20mL:(0.02～0.03 with the ratio of amount of substance with the 1-brominated alkanes) mol, the quality of described NaOH is (0.1～0.2) g:0.01mol with the ratio of the amount of substance of ethylenediamine, described ethanol water is mixed by the second alcohol and water, wherein the volume ratio of ethanol and water (4～6): 1;
Two, the N that step 1 is obtained, N'-Dialkylaminoethylamine and triethylamine are dissolved in the reaction vessel that carrene is housed, then reaction vessel is placed in to ice-water bath, low whipping speed is under the condition of 800r/pm～1200r/pm, the constant rate of addition of take is 3mL/min～5mL/min, in reaction vessel, drip chloracetyl chloride, dropwising rear continuation take mixing speed and reacts 4h～6h as 800r/pm～1200r/pm, course of reaction is monitored with TLC, after finishing, reaction obtains pressed powder except desolventizing, after being washed to 3～5 times with distilled water, the pressed powder obtained is recrystallized at ambient temperature with ethanol, obtain N, N'-(ethane-1, 2-bis-bases) two (N-alkyl-2-chloroacetamides), wherein said N, the N'-Dialkylaminoethylamine is 1:(3～5 with the ratio of the amount of substance of triethylamine), the amount of substance of described triethylamine is 2mmol:(4～6 with the ratio of the volume of carrene) mL, described chloracetyl chloride is 1:(0.5～1.5 with the ratio of the amount of substance of triethylamine),
Three, N step 2 obtained, N'-(ethane-1,2-bis-bases) after two (N-alkyl-2-chloroacetamides), N-methylimidazole and acetonitrile mix, in temperature, be that 50～70 ℃ and supersonic frequency are ultrasonic reaction 6h～8h under the condition of 30KHz～50KHz, except after desolventizing, washing 3～5 times with acetone, then in temperature, be dry 5h～6h under the condition of 50～70 ℃, obtain amido link and connect imidazoles alkali Gemini surface active agent; Wherein said N, N'-(ethane-1,2-bis-bases) two (N-alkyl-2-chloroacetamides) are 1:(3～5 with the ratio of the amount of substance of N-methylimidazole), the amount of substance of described N-methylimidazole is (4～6) mmol:2mL with the ratio of the volume of acetonitrile.
Present embodiment design, the synthetic Gemini surface active agent two imidazoles alkali are connected into two amido links, this compounds makes through N-alkylation, amidatioon and quaternized three-step reaction, and the preparation method of present embodiment has following advantage: (1), three-step reaction are simple to operate, (2), N-alkylated reaction temperature is 30～35 ℃, reaction time is 5h～6h, alkylated reaction temperature-10～50 ℃ than a kind of Gemini surfactant in background technology, reaction time is 1h～10h, the ammoxidation temperature is 100～180 ℃, reaction time is 2h～10h, the method reaction condition milder of present embodiment, reaction time is shorter, the amidation process temperature is the ice-water bath temperature, reaction time is 4h～6h, than 50～180 ℃ of the amidation process temperature of a kind of Gemini surfactant in background technology, reaction time is 10h～60h, method reaction temperature of the present invention is low, reaction time has shortened 4h～56h, although the quaterisation temperature of present embodiment is slightly high than the salify temperature of a kind of Gemini surfactant in background technology, time is slightly long, but from reacting whole process, the method temperature milder of present embodiment, easily reach, and shortened the reaction time, (3), present embodiment solvent for use toxicity is less, (4), present embodiment is raw materials used cheap and easy to get, (5), introducing and two nitrogen cation heads of strong polarity amido link make it water-soluble better in its molecular structure of surfactant of present embodiment, the introducing of nitrogen heterocyclic ring and amido link simultaneously makes it have good biological degradability, and bactericidal activity is stronger.
The Gemini surface active agent of imidazoles alkali is because containing imidazoles head base simultaneously, so have in stronger self aggregation tendency, reverse micelle to endorse to hold between more solute, heterocycle head base and cosurfactant and have stronger sucking action, and the secondary structure that more easily makes protein destroyed and sex change occurs, therefore can be used as bactericide.Imidazoles alkali in molecule and the activity of long alkyl chain are stronger; molecule more easily forms diaphragm at the steel surface close-packed arrays; thereby make it high and consumption is low to the inhibition efficiency of carbon steel in hydrochloric acid, so this class Gemini surface active agent can be used for suppressing metal erosion.Such surfactant is expected to be widely used in a plurality of fields such as cleaning, sterilization, inhibition metal erosion and sewage disposals in sum.
The specific embodiment three: what present embodiment was different from the specific embodiment two is: the ethylenediamine described in step 1 is 1:2.75 with the ratio of the amount of substance of 1-brominated alkanes.Other step and parameter are identical with the specific embodiment two.
The specific embodiment four: what present embodiment was different from the specific embodiment two or three is: the volume of the dimethyl formamide described in step 1 is 20mL:0.0275mol with the ratio of the amount of substance of 1-brominated alkanes.Other step and parameter are identical with the specific embodiment two or three.
The specific embodiment five: the quality of the NaOH described in step 1 is 0.15g:0.01mol with the ratio of the amount of substance of ethylenediamine.Other step and parameter are identical with one of specific embodiment two to four.
The specific embodiment six: what present embodiment was different from one of specific embodiment two to five is: the N described in step 2, the N'-Dialkylaminoethylamine is 1:4 with the ratio of the amount of substance of triethylamine.Other step and parameter are identical with one of specific embodiment two to five.
The specific embodiment seven: what present embodiment was different from one of specific embodiment two to six is: the amount of substance of the triethylamine described in step 2 is 2mmol:5mL with the ratio of the volume of carrene.Other step and parameter are identical with one of specific embodiment two to six.
The specific embodiment eight: what present embodiment was different from one of specific embodiment two to seven is: the chloracetyl chloride described in step 2 is 1:1 with the ratio of the amount of substance of triethylamine.Other step and parameter are identical with one of specific embodiment two to seven.
The specific embodiment nine: what present embodiment was different from one of specific embodiment two to eight is: the N described in step 3, N'-(ethane-1,2-bis-bases) two (N-alkyl-2-chloroacetamides) is 1:4 with the ratio of the amount of substance of N-methylimidazole.Other step and parameter are identical with one of specific embodiment two to eight.
The specific embodiment ten: what present embodiment was different from one of specific embodiment two to nine is: the amount of substance of the N-methylimidazole described in step 3 is 5mmol:2mL with the ratio of the volume of acetonitrile.Other step and parameter are identical with one of specific embodiment two to nine.
With following verification experimental verification beneficial effect of the present invention:
Test one, prepare structural formula and be
One, 0.01mol ethylenediamine and 0.0275mol bromododecane are joined in the 20mL solvent dimethylformamide, then add 0.15gNaOH, in room temperature and mixing speed, be under the condition of 1000rpm, reaction 28h, reacted rear filtration, obtain white solid, with mass fraction, be 60% NaOH solution washing white solid 4 times, then with ethanol water, be recrystallized, by crystal, be 0.1MPa in vacuum, temperature is dry 6h under the condition of 30 ℃, obtains N, N'-bis-(dodecyl) ethylenediamine; Described ethanol water is mixed by the second alcohol and water, wherein the volume ratio 5:1 of ethanol and water;
N in this step, the yield of N'-bis-(dodecyl) ethylenediamine is 66%, mp:44～45 ℃.
Adopt the Nicolet750MagnaR Fourier infrared spectrograph of U.S. Perkin-Elmer, the N this step obtained with pellet technique, N'-bis-(dodecyl) ethylenediamine carries out the infrared spectrum detection, obtains infrared spectrum spectrogram as shown in Figure 1, as can be seen from the figure at 3247cm
-1There is the N-H characteristic absorption peak at place, at 2963,2918,2847cm
-1Place has-CH
3With-CH
2-symmetry and antisymmetry characteristic absorption peak, at 1631cm
-1There is N-H in-plane bending characteristic absorption peak at place, at 1466cm
-1Place has-CH
2-the scissoring vibration absworption peak, at 1133cm
-1There is the characteristic absorption peak of C-N at place, at 723cm
-1There is long-chain-CH at place
2-characteristic absorption peak, confirm to have obtained product N, N'-bis-(dodecyl) ethylenediamine.
Adopt the AV400 NMR of Switzerland Bruker company, make solvent with chloroform, to the N that this step obtains, N'-bis-(dodecyl) ethylenediamine carries out magnetic resonance detection, obtain as shown in Figure 2 proton nmr spectra (
1HNMR), as can be seen from the figure IR (KBr, cm
-1) υ: 3247,2962,2919,2843,1132,723;
1H NMR (400MHz, CDCl
3) δ 2.72 (s, 4H, CH
2), 2.59 (t, 4H, J=7.2Hz, CH
2), 1.61 (s, 2H, NH), 1.47 (m, 4H, CH
2), 1.22 – 1.28 (m, 36H, CH
2), 0.88 (t, 6H, J=6.8Hz, CH
3).Determine that its structural formula is C
12H
25HN (CH
2)
2NHC
12H
25, confirm to have obtained product N, N'-bis-(dodecyl) ethylenediamine.
Two, the N that the 2mmol step 1 is obtained, N'-bis-(dodecyl) ethylenediamine and 8mmol triethylamine are dissolved in the reaction vessel of the carrene that 20mL is housed, then reaction vessel is placed in to ice-water bath, low whipping speed is under the condition of 1000rpm, the constant rate of addition of take is 4mL/min, in reaction vessel, drip the 8mmol chloracetyl chloride, dropwising rear continuation take mixing speed and is 1000rpm reaction 5h, course of reaction is monitored with TLC, after finishing, reaction obtains pressed powder except desolventizing, after being washed to 4 times with distilled water, the pressed powder obtained is recrystallized at ambient temperature with ethanol, obtain N, N'-(ethane-1, 2-bis-bases) two (N-dodecyl-2-chloroacetamides),
N in this step, the yield of N'-(ethane-1,2-bis-bases) two (N-dodecyl-2-chloroacetamides) is 80%, mp:37～38 ℃.
Adopt the Nicolet750MagnaR Fourier infrared spectrograph of U.S. Perkin-Elmer, the N this step obtained with pellet technique, N'-(ethane-1,2-bis-bases) two (N-dodecyl-2-chloroacetamides) carry out the infrared spectrum detection, obtain infrared spectrum spectrogram as shown in Figure 3, as can be seen from the figure at 2918,2843cm
-1Place has-CH
3With-CH
2-symmetry and antisymmetry characteristic absorption peak, at 1641cm
-1There is the C=O characteristic absorption peak at place, at 1466cm
-1Place has-CH
2-the scissoring vibration absworption peak, at 1135cm
-1There is the characteristic absorption peak of C-N at place, at 719cm
-1There is long-chain-CH at place
2-characteristic absorption peak, at 671cm
-1There is the characteristic absorption peak of C-Cl at place, confirms to have obtained product N, N'-(ethane-1,2-bis-bases) two (N-dodecyl-2-chloroacetamides).
Adopt the AV400 NMR of Switzerland Bruker company, with chloroform, make solvent, to the N that this step obtains, N'-(ethane-1,2-bis-bases) two (N-dodecyl-2-chloroacetamides) carry out magnetic resonance detection, obtain as shown in Figure 4 proton nmr spectra (
1HNMR), as can be seen from the figure IR (KBr, cm
-1) υ: 2918,2845,1640,1125,712;
1HNMR (400MHz, CDCl
3) δ 4.07 (s, 4H, CH
2), 3.49 (s, 4H, CH
2), 3.33 (t, 4H, J=8.0Hz, CH
2), 1.60 (m, 4H, CH
2), 1.23 – 1.28 (m, 36H, CH
2), 0.88 (t, 6H, J=6.8Hz, CH
3).Confirm that its structural formula is
Three, the N 1mmol step 2 obtained, N'-(ethane-1,2-bis-bases) after two (N-dodecyl-2-chloroacetamides), 4mmolN-methylimidazole and 10mL acetonitrile mix, in temperature, it is 60 ℃, supersonic frequency is under the condition of 40KHz, and ultrasonic reaction 7h goes out after desolventizing with acetone washing 4 times, then in temperature, be dry 6h under the condition of 60 ℃, obtain amido link and connect imidazoles alkali Gemini surface active agent.
The yield that amido link in this step connects imidazoles alkali Gemini surface active agent is 80%, mp:149～150 ℃.
Adopt the Nicolet750MagnaR Fourier infrared spectrograph of U.S. Perkin-Elmer, with the amido link that pellet technique obtains this step, connect imidazoles alkali Gemini surface active agent and carry out the infrared spectrum detection, obtain infrared spectrum spectrogram as shown in Figure 5, as can be seen from the figure at 3079cm
-1There is C-H characteristic absorption peak on imidazole ring at place, at 2922,2852cm
-1Place has-CH
3With-CH
2-symmetry and antisymmetry characteristic absorption peak, at 1647cm
-1There is the C=O characteristic absorption peak at place, at 1578,1418cm
-1There is the skeletal vibration characteristic peak of imidazole ring at place, at 1470cm
-1Place has-CH
2-the scissoring vibration absworption peak, at 1183cm
-1There is the characteristic absorption peak of C-N at place, at 825cm
-1Place has the imidazoles anchor ring to be out of shape the shock absorbing peak outward, at 629cm
-1Place has-CH
2-characteristic absorption peak, confirm to have obtained the product amido link and connect imidazoles alkali Gemini surface active agent.
Adopt the AV400 NMR of Switzerland Bruker company, make solvent with chloroform, the amido link that this step is obtained connects imidazoles alkali Gemini surface active agent and carries out magnetic resonance detection, obtain as shown in Figure 6 proton nmr spectra (
1HNMR), as can be seen from the figure IR (KBr, cm
-1) υ: 3079,2922,2852,1647,1578,1470,1183,825,629;
1H NMR (400MHz, CDCl
3) δ 9.84 (s, 2H, H of imidazole ring); (7.64 s, 2H, H of imidazole ring); (7.05 s, 2H, H of imidazole ring), 6.61 (s, 4H, CH
2), 3.88 (s, 6H, CH
3), 3.87 (s, 4H, CH
2), 3.31 (t, 4H, J=7.6Hz, CH
2), 2.14 (s, 4H, CH
2), 1.55 (m, 4H, CH
2), 1.25 – 1.28 (m, 36H, CH
2), 0.87 (t, 6H, J=6.8Hz, CH
3).Confirm to have obtained the product amido link and connect imidazoles alkali Gemini surface active agent.Product structure is as follows:
Claims (10)
1. novel amido link connects imidazoles alkali Gemini surface active agent, it is characterized in that the general structure of novel amido link connection imidazoles alkali Gemini surface active agent is as follows:
R=C wherein
nH
2n+1, n=6,8,10,12,14,16,18.
2. prepare the method that novel amido link as claimed in claim 1 connects imidazoles alkali Gemini surface active agent, it is characterized in that the preparation method of novel amido link connection imidazoles alkali Gemini surface active agent carries out according to the following steps:
One, ethylenediamine and 1-brominated alkanes are joined in solvent dimethylformamide, then add NaOH, in room temperature and mixing speed, be under the condition of 800r/pm～1200r/pm, reaction 26h～30h, reacted rear filtration, obtain white solid, with mass fraction, be 50%～70% NaOH solution washing white solid 3～5 times, then with ethanol water, be recrystallized, by crystal, be 0.09MPa～0.1MPa in vacuum, temperature is dry 5h～6h under the condition of 30～35 ℃, obtains N, the N'-Dialkylaminoethylamine; Wherein said and 1-brominated alkanes chemical formula is C
nH
2n+1Br, n=6,8,10,12,14,16,18, described ethylenediamine is 1:(2～3 with the ratio of the amount of substance of 1-brominated alkanes), the volume of described dimethyl formamide is 20mL:(0.02～0.03 with the ratio of amount of substance with the 1-brominated alkanes) mol, the quality of described NaOH is (0.1～0.2) g:0.01mol with the ratio of the amount of substance of ethylenediamine, described ethanol water is mixed by the second alcohol and water, wherein the volume ratio of ethanol and water (4～6): 1;
Two, the N that step 1 is obtained, N'-Dialkylaminoethylamine and triethylamine are dissolved in the reaction vessel that carrene is housed, then reaction vessel is placed in to ice-water bath, low whipping speed is under the condition of 800r/pm～1200r/pm, the constant rate of addition of take is 3mL/min～5mL/min, in reaction vessel, drip chloracetyl chloride, dropwising rear continuation take mixing speed and reacts 4h～6h as 800r/pm～1200r/pm, after finishing, reaction obtains pressed powder except desolventizing, after being washed to 3～5 times with distilled water, the pressed powder obtained is recrystallized at ambient temperature with ethanol, obtain N, N'-(ethane-1, 2-bis-bases) two (N-alkyl-2-chloroacetamides), wherein said N, the N'-Dialkylaminoethylamine is 1:(3～5 with the ratio of the amount of substance of triethylamine), the amount of substance of described triethylamine is 2mmol:(4～6 with the ratio of the volume of carrene) mL, described chloracetyl chloride is 1:(0.5～1.5 with the ratio of the amount of substance of triethylamine),
Three, N step 2 obtained, N'-(ethane-1,2-bis-bases) after two (N-alkyl-2-chloroacetamides), N-methylimidazole and acetonitrile mix, in temperature, be that 50～70 ℃ and supersonic frequency are ultrasonic reaction 6h～8h under the condition of 30KHz～50KHz, except after desolventizing, washing 3～5 times with acetone, then in temperature, be dry 5h～6h under the condition of 50～70 ℃, obtain amido link and connect imidazoles alkali Gemini surface active agent; Wherein said N, N'-(ethane-1,2-bis-bases) two (N-alkyl-2-chloroacetamides) are 1:(3～5 with the ratio of the amount of substance of N-methylimidazole), the amount of substance of described N-methylimidazole is (4～6) mmol:2mL with the ratio of the volume of acetonitrile.
3. novel amido link according to claim 2 connects the preparation method of imidazoles alkali Gemini surface active agent, it is characterized in that the ethylenediamine described in step 1 and the ratio of the amount of substance of 1-brominated alkanes are 1:2.75.
4. according to the described novel amido link of claim 2 or 3, connect the preparation method of imidazoles alkali Gemini surface active agent, it is characterized in that the volume of the dimethyl formamide described in step 1 and the ratio of the amount of substance of 1-brominated alkanes are 20mL:0.0275mol.
5. novel amido link according to claim 4 connects the preparation method of imidazoles alkali Gemini surface active agent, it is characterized in that the quality of the NaOH described in step 1 and the ratio of the amount of substance of ethylenediamine are 0.15g:0.01mol.
6. novel amido link according to claim 4 connects the preparation method of imidazoles alkali Gemini surface active agent, it is characterized in that the N described in step 2, and the N'-Dialkylaminoethylamine is 1:4 with the ratio of the amount of substance of triethylamine.
7. novel amido link according to claim 4 connects the preparation method of imidazoles alkali Gemini surface active agent, it is characterized in that the amount of substance of the triethylamine described in step 2 and the ratio of the volume of carrene are 2mmol:5mL.
8. novel amido link according to claim 4 connects the preparation method of imidazoles alkali Gemini surface active agent, it is characterized in that the chloracetyl chloride described in step 2 and the ratio of the amount of substance of triethylamine are 1:1.
9. novel amido link according to claim 4 connects the preparation method of imidazoles alkali Gemini surface active agent, it is characterized in that the N described in step 3, N'-(ethane-1,2-bis-bases) two (N-alkyl-2-chloroacetamides) is 1:4 with the ratio of the amount of substance of N-methylimidazole.
10. novel amido link according to claim 4 connects the preparation method of imidazoles alkali Gemini surface active agent, it is characterized in that the amount of substance of the N-methylimidazole described in step 3 and the ratio of the volume of acetonitrile are 5mmol:2mL.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951702A (en) * | 2014-05-09 | 2014-07-30 | 齐齐哈尔大学 | 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium compound and preparation method thereof |
| CN104607099A (en) * | 2015-01-16 | 2015-05-13 | 齐齐哈尔大学 | (3, 3'-p-phenylenediamine formoxyl) bis-N-alkyl pyridine bromide surfactant and preparation method thereof |
| CN105693615A (en) * | 2016-04-15 | 2016-06-22 | 南京工业大学 | Synthesizing method of imidazole type Gemini surfactant |
| CN105727828A (en) * | 2016-03-03 | 2016-07-06 | 江南大学 | Cationic gemini surfactants and preparation method thereof |
| CN105820274A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Cationic surface active initiator and preparation method thereof |
| CN105820275A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Gemini type cationic surface active initiator and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815590B (en) * | 2015-05-07 | 2016-08-24 | 齐齐哈尔大学 | A kind of synthetic method of diethyl-three [(1-alkyl-3-carbamoylmethyl) imidazole salts] surfactant |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030027742A1 (en) * | 2001-06-04 | 2003-02-06 | Rhodia, Inc. | Compositions of alkanolamine salts of alkyl phosphate esters |
| CN101279218A (en) * | 2008-01-10 | 2008-10-08 | 西南石油大学 | Novel kation gemini surfactant and process for synthesizing the same |
| CN101607183A (en) * | 2008-06-20 | 2009-12-23 | 中国科学院成都有机化学有限公司 | Carboxylic acid betaine type gemini surfactant and preparation method |
| WO2010041346A1 (en) * | 2008-10-09 | 2010-04-15 | ポリプラスチックス株式会社 | Method for producing modified polyacetal resin having hydroxy group |
| CN101972613A (en) * | 2010-09-25 | 2011-02-16 | 长江大学 | Carboxylate type gemini surfactant and synthesis method thereof |
-
2013
- 2013-08-20 CN CN201310364593.5A patent/CN103406065B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030027742A1 (en) * | 2001-06-04 | 2003-02-06 | Rhodia, Inc. | Compositions of alkanolamine salts of alkyl phosphate esters |
| CN101279218A (en) * | 2008-01-10 | 2008-10-08 | 西南石油大学 | Novel kation gemini surfactant and process for synthesizing the same |
| CN101607183A (en) * | 2008-06-20 | 2009-12-23 | 中国科学院成都有机化学有限公司 | Carboxylic acid betaine type gemini surfactant and preparation method |
| WO2010041346A1 (en) * | 2008-10-09 | 2010-04-15 | ポリプラスチックス株式会社 | Method for producing modified polyacetal resin having hydroxy group |
| CN101972613A (en) * | 2010-09-25 | 2011-02-16 | 长江大学 | Carboxylate type gemini surfactant and synthesis method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MINGQI AO ET AL: "Synthesis and properties of ionic liquid-type Gemini imidazolium surfactants", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 刘国宇等: "离子液体双子咪唑表面活性剂的合成", 《哈尔滨工业大学学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951702A (en) * | 2014-05-09 | 2014-07-30 | 齐齐哈尔大学 | 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium compound and preparation method thereof |
| CN104607099A (en) * | 2015-01-16 | 2015-05-13 | 齐齐哈尔大学 | (3, 3'-p-phenylenediamine formoxyl) bis-N-alkyl pyridine bromide surfactant and preparation method thereof |
| CN104607099B (en) * | 2015-01-16 | 2016-06-29 | 齐齐哈尔大学 | (3,3 '-to diamino-benzene formoxyl) double; two N-alkyl pyridine bromine salt surfactants and preparation method thereof |
| CN105820274A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Cationic surface active initiator and preparation method thereof |
| CN105820275A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Gemini type cationic surface active initiator and preparation method thereof |
| CN105820275B (en) * | 2015-07-08 | 2018-03-30 | 宁波大学 | A kind of double type cation surface activating initiator and preparation method thereof |
| CN105727828A (en) * | 2016-03-03 | 2016-07-06 | 江南大学 | Cationic gemini surfactants and preparation method thereof |
| CN105693615A (en) * | 2016-04-15 | 2016-06-22 | 南京工业大学 | Synthesizing method of imidazole type Gemini surfactant |
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