CN101891679A - Preparation method of pyridinedicarboxylic acid and diaminopyridine proton transfer compound - Google Patents

Preparation method of pyridinedicarboxylic acid and diaminopyridine proton transfer compound Download PDF

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CN101891679A
CN101891679A CN2009100515399A CN200910051539A CN101891679A CN 101891679 A CN101891679 A CN 101891679A CN 2009100515399 A CN2009100515399 A CN 2009100515399A CN 200910051539 A CN200910051539 A CN 200910051539A CN 101891679 A CN101891679 A CN 101891679A
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pyridine
diamino
preparation
dioctyl phthalate
diaminopyridine
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CN101891679B (en
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蔡梦军
陈建定
杨景辉
吴秋芳
马新胜
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Shanghai Huaming Hi Tech Group Co Ltd
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Abstract

The invention provides a preparation method of a pyridinedicarboxylic acid and diaminopyridine proton transfer compound, which comprises the following steps of: by using pyridine-2,6-dicarboxylic acid and 2,6-diaminopyridine as raw materials, carrying out reaction in water or an organic solvent under the action of ultrasonic waves, and then collecting a pyridine-2,6-dicarboxylic acid and 2,6-diaminopyridine proton transfer compound [pyda.H2]2+[pydc]2-. The method has less time consumption, short synthetic route, simple process, high purity and low cost; in addition, the preparation method not only breaks through the limitation of reactant raw materials for smaller concentration ranges, but also can select grain alcohol and the like with smaller toxicity as the organic solvent and avoids the environmental pollution of other organic solvents, so that the invention has remarkable economic benefit and social benefit; and the yield of a product is higher and can reach 80-90 percent.

Description

The preparation method of dinicotinic acid and diamino-pyridine prototropy compound
Technical field
The present invention relates to the preparation method of a kind of dinicotinic acid and diamino-pyridine compound prototropy compound, particularly relate to pyridine-2,6-dioctyl phthalate and 2,6-diamino-pyridine organic heterocyclic class prototropy compound [pydaH 2] 2+[pydc] 2-The preparation method.
Background technology
Pyridine-2, and the 6-dioctyl phthalate (2,6-Pyridinedicarboxylic acid; Dipicolinic acid; Pyridine-2,6-dicarboxylic acid), abbreviated formula is pydcH 2, molecular formula C 7H 5NO 4, the white solid powder.It is the material of biologically active in vivo, and its derivative, title complex all obtain extensive studies and application in the fields such as reaction, biological chemistry simulator and analytical chemistry such as stereochemistry, magnetic, spectrum kinetics and reaction mechanism and part.
2, and the 6-diamino-pyridine (2,6-Diaminopyridine; 2,6-Pyridinediamine), abbreviated formula is pyda, molecular formula C 5H 7N 3, little yellow solid powder.It is a weak organic bases that contains nitrogen heteroatom in the ring, a kind of as in the pyridine derivate series product, it is important intermediate in the fields such as medicine, agricultural chemicals, dyestuff, foodstuff additive, being widely used in the organic synthesis, is to produce the important source material of benzeneazo pyridine-mono-hydrochloric salts and organic dye common, simple in structure.
Pyridine-2,6-dioctyl phthalate and 2,6-diamino-pyridine prototropy compound [pydaH 2] 2+[pydc] 2-Be a kind of xanchromatic pressed powder, be dissolved in hot water and dimethyl sulfoxide (DMSO), be insoluble to ethanol, ether, tetrahydrofuran (THF), butanone, be used to prepare the organic ligand of various metal-organic coordination compounds.
A.Moghimi etc. (Journal of Molecular Structure, 2002,605:133-149) a kind of preparation pyridine-2 is disclosed, 6-dioctyl phthalate and 2,6-diamino-pyridine prototropy compound [pydaH 2] 2+[pydc] 2-Method: with 0.042molL -12,6-diamino-pyridine tetrahydrofuran solution and 0.084molL -1The tetrahydrofuran solution of triethylamine dropwise add to 0.042molL -12, in the 6-diamino-pyridine tetrahydrofuran solution, violent stirring is disperseed 15min, reflux 16h under the katalysis of triethylamine at room temperature stirs 24h then, obtains xanchromatic suspension.After filtration, obtain the xanchromatic pressed powder after the washing, drying, productive rate is 88%.Characterize after tested, the chemical constitution of product is [pydaH 2] 2+[pydc] 2-, fusing point is 235～237 ℃.
This compound [pydaH 2] 2+[pydc] 2-The preparation method, use tetrahydrofuran (THF) to be solvent, triethylamine is a catalyzer, and concentration of reactants is low, the reaction times is longer, therefore cost is higher, all has significantly deficiency on preparation technology, time and cost.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of dinicotinic acid and diamino-pyridine prototropy compound is to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
With pyridine-2,6-dioctyl phthalate and 2,6-diamino-pyridine are raw material, in water or organic solvent, under the ultrasonic wave effect, react, and collect described pyridine-2,6-dioctyl phthalate and 2,6-diamino-pyridine prototropy compound [pydaH then from reaction product 2] 2+[pydc] 2-
Pyridine-2,6-dioctyl phthalate and 2, the mole proportioning of 6-diamino-pyridine is n Pydc/ n Pyda=0.66～1.5, preferred proportioning is 1;
In water or the organic solvent, pyridine-2,6-dioctyl phthalate or 2, the volumetric molar concentration of 6-diamino-pyridine is 0.01～0.3molL -1, preferred volumetric molar concentration is 0.1～0.2molL -1
The ultrasonic vibration time is 5～60min, and the preferred ultrasonic vibration time is 10～15min;
Described organic solvent is one or more in alcohols, ethers, ketone, benzene class, halohydrocarbon or the heterocyclic;
Described alcoholic solvent is one or more in the monohydroxy-alcohol of C1～C5, is preferably methyl alcohol or ethanol;
Described ethers is methyl ether or ether or its mixture, is preferably ether;
Described ketone is one or more in C3～C6 ketone, is preferably acetone or butanone;
Described benzene class is one or more in the benzene,toluene,xylene, is preferably toluene or dimethylbenzene;
Described halohydrocarbon is one or more in the chlorinated hydrocarbon among C1～C4, is preferably trichloromethane or tetracol phenixin;
Described heterocyclic is one or more of ring compound that contain oxygen, sulphur class, is preferably tetrahydrofuran (THF);
Through characterization test, the unanimity in the chemical constitution of compound, structure and various physico-chemical property and the document (Journal ofMolecular Structure, 2002,605:133～149), its productive rate is 80～90%.
Advantage of the present invention and beneficial effect:
(1) preparation method is simple, and the method for ultrasonic vibration is commonplace; (2) preparation time is shorter, only needs several minutes; (3) product purity is higher; (4) preparation cost is lower, only need a spot of organic solvent, and power cost is also less; (5) productive rate of product is higher, can reach 80～90%.
Prepare prototropy compound [pydaH with above-mentioned preparation method 2] 2+[pydc] 2-Consuming time few during product, synthetic route is short, and technology is simple, and the purity height is with low cost; In addition, in above-mentioned preparation method, not only broken through reactant feed to concentration restriction more among a small circle, but also can select for use the less ethanol of toxicity etc. as organic solvent, and avoid of the pollution of other organic solvent to environment, therefore have tangible economic benefit and social benefit.
Embodiment
Embodiment 1
With pyridine-2,6-dioctyl phthalate 0.1672g and 2,6-diamino-pyridine 0.1092g and is placed in the Ultrasonic Cleaners in the round-bottomed flask of 50mL, add 10mL ethanol after, ultra-sonic dispersion 10min, leave standstill the 1h after-filtration, use washing with alcohol, dry in 80 ℃ of baking ovens, can obtain the xanchromatic pressed powder, productive rate is 99.5%.
Adopt conventional fusing point measurement and elemental analysis method that the pressed powder product purity is analyzed, product purity is 99.5% (weight);
Adopt Journal of Molecular Structure, 2002, the used method of 605:133～149 documents is carried out characterization test, and the chemical constitution of compound, structure and various physico-chemical property are as follows:
Chemical constitution: C 12H 12N 4O 4
Chemical structural formula: [pydaH 2] 2+[pydc] 2-
Fusing point: 236 ℃;
With the unanimity in the document (Journal of Molecular Structure, 2002,605:133～149).
Embodiment 2
With pyridine-2,6-dioctyl phthalate 0.1672g and 2,6-diamino-pyridine 0.1092g is in the there-necked flask of 100mL, and be placed in the Ultrasonic Cleaners, add behind the 40mL trichloromethane ultra-sonic dispersion 20min immediately, leave standstill the 2h after-filtration, with a spot of trichloromethane washing, dry in 80 ℃ of baking ovens, can obtain the xanchromatic pressed powder, productive rate is 81%.
The purity of test products therefrom is identical with the data of embodiment 1 product with various physico-chemical properties.
Embodiment 3
Take by weighing pyridine-2,6-dioctyl phthalate 0.1003g and 2,6-diamino-pyridine 0.0655g is in the round-bottomed flask of 50mL, and be placed in the Ultrasonic Cleaners, add behind the 20mL methyl alcohol ultra-sonic dispersion 15min immediately, leave standstill the 2h after-filtration, use a spot of methanol wash, dry in 70 ℃ of baking ovens, can obtain the xanchromatic pressed powder, productive rate is 85%.
The purity of test products therefrom is identical with the data of embodiment 1 product with various physico-chemical properties.
Embodiment 4
Take by weighing pyridine-2,6-dioctyl phthalate 0.2507g and 2,6-diamino-pyridine 0.1637g is in the round-bottomed flask of 50mL, and be placed in the Ultrasonic Cleaners, add behind the 30mL tetrahydrofuran (THF) ultra-sonic dispersion 30min immediately, leave standstill the 1h after-filtration, with a spot of tetrahydrofuran (THF) washing, dry in 70 ℃ of baking ovens, can obtain the xanchromatic pressed powder, productive rate is 82%.
The purity of test products therefrom is identical with the data of embodiment 1 product with various physico-chemical properties.
Embodiment 5
Take by weighing pyridine-2,6-dioctyl phthalate 0.2006g and 2,6-diamino-pyridine 0.1310g is in the round-bottomed flask of 50mL, and be placed in the Ultrasonic Cleaners, add behind the 25mL acetone ultra-sonic dispersion 30min immediately, leave standstill the 1h after-filtration, use a spot of washing with acetone, dry in 70 ℃ of baking ovens, can obtain the xanchromatic pressed powder, productive rate is 88%.
The purity of test products therefrom is identical with the data of embodiment 1 product with various physico-chemical properties.
Embodiment 6
Take by weighing pyridine-2,6-dioctyl phthalate 0.2006g and 2,6-diamino-pyridine 0.1310g is in the round-bottomed flask of 50mL, and be placed in the Ultrasonic Cleaners, add behind the 25mL toluene ultra-sonic dispersion 20min immediately, leave standstill the 1h after-filtration, use a spot of toluene wash, dry in 100 ℃ of baking ovens, can obtain the xanchromatic pressed powder, productive rate is 82%.
The purity of test products therefrom is identical with the data of embodiment 1 product with various physico-chemical properties.
Embodiment 7
With pyridine-2,6-dioctyl phthalate 0.1672g and 2,6-diamino-pyridine 0.1092g and is placed in the Ultrasonic Cleaners in the round-bottomed flask of 50mL, add 10mL water after, ultra-sonic dispersion 5min, leave standstill the 30min after-filtration, wash with water, dry in 100 ℃ of baking ovens, can obtain the xanchromatic pressed powder, productive rate is 80%.
The purity of test products therefrom is identical with the data of embodiment 1 product with various physico-chemical properties.
Embodiment 8
With pyridine-2,6-dioctyl phthalate 0.1672g and 2,6-diamino-pyridine 0.1092g and is placed in the Ultrasonic Cleaners in the round-bottomed flask of 50mL, add the 15mL ether after, ultra-sonic dispersion 10min, filter, with the ether washing, dry in 80 ℃ of baking ovens, can obtain the xanchromatic pressed powder, productive rate is 87%.
The various physicochemical property test datas of product are identical with corresponding data among the embodiment 1.

Claims (10)

1. the preparation method of dinicotinic acid and diamino-pyridine prototropy compound, it is characterized in that, comprise the steps: that with pyridine-2 6-dioctyl phthalate and 2,6-diamino-pyridine are raw material, in water or organic solvent, under the ultrasonic wave effect, react, collect described pyridine-2 then, 6-dioctyl phthalate and 2,6-diamino-pyridine prototropy compound [pydaH 2] 2+[pydc] 2-
2. method according to claim 1 is characterized in that, pyridine-2, and 6-dioctyl phthalate and 2, the mole proportioning of 6-diamino-pyridine is n Pydc/ n Pyda=0.66～1.5, in water or the organic solvent, pyridine-2,6-dioctyl phthalate or 2, the volumetric molar concentration of 6-diamino-pyridine is 0.01～0.3molL -1
3. method according to claim 1 is characterized in that, the ultrasonic vibration time is 5～60min.
4. method according to claim 1 is characterized in that, described organic solvent is one or more in alcohols, ethers, ketone, benzene class, halohydrocarbon or the heterocyclic.
5. method according to claim 4 is characterized in that, described alcoholic solvent is one or more in the monohydroxy-alcohol of C1～C5.
6. method according to claim 4 is characterized in that, described ethers is methyl ether or ether or its mixture.
7. method according to claim 4 is characterized in that, described ketone is one or more in C3～C6 ketone, is preferably acetone or butanone.
8. method according to claim 4 is characterized in that, described benzene class is one or more in the benzene,toluene,xylene.
9. method according to claim 4 is characterized in that, described halohydrocarbon is one or more in the chlorinated hydrocarbon among C1～C4.
10. method according to claim 4 is characterized in that, described heterocyclic is one or more of ring compound that contain oxygen, sulphur class.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103694266A (en) * 2014-01-02 2014-04-02 华东理工大学 Hydrogen-bonded rare-earth metal europium complex fluorescent material and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1363909A (en) * 1970-11-10 1974-08-21 Bayer Ag Process for the production of pyridine carboxylic
WO1994020469A1 (en) * 1991-12-20 1994-09-15 Basf Aktiengesellschaft Process for producing diamino pyridines
CN1264371A (en) * 1997-07-17 2000-08-23 罗纳-布朗克罗莱尔股份有限公司 Pyrazine derivatives, their preparation and medicines containing them
JP2002086613A (en) * 2000-07-14 2002-03-26 Nippon Steel Corp Surface coated metal material
CN1915975A (en) * 2005-08-15 2007-02-21 中国科学院福建物质结构研究所 Non-linear optic crystal material of coordination polymer of dinicotinic acid
CN101456875A (en) * 2008-10-31 2009-06-17 上海华明高技术（集团）有限公司 Hydrogen bond type rare-earth metal complexes and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1363909A (en) * 1970-11-10 1974-08-21 Bayer Ag Process for the production of pyridine carboxylic
WO1994020469A1 (en) * 1991-12-20 1994-09-15 Basf Aktiengesellschaft Process for producing diamino pyridines
CN1264371A (en) * 1997-07-17 2000-08-23 罗纳-布朗克罗莱尔股份有限公司 Pyrazine derivatives, their preparation and medicines containing them
JP2002086613A (en) * 2000-07-14 2002-03-26 Nippon Steel Corp Surface coated metal material
CN1915975A (en) * 2005-08-15 2007-02-21 中国科学院福建物质结构研究所 Non-linear optic crystal material of coordination polymer of dinicotinic acid
CN101456875A (en) * 2008-10-31 2009-06-17 上海华明高技术（集团）有限公司 Hydrogen bond type rare-earth metal complexes and preparation method thereof

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
A MOGHIMI,等: "A novel pyridine containing self-assembling system: synthesis, characterization, X-ray crystal structure, 13C solid phase NMR and solution studies", 《JOURNAL OF MOLECULAR STRUCTURE》 *
AGHABOZORG,HOSSEIN, 等: "2,6-Diaminopyridinium pyridinium-2,6-dicarboxylate:a redetermination", 《ACTA CRYSTALLOGRAPHICA, SECTION E: STRUCTURE REPORTS》 *
HOSSEIN AGHABOZORG,等: "Novel Complexes of Gallium(III), Indium(III), and Thallium(III) with Pyridine-Containing Proton Transfer Ion Pairs Obtained from Dipicolinic Acid-Synthesis, Characterization and X-ray Crystal Structure", 《Z.ANORG.ALLG.CHEM.》 *
MARYAM RANJBAR,等: "Crystal structure of Bi(III) complex of a pyridine containing self-assembling system", 《ANALYTICAL SCIENCES》 *
SNEH L.JAIN,等: "New pyridine carboxamide ligands and their complexation to copper(II ). X-Ray crystal structures of mono-, di, tri- and tetranuclear copper complexes", 《DALTON TRANS.》 *
刘永,等: "超声波应用于有机合成的最新进展", 《广东化工》 *
张国福: "微波辐射条件下毗咤#2,-二甲酸及其衍生物的合成", 《西北师范大学高校教师硕士学位论文》 *
张新波,等: "超声波在有机合成中的应用", 《化学试剂》 *
荣建辉: "超声波在有机合成方面的新进展", 《化学通报》 *
覃兆海,等: "超声波在有机合成中的应用", 《化学进展》 *
赵志明,等: "芳杂环类多重氢键分子钳人工受体的设计合成", 《四川大学学报(自然科学版)》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103694266A (en) * 2014-01-02 2014-04-02 华东理工大学 Hydrogen-bonded rare-earth metal europium complex fluorescent material and preparation method thereof

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