CN103694262A - Salicylic metal complex containing quaternary ammonium cation and preparation method thereof - Google Patents
Salicylic metal complex containing quaternary ammonium cation and preparation method thereof Download PDFInfo
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Abstract
The invention provides a salicylic metal complex containing quaternary ammonium cation in a molecular structure, which aims at (1) improving water solubility of salicylic metal complex by virtue of water solubility and surface activity feature of quaternary ammonium salt, and facilitating blending and application of the salicylic metal complex as a bioactivity reagent; (2) by virtue of positive charge characteristics of quaternary ammonium salt, promoting the salicylic metal complex to contact bacteria, fungi or cells and effect quickly; (3) producing cooperative and efficient bioactivity and effects by virtue of bioactivities of quaternary ammonium salt and salicylic metal complex, such as double bactericidal activity, anti-microbial activity and bacteriostatic activity.
Description
Technical field
The present invention relates to a kind of salicylic acid metal title complex, particularly in molecular structure, contain the Whitfield's ointment of quaternary ammonium cation and the title complex of transition metal or rare earth metal, belong to Field of Fine Chemicals.
Technical background
Whitfield's ointment easily and transition metal ion or rare earth ion form stable title complex, the title complex that studies confirm that in a large number Whitfield's ointment and transition metal ion or rare earth ion has multifarious biological effect, if any good anti-inflammatory, antibacterial, sterilization, anticancer, anticoagulation, analgesic activity.And the more former part of transition metal or rare earth compounding has effect in various degree to improve, and the poison effect of paying decreases.In addition, Whitfield's ointment and derivative thereof also have the multiple pharmacological effect such as sterilization, anti-inflammatory, Antipyretic, are used as for a long time clinical medicine to be widely used always; Secondly Whitfield's ointment and transition metal ion or rare earth compounding have represented application prospect widely in the new science and technology groups such as information, novel material, new forms of energy, space and ocean.But the insoluble feature of not melting of Whitfield's ointment transition metal ion or rare earth compounding, causes its processing to use very inconvenience.
Quaternary ammonium salt is the easy organic compound of the synthetic production of a class, because it has the good characteristics such as solvable meltable, low toxicity are non-stimulated, with low cost, sterilizing has a broad antifungal spectrum, be conventional sterilizing agent, disinfectant and the antiseptic-germicides in field such as agricultural, public health, clinical medicine, Biochemical Research.At present, develop into five generation-gemini quaternary ammonium salt of the antibacterial research of small molecules quaternary ammonium salt antiseptic-germicide.The invention of gemini quaternary ammonium salt antiseptic-germicide, has improved antimicrobial efficiency greatly, opens the new page of antiseptic-germicide, but in the face of the medicine resistance ability after the quick variation of bacteriotoxin, the antibacterial sterilization predicament of gemini quaternary ammonium salt is still heavy.So far, people have studied quaternary ammonium salt polymer antibacterial agent, have higher electric density, antibacterial ability is stronger, and chemical stability is high, and residual toxicity is low, the features such as easy processing, become the new lover of high-molecular anti-bacteria Material Field, but still have awkward defect in numerous areas.
Summary of the invention
For existing salicylic acid metal title complex or quaternary ammonium salt antiseptic, cannot meet defect and the deficiency of various application scenarios demand, the present invention by chemical bond by quaternary ammonium salt together with salicylic acid metal complex-bound, give full play to advantage separately, produce synergistic effect, thereby possess higher biological activity and more complete effect.For this reason, the invention provides the compound that contains quaternary ammonium cation and two kinds of function bases of salicylic acid metal title complex in a kind of molecular structure, its effect of having a mind to is 1. by the water-soluble and surfactivity of quaternary ammonium cation, to improve the water-soluble of salicylic acid metal title complex, facilitates salicylic acid metal title complex as allotment and the use of biologically active agent; 2. by the positive charge characteristic of quaternary ammonium cation, promote salicylic acid metal title complex and electronegative bacterium, fungi or cells contacting, quick acting; 3. by biological activitys such as the double sterilization of quaternary ammonium cation and salicylic acid metal title complex, antibacterial and bacteriostatic activities, thereby produce collaborative efficient biological activity effect.
The invention provides a kind of salicylic acid metal title complex that contains quaternary ammonium cation, there is chemical structure shown in general formula (I):
M in its formula of (I)
n+refer to a kind of in transition metal ion or rare earth ion; R
1, R
2and R
3choose respectively C
1～C
20alkyl; X
-be selected from F
-, Cl
-, Br
-, NO
3 -, HSO
4 -, H
2pO
4 -or CH
3cOO
-in a kind of; N is selected from a kind of in 1,2,3 or 4, and m chooses the natural number in 0～10;
Prepare the salicylic acid metal title complex that contains quaternary ammonium cation in the described molecular structure of general formula (I), the following step of process:
Step 1: take general formula (II) tertiary amine and 5-chloromethyl salicylaldehyde is raw material, by nucleophilic substitution reaction, makes the salicylic aldehyde that quaternary ammonium cation replaces, and sees that reaction formula is 1.:
The R of reaction formula in 1. wherein
1, R
2and R
3choose respectively C
1～C
20alkyl; Reaction formula 1. described solvent can be selected aprotic polar solvent, as acetone, butanone, chloroform, 1,4-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, ethyl acetate, methyl acetate, butylacetate, also can select aproticapolar solvent, as 1,2-ethylene dichloride, tetracol phenixin, toluene, dimethylbenzene, methyl-phenoxide, chlorobenzene, methylcyclohexane, also can select the mixture of described aprotic polar solvent and aproticapolar solvent.The solvent object of choosing carefully is to guarantee that mutual-through type (II) and 5-chloromethyl salicylaldehyde all have high solubleness in solvent, and in solvent, there is low solubleness for general formula (III) quaternary ammonium cation substituted salicylic aldehydes, so be conducive to improve reaction efficiency, by simple filtration technology, can make highly purified general formula (III).
Reaction formula 1. described 5-chloromethyl salicylaldehyde mole dosage phase mutual-through type (II) is excessive, and object is in order to prevent the dehydrochlorination polymerization side reactions of himself, especially excessive at tertiary amine and the too high situation of temperature of reaction.Under suitable reaction conditions, the nucleophilic substitution reaction between described general formula (II) tertiary amine and 5-chloromethyl salicylaldehyde is clearly, and quaternary ammonium salinization reaction efficiency is high.A consumption mole proportioning for general formula (II) and 5-chloromethyl salicylaldehyde is controlled at 1: 1～and 1.5, optimal control is 1: 1.05～1.1.
Step 2: in the salicylic aldehyde water soluble that the general formula that step 1 makes (III) quaternary ammonium cation replaces, Glacial acetic acid, ethanol, methyl alcohol, ethylene glycol solvent, use oxygenant general formula (III) quaternary ammonium cation substituted salicylic aldehydes to be converted into the Whitfield's ointment that contains quaternary ammonium cation of structure shown in general formula (IV), see that reaction formula is 2.:
Wherein said oxygenant is selected from a kind of in clorox, sodium dichromate 99, potassium bichromate, potassium permanganate or sodium permanganate, the R of reaction formula in 2.
1, R
2and R
3choose respectively C
1～C
20alkyl; The consumption mol ratio of described general formula (III) quaternary ammonium-substituted salicylic aldehyde and oxygenant is controlled at 1: 0.5～and 1: 1.1.
2. it is general formula (IV) inner salt that the general formula making according to reaction formula (IV) very easily loses hydrogenchloride molecular conversion, that is to say general formula (IV) amphoteric substance, for the preparation of next step lays the foundation and facilitates condition.
Step 3: chelatropic reaction occurs in the aqueous solution for general formula (IV) and transition metal salt or rare earth metal salt, generates the salicylic acid metal title complex that contains quaternary ammonium cation in the molecular structure of structure as shown in general formula (I), sees that reaction formula is 3.:
Wherein said transition metal salt or rare-earth salts refer to a kind of in fluorochemical, hydrochloride, bromide, nitrate, hydrosulfate, dihydrogen phosphate or the acetate of transition metal or rare earth metal;
The R of described reaction formula in 3.
1, R
2and R
3choose respectively C
1～C
20alkyl MX
nrefer to transition metal salt or rare-earth salts, M
n+refer to a kind of in transition metal ion or rare earth ion, X
-be selected from F
-, Cl
-, Br
-, NO
3 -, HSO
4 -, H
2pO
4 -or CH
3cOO
-in a kind of; N is selected from a kind of in 1,2,3 or 4, and m chooses the natural number in 0～10;
The mole dosage ratio of described general formula (VI) and transition metal salt or rare earth metal salt is 2～4: 1.
The concrete preparation method of the salicylic acid metal title complex that general formula provided by the invention (I) contains quaternary ammonium cation comprises the steps:
The preparation of step 1 general formula (III)
Take general formula (II) tertiary amine and 5-chloromethyl salicylaldehyde and be dissolved in respectively in solvent, make described general formula (II) ertiary amine solution and 5-chloromethyl salicylaldehyde solution.Under room temperature, 5-chloromethyl salicylaldehyde solution is added in general formula (II) ertiary amine solution, after stirring reaction 2～6 hours, heat up 60～85 ℃, continue stirring reaction 2～6 hours, reaction mass temperature is down to room temperature, filter, be dried, make the salicylic aldehyde that contains quaternary ammonium cation of structure shown in general formula (III), see that reaction formula is 1.:
The R of reaction formula 1. and in general formula (II) wherein
1, R
2and R
3choose respectively C
1～C
20alkyl; Described solvent is selected from acetone, butanone, chloroform, 1,2-ethylene dichloride, one or more in tetracol phenixin, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene, methyl-phenoxide, chlorobenzene, ethyl acetate, methyl acetate, butylacetate or methylcyclohexane; The mass ratio of described general formula (II) tertiary amine/5-chloromethyl salicylaldehyde/solvent is 1: 0.2～2.5: 2～20;
The preparation of step 2 general formula (IV)
Taking the general formula (III) that step 1 makes is dissolved in water, temperature control-10～25 ℃, stir the aqueous oxidizing agent solution that lower dropping mass percentage concentration is 5～10%, react after 6～20 hours, make the aqueous solution of salicylic acid that general formula (VI) contains quaternary ammonium cation, see that reaction formula is 2.:
Wherein said oxygenant is selected from a kind of in clorox, sodium dichromate 99, potassium bichromate, potassium permanganate or sodium permanganate, the R of reaction formula in 2.
1, R
2and R
3choose respectively C
1～C
20alkyl; The consumption mol ratio of described general formula (III) quaternary ammonium cation substituted salicylic aldehydes and oxygenant is controlled at 1: 0.5～and 1: 1.1;
The preparation of step 3 general formula (I)
Described general formula (VI) aqueous solution pH=6 that regulating step two makes, the transition metal salt that is 5～10% by mass percentage concentration again or rare earth salt aqueous solution add in the aqueous solution of described general formula (VI), heat up 60～85 ℃, react after 6～20 hours, concentrated, separate out the precipitation of general formula (I), filter, dry, make the salicylic acid metal title complex that contains quaternary ammonium cation in the molecular structure of structure shown in general formula (I), see that reaction formula is 3.:
Wherein said transition metal salt or rare-earth salts refer to a kind of in fluorochemical, hydrochloride, bromide, nitrate, hydrosulfate, dihydrogen phosphate or the acetate of transition metal or rare earth metal;
The M of described reaction formula in 3.
n+refer to a kind of in transition metal ion or rare earth ion, X
-be selected from F
-, Cl
-, Br
-, NO
3 -, HSO
4 -, H
2pO
4 -or CH
3cOO
-in a kind of; N is selected from a kind of in 1,2,3 or 4, and m chooses the natural number in 0～10;
Described R
1, R
2and R
3choose respectively C
1～C
20alkyl;
Described general formula (VI) and transition metal salt or rare-earth salts mole dosage ratio are 2～4: 1.
Specific embodiment
By embodiment below, salicylic acid metal title complex and the preparation method who contains quaternary ammonium cation provided by the invention further illustrated, its object is to understand better content of the present invention.Therefore salicylic acid metal title complex that, contains quaternary ammonium cation in unlisted molecular structure in embodiment and preparation method thereof should not be considered as limiting the scope of the invention.Anyly for improvement of the present invention, all belong to intellecture property aggressive behavior.
Embodiment 1Zn (QAS-HSal)
3-1 preparation
The preparation of step 1, QAS-Sa-1
Take N, 20 grams of 13 grams of N-dimethyl benzylamines and 5-chloromethyl salicylaldehydes are dissolved in respectively in 50 grams of ethyl acetate, make described N, the ethyl acetate solution of the ethyl acetate solution of N-dimethyl benzylamine and 5-chloromethyl salicylaldehyde, under room temperature, adds N by the ethyl acetate solution of 5-chloromethyl salicylaldehyde, in the ethyl acetate solution of N-dimethyl benzylamine, after stirring reaction 4 hours, heat up 60～65 ℃, continue stirring reaction 6 hours.Reaction system is standing, naturally cools to room temperature, filters and obtains cream-coloured crystalline material, through recrystallization with after being dried, makes 29.8 grams of QAS-Sa-1, yield 96.8%, 162～163 ℃ of fusing points.
The preparation of step 2, QAS-Sal-1
29.8 grams of QAS-Sa-1 that step 1 is made are dissolved in 100 ml waters, 0～5 ℃ of temperature control, 17 grams of the aqueous sodium hypochlorite solutions that under stirring, dropping mass percentage concentration is 4.6%, react after 6 hours, regulate pH=6, make the aqueous solution of QAS-SA-1, without separation, standby.
Step 3, Zn (QAS-HSal)
2-1 preparation
Take 17 gram of six hydration zinc chloride and be dissolved in 50 ml waters, stir after lower dissolving, filter and remove solid matter, gained filtrate joins in the aqueous solution of the QAS-Sal-1 that step 1 makes, 60～65 ℃ of temperature controls, and stirring reaction is after half an hour, add 3.8 grams of triethylamines, continue 60～65 ℃ of stirring reactions of temperature control 2 hours, after concentrating, reaction system is cooled to-5～0 ℃, crystallization, filter, dry, make 37.3 grams of white powder Zn (QAS-HSal)
2-1, through ultimate analysis, confirming as molecular formula is C
34h
40cl
2znN
2o
9, with described Zn (QAS-HSal)
2-1 structural formula matches.
Embodiment 2Cr (QAS-HSal)
3-1 preparation
According to method and the operation steps of embodiment 1, the zinc chloride of embodiment 1 step 3 is changed as chromium chloride, make puce Cr (QAS-HSal)
3-1, through ultimate analysis, confirm as the Whitfield's ointment chromic compound that contains quaternary ammonium cation of six hydrations.
Embodiment 3La (QAS-HSal)
2-1 preparation
According to method and the operation steps of embodiment 1, the zinc chloride of embodiment 1 step 3 kind is changed as Lanthanum trichloride, make the La (QAS-HSal) of white powder
3-1, through ultimate analysis, confirming as molecular formula is C
51h
61cl
3laN
3o
11, with described La (QAS-HSal)
3-1 structural formula matches.
Embodiment 4Sm (QAS-HSal)
3-1 preparation
According to method and the operation steps of embodiment 1, by the N of embodiment 1 step 1, N-dimethyl benzylamine changes as N, N-dimethyl dodecyl tertiary amine, and it is six hydration samarium trichlorides that the zinc chloride of step 3 changes, and makes faint yellow Sm (QAS-HSal)
3-1, through ultimate analysis, confirm as the Whitfield's ointment samarium complex of dihydrated quaternary ammonium-substituted.
Embodiment 5Ce (QAS-HSal)
3-1 preparation
According to method and the operation steps of embodiment 1, by the N of embodiment 1 step 1, N-dimethyl benzylamine changes as N, N-dimethyl dodecyl tertiary amine, and the zinc chloride of step 3 changes as Cerous chloride heptahydrate, makes light green Ce (QAS-HSal)
3-1, through ultimate analysis, confirm as the Whitfield's ointment cerium complexes that contains quaternary ammonium cation of three hydrations.
The characteristic that embodiment 6 contains quaternary ammonium cation salicylic acid metal title complex
What table 1 had been listed embodiment 1～embodiment 5 contains the solvability of quaternary ammonium cation salicylic acid metal title complex in water, methyl alcohol, ethanol, chloroform solvent:
The character of the salicylic acid metal title complex that table 1. embodiment 1～5 contains quaternary ammonium cation
In table 1, v represents solublely, and s represents dissolving, and i represents micro dissolution, and u does not dissolve.
Claims (2)
1. a salicylic acid metal title complex that contains quaternary ammonium cation, has chemical structure shown in general formula (I):
M in its formula of (I)
n+refer to a kind of in transition metal ion or rare earth ion; R
1, R
2and R
3choose respectively C
1～C
20alkyl; X
-be selected from F
-, Cl
-, Br
-, I
-, NO
3 -, HSO
4 -, H
2pO
4 -or CH
3cOO
-in a kind of; N is selected from a kind of in 1,2,3 or 4, and m chooses the natural number in 0～10.
2. according to the preparation method of the salicylic acid metal title complex that contains quaternary ammonium cation claimed in claim 1, it is characterized in that step as described below:
The preparation of step 1 general formula (III)
Taking general formula (II) tertiary amine and 5-chloromethyl salicylaldehyde is dissolved in respectively in solvent, make described general formula (II) ertiary amine solution and 5-chloromethyl salicylaldehyde solution, under room temperature, 5-chloromethyl salicylaldehyde solution is added in general formula (II) ertiary amine solution, after stirring reaction 2～6 hours, heat up 60～85 ℃, continue stirring reaction 2～6 hours, reaction mass temperature is down to room temperature, filter, be dried, make the salicylic aldehyde that contains quaternary ammonium cation of structure shown in general formula (III), see that reaction formula is 1.:
The R of reaction formula 1. and in general formula (II) wherein
1, R
2and R
3choose respectively C
1～C
20alkyl; Described solvent is selected from acetone, butanone, chloroform, 1,2-ethylene dichloride, one or more in tetracol phenixin, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene, methyl-phenoxide, chlorobenzene, ethyl acetate, methyl acetate, butylacetate or methylcyclohexane; The mass ratio of described general formula (II) tertiary amine/5-chloromethyl salicylaldehyde/solvent is 1: 0.2～2.5: 2～20;
The preparation of step 2 general formula (IV)
Taking the general formula (III) that step 1 makes is dissolved in water, temperature control-10～25 ℃, stir the aqueous oxidizing agent solution that lower dropping mass percentage concentration is 5～10%, react after 6～20 hours, make the aqueous solution of salicylic acid that general formula (VI) quaternary ammonium cation replaces, see that reaction formula is 2.:
Wherein said oxygenant is selected from a kind of in clorox, sodium dichromate 99, potassium bichromate, potassium permanganate or sodium permanganate, the R of reaction formula in 2.
1, R
2and R
3choose respectively C
1～C
20alkyl; The consumption mol ratio of described general formula (III) quaternary ammonium cation substituted salicylic aldehydes and oxygenant is controlled at 1: 0.5～and 1: 1.1;
The preparation of step 3 general formula (I)
Described general formula (VI) aqueous solution pH=6 that regulating step two makes, the transition metal salt that is 5～10% by mass percentage concentration again or rare earth salt aqueous solution add in the aqueous solution of described general formula (VI), heat up 60～85 ℃, react after 6～20 hours, concentrated, separate out the precipitation of general formula (I), filter, dry, make the salicylic acid metal title complex that contains quaternary ammonium cation in the molecular structure of structure shown in general formula (I), see that reaction formula is 3.:
Wherein said transition metal salt or rare-earth salts refer to a kind of in fluorochemical, hydrochloride, bromide, nitrate, hydrosulfate, dihydrogen phosphate or the acetate of transition metal or rare earth metal;
The M of described reaction formula in 3.
n+refer to a kind of in transition metal ion or rare earth ion, X
-be selected from F
-, Cl
-, Br
-, NO
3 -, HSO
4 -, H
2pO
4 -or CH
3cOO
-in a kind of n be selected from a kind of in 1,2,3 or 4, m chooses the natural number in 0～10;
Described R
1, R
2and R
3choose respectively C
1～C
20alkyl;
Described general formula (VI) and transition metal salt or rare-earth salts mole dosage ratio are 2～4: 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086581A (en) * | 2014-07-02 | 2014-10-08 | 淮海工学院 | Organic silicon functional monomer containing quaternary ammonium cations and salicylaldehyde |
| JP2017043559A (en) * | 2015-08-27 | 2017-03-02 | 住化エンバイロメンタルサイエンス株式会社 | Antibacterial agent composition |
| CN109232269A (en) * | 2018-10-31 | 2019-01-18 | 江西肯特化学有限公司 | A kind of method of one step Bei Benzyl base front three ammonium chloride of semidry process |
| CN111303440A (en) * | 2020-02-17 | 2020-06-19 | 忻州师范学院 | Aliphatic tertiary amine functional zirconium-based metal organic framework material and preparation method thereof |
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| CN102766150A (en) * | 2012-07-10 | 2012-11-07 | 淮海工学院 | Polymerizable salicylic aldehyde complex containing quaternary ammonium salt and preparation method thereof |
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2013
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| CN102766150A (en) * | 2012-07-10 | 2012-11-07 | 淮海工学院 | Polymerizable salicylic aldehyde complex containing quaternary ammonium salt and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086581A (en) * | 2014-07-02 | 2014-10-08 | 淮海工学院 | Organic silicon functional monomer containing quaternary ammonium cations and salicylaldehyde |
| JP2017043559A (en) * | 2015-08-27 | 2017-03-02 | 住化エンバイロメンタルサイエンス株式会社 | Antibacterial agent composition |
| CN109232269A (en) * | 2018-10-31 | 2019-01-18 | 江西肯特化学有限公司 | A kind of method of one step Bei Benzyl base front three ammonium chloride of semidry process |
| CN111303440A (en) * | 2020-02-17 | 2020-06-19 | 忻州师范学院 | Aliphatic tertiary amine functional zirconium-based metal organic framework material and preparation method thereof |
| CN111303440B (en) * | 2020-02-17 | 2021-11-19 | 忻州师范学院 | Aliphatic tertiary amine functional zirconium-based metal organic framework material and preparation method thereof |
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Application publication date: 20140402 |