CN106316826B - The preparation method of 4,4 '-dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agents - Google Patents
The preparation method of 4,4 '-dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agents Download PDFInfo
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- C07C51/41—Preparation of salts of carboxylic acids
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Abstract
A kind of preparation method of 4,4 ' dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agents, includes the following steps：(1) by H2OBA (4,4 ' dicarboxydiphenyl ether) is dissolved in the in the mixed solvent of DMF and water, and rare earth nitrades Re (NO are added3)3, wherein one kind in tetra- kinds of Re La, Ce, Sm, Er rare earth elements, H2OBA and Re (NO3)3Molar ratio be 1: (1.3~2.2)；(2) 10~30min is stirred at room temperature after it becomes five colors clarification from cotton-shaped suspension in the solution of step (1), be fitted into the reaction kettle of polytetrafluoroethyllining lining, in 120 ± 1 DEG C of 70~72h of constant temperature；(3) 10~12h is kept the temperature when the reactant after constant temperature being down to 100 ± 2 DEG C, room temperature is then down to the rate of 6 DEG C/h, obtains [Re2(OBA)3(H2O)5]·H2O.Synthetic method of the present invention is simple, and generated time is short, and yield is high, and the generated time of the rare earth complex compoud currently used for bacteriostatic agent is shortened half.
Description
Technical field：
The present invention relates to the synthesis technical fields of carboxylic acids rare earth complex compoud, specifically, being related to one kind 4,4 '-two
The preparation method of carboxyl diphenyl ether rare earth complex compoud bacteriostatic agent.
Background technology：
In recent years, with the research to rare earth compound, unique property make its high-technology field demand not
Disconnected increase.Luminous, fluorescence and catalytic field are concentrated mainly on to the research of rare earth material at present, consumption market is mainly concentrated
In U.S., day, Europe, it is related to including the production of the technologies such as cleaning catalyst for tail gases of automobiles, petroleum refining catalyst, permanent-magnet material, fluorescent powder
Industry.Such as：Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences application No. is 201410122975.1 patents to disclose a kind of use
Make the preparation method of the lactic acid rare earth compounding of catalyst；Shanghai Silicate Inst., Chinese Academy of Sciences application No. is
200910050880.2 patent disclose a kind of preparation method of the rare earth compounding as luminescent material.
The advantages that rare earth compounding bacteriostatic agent has sterilizing ability strong, and antimicrobial spectrum is wide, and solution acidic is close to physiological pH, because
This, more and more scholar are dedicated to the research of rare earth drugs both at home and abroad, and achieve gratifying achievement.Comprehensive literature report,
Rare earth compounding with bacteriostasis, ligand majority are containing carboxyl, hydroxyl or sulfonic aromatic compound.Rare earth
Have efficient, stable the advantages of aromatic carboxylic acids class complex integrates inorganic rare earth metal ion and organic carboxylic acid compounds
Bacteriostatic activity, have important application in the fields such as chemistry, biology, pharmacy.
Currently, the reaction time needed for the synthetic method of such complex is long.Such as：Strong equal (CrystEngComm,
2013,15,315) under conditions of ethylidene-urea hemihydrate is added, rare earth compounding [Tm is obtained within 5 days in 140 DEG C of reactions2
(oba)3(H2O)5]·H2O, yield 79%；Luo Yun etc. (CrystEngComm, 2013,15,706) utilizes solvent evaporation method,
Serial rare-earth complex [Ln is obtained after reaction a few weeks longer2(oba)3(H2O)5]·H2O, yield 81%.
Based on this, under conditions of ensureing yield, improving the aggregate velocity of hexichol class rare earth complex compoud becomes at present
One research direction.
Invention content：
In view of the foregoing, it is necessary to it is dilute to invent 4, the 4 '-dicarboxydiphenyl ethers that a kind of yield is high and generated time is short
The preparation method of native complex bacteriostatic agent.
A kind of preparation method of 4,4 '-dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agents, includes the following steps：
(1) by H2OBA (4,4 '-dicarboxydiphenyl ether) is dissolved in the in the mixed solvent of DMF and water, and rare earth nitrades are added
Re(NO3)3, wherein one kind in tetra- kinds of Re La, Ce, Sm, Er rare earth elements, H2OBA and Re (NO3)3Molar ratio be 1:
(1.3~2.2)；
(2) 10~30min is stirred at room temperature when it is become colorless clarification by cotton-shaped suspension in the solution of step (1)
Afterwards, it is fitted into the reaction kettle of polytetrafluoroethyllining lining, in 120 ± 1 DEG C of 70~72h of constant temperature；
(3) 10~12h is kept the temperature when the reactant after constant temperature being down to 100 ± 2 DEG C, room is then down to the rate of 6 DEG C/h
Temperature obtains target product [Re2(OBA)3(H2O)5]·H2O。
Preferably, the molar ratio of in the mixed solvent water and DMF are 1: (2~3.5).
Preferably, H2OBA and Re (NO3)3Molar ratio be 1: 1.8.
Preferably, mixing time 15min.
Preferably, step (2) thermostat temperature is 120 DEG C.
Preferably, the molar ratio of water and DMF are 1: 3.
Preferably, the solution being fitted into step (2) in reaction kettle is 15mL.
The present invention has the beneficial effect that：
Synthetic method is simple, and generated time is short, and yield is high, by the synthesis currently used for the rare earth complex compoud of bacteriostatic agent
Time shortens half.
Description of the drawings：
Attached drawing 1 is the crystal structure figure of 4,4 '-dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agents.
Attached drawing 2 is the powder x-ray diffraction figure of 4,4 '-dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agents.
Attached drawing 3 is suppression curve figure of the various concentration complex to micrococcus luteus growth rate constant.
Specific implementation mode：
4,4 '-dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agents, molecular formula Re2C42O21H36, (Re=La,
Ce, Sm, Er), chemical formula [Re2(OBA)3(H2O)5]·H2O, crystal structure figure are as shown in Figure 1.
A kind of yield is high and the preparation of 4,4 '-short dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agents of generated time
Method：
Embodiment 1
(1) by 12.9mg (0.05mmol) H2OBA (4,4 '-dicarboxydiphenyl ether)It is molten
In the in the mixed solvent of 12mL DMF and water, 30.24mg (0.09mmol) Sm (NO are added3)3；
(2) 10~30min is stirred at room temperature when it is become colorless clarification by cotton-shaped suspension in the solution of step (1)
Afterwards, it is fitted into the reaction kettle of 15mL polytetrafluoroethyllining linings, in 120 DEG C of constant temperature 72h；
(3) 11h is kept the temperature when the reactant after constant temperature being down to 100 DEG C, and room temperature is then down to the rate of 6 DEG C/h, is obtained
Target product, yield 92%, (in addition curve (1), (2), (4) correspond to the curve (3) that powder diagram is shown in attached drawing 2 respectively
The complex of three kinds of rare earth elements), it is [Sm that can obtain the compound by figure2(OBA)3(H2O)5]·H2O。
Embodiment 2
It is similar to Example 1, unlike：Take H2OBA 12.9mg (0.05mmol), Sm (NO3)321.84mg
(0.065mmol), H2OBA and Sm (NO3)3Molar ratio be 1: 1.3, solvent-thermal method obtains target compound, yield 61%.
Embodiment 3
It is similar to Example 1, unlike：Take H2OBA 12.9mg (0.05mmol), Sm (NO3) 336.96mg
The molar ratio of (0.11mmol), H2OBA and Sm (NO3) 3 are 1: 2.2, and solvent-thermal method obtains target compound, yield 79%.
Embodiment 4
It is similar to Example 1, unlike：The molar ratio of water and DMF are 1: 2, and solvent-thermal method obtains target compound, production
Rate 71%.
Embodiment 5
It is similar to Example 1, unlike：The molar ratio of water and DMF are 1: 3.5, and solvent-thermal method obtains target compound,
Yield 83%.
Embodiment 6
It is similar to Example 1, unlike：Stirring 10 minutes, solvent-thermal method obtains target compound, yield 80%.
Embodiment 7
It is similar to Example 1, unlike：Stirring 30 minutes, solvent-thermal method obtains target compound, yield 86%.
Claims (3)
1. the preparation method of 4,4 '-dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agent of one kind, which is characterized in that including with
Lower step：
(1) by H2OBA is dissolved in the in the mixed solvent of DMF and water, and rare earth nitrades Re (NO are added3)3, wherein Re La, Ce,
One kind in tetra- kinds of rare earth elements of Sm, Er, H2OBA and Re (NO3)3Molar ratio be 1: 1.8, the in the mixed solvent water and DMF
Molar ratio be 1: 3；
(2) 15min is stirred at room temperature after it becomes colorless clarification by cotton-shaped suspension in the solution of step (1), be packed into poly-
In the reaction kettle of tetrafluoroethene liner, in 120 ± 1 DEG C of 70~72h of constant temperature；
(3) 10~12h is kept the temperature when the reactant after constant temperature being down to 100 ± 2 DEG C, room temperature is then down to the rate of 6 DEG C/h, is obtained
To target product [Re2(OBA)3(H2O)5]·H2O。
2. the preparation method of as described in claim 14,4 '-dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agents, special
Sign is：Step (2) thermostat temperature is 120 DEG C.
3. the preparation method of as described in claim 14,4 '-dicarboxydiphenyl ether rare earth complex compoud bacteriostatic agents, special
Sign is：The solution being fitted into step (2) in reaction kettle is 15mL.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617620A (en) * | 2012-03-07 | 2012-08-01 | 上海师范大学 | Heterocyclic ligand-containing efficiently-antibacterial rare earth ternary complexes, and preparation method and application thereof |
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- 2016-07-08 CN CN201610559928.2A patent/CN106316826B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617620A (en) * | 2012-03-07 | 2012-08-01 | 上海师范大学 | Heterocyclic ligand-containing efficiently-antibacterial rare earth ternary complexes, and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Structural diversity of luminescent lanthanide metal–organic frameworks based on a V-shaped ligand;Yan-Fei He等;《CrystEngComm》;20151231;第17卷;第2471-2478页 * |
| Synthesis, crystal structure and luminescent properties of new lanthanide-containing coordination polymers involving 4,49-oxy-bis-benzoate as ligand;Yun Luo等;《CrystEngComm》;20131231;第706-720页 * |
| Urothermal synthesis of photoluminescent lanthanide–organic frameworks with unusual topologies;Zhi-Qiang Jiang等;《CrystEngComm》;20131231;第15卷;第315-323页 * |
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