CN104892503A - Preparation method of 2,2'-bipyridine-4,4'-dicarboxylic acid - Google Patents
Preparation method of 2,2'-bipyridine-4,4'-dicarboxylic acid Download PDFInfo
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- CN104892503A CN104892503A CN201510291480.6A CN201510291480A CN104892503A CN 104892503 A CN104892503 A CN 104892503A CN 201510291480 A CN201510291480 A CN 201510291480A CN 104892503 A CN104892503 A CN 104892503A
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- dipyridyl
- potassium permanganate
- dioctyl phthalate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
- C07D213/807—Processes of preparation by oxidation of pyridines or condensed pyridines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
Abstract
The invention discloses a preparation method of 2'-bipyridine-4,4'-dicarboxylic acid, belonging to the technical field of synthesis of sensitization fuel and medicinal intermediates. The point of the technical scheme adopted in the invention is as follows: 4,4'-dimethyl-2,2'-bipyridine is dissolved in a mixed system of water and nitric acid, and the 2'-bipyridine-4,4'-dicarboxylic acid is prepared through the oxidation of potassium permanganate. The method disclosed by the invention is easy to operate, the reaction conditions are mild, the reaction time is relatively short, and the yield of the obtained product is relatively high; and moreover, the after-treatment of the reaction is simple, the product is easily crystallized and separated from the system and is convenient to separate to obtain the target compound, and the method is suitable for large-scale production.
Description
Technical field
The invention belongs to the synthesis technical field of sensitization fuel and medicine intermediate, be specifically related to a kind of preparation method of 2,2'-dipyridyl-4,4'-dioctyl phthalate.
Background technology
Bipyridyliums derivative is the important source material of complex functionality shaped material, can form the title complex with conjugated electrons system with various metals, and these title complexs have good photoelectric conversion effect.They, as Conversion of energy material-dye sensitizing agent, play an important role in dye sensitization solar battery.Wherein 2,2'-dipyridyls are one important in Bipyridine compound, and it can form title complex with each metal ion species as important chemical industry synthetic intermediate, can be widely used in and detect the existence of trace metal ion and content thereof etc.It can also form important noble metal complexes ligand, for the preparation of photoelectron transfer Complexes, for the preparation of solar cell.2,2'-dipyridyl-4,4'-dioctyl phthalate has the carboxyl ligand of N heterocyclic ligand and O, it has important effect with the title complex of some metal on dye sensitization solar battery and C-C key are coupled, and the green high-efficient synthetic method therefore studying this this compounds is of great significance and value.Publication number be the patent of CN 103183636A with 2-chloroisonicotinic acid under palladium chtalyst, in the reduction system of mineral alkali and glycerol, carry out obtained 2, the 2'-dipyridyl-4 of reductive coupling reaction, the method of 4'-dioctyl phthalate, by product is more, and reaction is more complicated, and reaction conditions is also harsher.The simple preparation method of one of 2,2'-dipyridyl-4,4'-dioctyl phthalate is obtained by the methyl be oxidized on 4,4'-dimethyl-2,2'-dipyridyl, studies and the effective method for oxidation exploring 4,4'-dimethyl-2,2'-dipyridyl is necessary.The multiplex potassium bichromate of current method for oxidation or chromium trioxide react in sulfuric acid system, although these are swift in response, simple to operate, but be the use of corrodibility and the larger vitriol oil of hazardness, the environmental hazard of heavy metal chromium ion pair is larger, reaction needs heating, has certain danger, is not suitable for large-scale industrial production.Publication number is the patent of CN 102321017A is by 4,4'-dimethyl-2,2'-dipyridyl avoids the use of potassium bichromate and sulfuric acid in the mixed system of Glacial acetic acid and water by the method for potassium permanganate oxidation, but target product is not easily separated from reaction system, and aftertreatment is comparatively complicated.
Summary of the invention
The technical problem that the present invention solves there is provided a kind of simple to operate, safe and reliable and preparation method of 2,2'-dipyridyl-4, the 4'-dioctyl phthalate that productive rate is higher.
The present invention adopts following technical scheme for solving the problems of the technologies described above, a kind of 2, 2'-dipyridyl-4, the preparation method of 4'-dioctyl phthalate, it is characterized in that: by 4, 4'-dimethyl-2, in the mixed system of the water-soluble and nitric acid of 2'-dipyridyl and by potassium permanganate oxidation obtained 2, 2'-dipyridyl-4, 4'-dioctyl phthalate, specifically comprise the following steps: (1) is by 4, 4'-dimethyl-2, 2'-dipyridyl is water-soluble with in the mixed system of nitric acid, stir and be heated to 80 DEG C, add potassium permanganate in batches, until the last batch of potassium permanganate reaction added to clarification, add the potassium permanganate of next batch again, maintain the temperature at 80 DEG C of reaction 6h, (2) reaction solution is cooled to room temperature, decompress filter, elimination insoluble substance, then the pH value adding concentrated hydrochloric acid adjustment filtrate in filtrate is 1, leave standstill crystallization, after crystallization is complete, decompress filter, filter cake deionized water wash, products therefrom obtains 2,2'-dipyridyl-4,4'-dioctyl phthalate after drying.
Further restriction, water 10-100mL in the corresponding mixed system of 1g 4,4'-dimethyl-2,2'-dipyridyl in preparation process.
Further restriction, in described mixed system, the volume ratio of nitric acid and water is 1-30:100.
Further restriction, in preparation process, the mol ratio of 4,4'-dimethyl-2,2'-dipyridyls and potassium permanganate is 1:2-8.
The present invention has following beneficial effect: (1) reaction system is simple, and only use potassium permanganate, water (solvent) and nitric acid (oxygenant), these reagent belong to general chemistry reagent, cheap and easy to get, and preparation cost is low; (2) this reaction meets the theory of Green Chemistry, avoids chromium trioxide or potassium bichromate etc. have the oxygenant of pollution use to environment; (3) easy and simple to handle, reaction conditions is gentle, and the reaction times is relatively short, and products therefrom yield is higher, and this post-reaction treatment is simple, and product is easy to crystallization from system, is convenient to be separated and obtain target compound, is applicable to scale operation.
The present invention compared with prior art, main innovation is to add nitric acid in reaction system, adding of nitric acid makes 4,4'-dimethyl-2,2'-dipyridyl is dissolved in reaction system, reaction is carried out in homogeneous system, and the sour environment that nitric acid provides simultaneously also enhances the oxidation capacity of potassium permanganate.With potassium permanganate oxidation 4 in the mixed system of water and nitric acid, 4'-dimethyl-2,2'-dipyridyl, reaction conditions is relatively gentle, and do not use environmentally harmful oxygenant, and the adjustment of pH makes target product 2,2'-dipyridyl-4,4'-dioctyl phthalate be easy to crystallization from system in aftertreatment.This reaction all can be carried out smoothly when laboratory and industrialization scale operation, has larger Practical significance.
Embodiment
Be described in further details foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
The synthesis of 2,2'-dipyridyl-4,4'-dioctyl phthalate
In the four-hole bottle that magneton, thermometer and reflux condensing tube are housed, add 3.7g (0.02mol) analytically pure 4,4 '-dimethyl-2,2 '-dipyridyl, is dissolved in the mixed system of 40mL water and 4mL nitric acid, 80 DEG C are heated under stirring, and keep this temperature to divide adding for five times potassium permanganate solid (altogether 6.3g, 0.04mol), until before the potassium permanganate reaction that once adds to molten clear after, add the potassium permanganate of next batch again, react after 6 hours and stop heating.After being cooled to room temperature, by reaction solution decompress filter, after elimination insoluble substance, in filtrate, add concentrated hydrochloric acid, adjust ph is 1.Leave standstill crystallization, adularescent crystal is separated out.Until crystallization completely after, carry out decompress filter, and with the white crystal of deionized water wash gained.Finally that product vacuum is dry, obtain target product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 4.2g, productive rate is 86%.
Embodiment 2
The synthesis of 2,2'-dipyridyl-4,4'-dioctyl phthalate
In the four-hole bottle that thermometer, magneton and reflux condensing tube are housed, add 3.7g (0.02mol) analytically pure 4,4 '-dimethyl-2,2 '-dipyridyl, is dissolved in the mixed system of 40mL water and 4mL nitric acid, 80 DEG C are heated under stirring, and keep this temperature to divide adding for five times potassium permanganate solid (altogether 12.6g, 0.08mol), until before the potassium permanganate reaction that once adds to molten clear after, add the potassium permanganate of next batch again, react after 6 hours and stop heating.After being cooled to room temperature, by reaction solution decompress filter, after elimination insoluble substance, in filtrate, add concentrated hydrochloric acid, adjust ph is 1.Leave standstill crystallization, adularescent crystal is separated out.Until crystallization completely after, carry out decompress filter, and with the white crystal of deionized water wash gained.Finally that product vacuum is dry, obtain target product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 4.35g, productive rate is 89%.
Embodiment 3
The synthesis of 2,2'-dipyridyl-4,4'-dioctyl phthalate
In the four-hole bottle that thermometer, magneton and reflux condensing tube are housed, add 3.7g (0.02mol) analytically pure 4,4 '-dimethyl-2,2 '-dipyridyl, is dissolved in the mixed system of 40mL water and 4mL nitric acid, 80 DEG C are heated under stirring, and keep this temperature to divide adding for five times potassium permanganate solid (altogether 25.28g, 0.16mol), until before the potassium permanganate reaction that once adds to molten clear after, add the potassium permanganate of next batch again, react after 6 hours and stop heating.After being cooled to room temperature, by reaction solution decompress filter, after elimination insoluble substance, in filtrate, add concentrated hydrochloric acid, adjust ph is 1.Leave standstill crystallization, adularescent crystal is separated out.Until crystallization completely after, carry out decompress filter, and with the white crystal of deionized water wash gained.Finally that product vacuum is dry, obtain target product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 4.44g, productive rate is 91%.
Embodiment 4
The synthesis of 2,2'-dipyridyl-4,4'-dioctyl phthalate
In the four-hole bottle that thermometer, magneton and reflux condensing tube are housed, add 3.7g (0.02mol) analytically pure 4,4 '-dimethyl-2,2 '-dipyridyl, is dissolved in the mixed system of 40mL water and 8mL nitric acid, 80 DEG C are heated under stirring, and keep this temperature to divide adding for five times potassium permanganate solid (altogether 12.6g, 0.08mol), until before the potassium permanganate reaction that once adds to molten clear after, add the potassium permanganate of next batch again, react after 6 hours and stop heating.After being cooled to room temperature, by reaction solution decompress filter, after elimination insoluble substance, in filtrate, add concentrated hydrochloric acid, adjust ph is 1.Leave standstill crystallization, adularescent crystal is separated out.Until crystallization completely after, carry out decompress filter, and with the white crystal of deionized water wash gained.Finally that product vacuum is dry, obtain target product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 4.59g, productive rate is 94%.
Embodiment 5
The synthesis of 2,2'-dipyridyl-4,4'-dioctyl phthalate
In the four-hole bottle that thermometer, magneton and reflux condensing tube are housed, add 3.7g (0.02mol) analytically pure 4,4 '-dimethyl-2,2 '-dipyridyl, is dissolved in the mixed system of 40mL water and 12mL nitric acid, 80 DEG C are heated under stirring, and keep this temperature to divide adding for five times potassium permanganate solid (altogether 12.6g, 0.08mol), until before the potassium permanganate reaction that once adds to molten clear after, add the potassium permanganate of next batch again, react after 6 hours and stop heating.After being cooled to room temperature, by reaction solution decompress filter, after elimination insoluble substance, in filtrate, add concentrated hydrochloric acid, adjust ph is 1.Leave standstill crystallization, adularescent crystal is separated out.Until crystallization completely after, carry out decompress filter, and with the white crystal of deionized water wash gained.Finally that product vacuum is dry, obtain target product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 4.49g, productive rate is 92%.
Embodiment 6
The synthesis of 2,2'-dipyridyl-4,4'-dioctyl phthalate
In the four-hole bottle that thermometer, magneton and reflux condensing tube are housed, add 3.7g (0.02mol) analytically pure 4,4 '-dimethyl-2,2 '-dipyridyl, is dissolved in the mixed system of 40mL water and 2mL nitric acid, 80 DEG C are heated under stirring, and keep this temperature to divide adding for five times potassium permanganate solid (altogether 12.6g, 0.08mol), until before the potassium permanganate reaction that once adds to molten clear after, add the potassium permanganate of next batch again, react after 6 hours and stop heating.After being cooled to room temperature, by reaction solution decompress filter, after elimination insoluble substance, in filtrate, add concentrated hydrochloric acid, adjust ph is 1.Leave standstill crystallization, adularescent crystal is separated out.Until crystallization completely after, carry out decompress filter, and with the white crystal of deionized water wash gained.Finally that product vacuum is dry, obtain target product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 4.59g, productive rate is 94%.
Embodiment 7
2, the synthesis of 2 '-dipyridyl-4,4 '-dioctyl phthalate
In the four-hole bottle that thermometer, magneton and reflux condensing tube are housed, add 3.7g (0.02mol) analytically pure 4,4 '-dimethyl-2,2 '-dipyridyl, is dissolved in the mixed system of 40mL water and 0.4mL nitric acid, 80 DEG C are heated under stirring, and keep this temperature to divide adding for five times potassium permanganate solid (altogether 12.6g, 0.08mol), until before the potassium permanganate reaction that once adds to molten clear after, add the potassium permanganate of next batch again, react after 6 hours and stop heating.After being cooled to room temperature, by reaction solution decompress filter, after elimination insoluble substance, in filtrate, add concentrated hydrochloric acid, adjust ph is 1.Leave standstill crystallization, adularescent crystal is separated out.Until crystallization completely after, carry out decompress filter, and with the white crystal of deionized water wash gained.Finally that product vacuum is dry, obtain target product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 4.69g, productive rate is 96%.
Embodiment 8
2, the synthesis of 2 '-dipyridyl-4,4 '-dioctyl phthalate
In the four-hole bottle that thermometer, magneton and reflux condensing tube are housed, add 3.7g (0.02mol) analytically pure 4,4 '-dimethyl-2,2 '-dipyridyl, is dissolved in the mixed system of 80mL water and 8mL nitric acid, 80 DEG C are heated under stirring, and keep this temperature to divide adding for five times potassium permanganate solid (altogether 12.6g, 0.08mol), until before the potassium permanganate reaction that once adds to molten clear after, add the potassium permanganate of next batch again, react after 6 hours and stop heating.After being cooled to room temperature, by reaction solution decompress filter, after elimination insoluble substance, in filtrate, add concentrated hydrochloric acid, adjust ph is 1.Leave standstill crystallization, adularescent crystal is separated out.Until crystallization completely after, carry out decompress filter, and with the white crystal of deionized water wash gained.Finally that product vacuum is dry, obtain target product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 4.10g, productive rate is 84%.
Embodiment 9
2, the synthesis of 2 '-dipyridyl-4,4 '-dioctyl phthalate
In the four-hole bottle that thermometer, magneton and reflux condensing tube are housed, add 3.7g (0.02mol) analytically pure 4,4 '-dimethyl-2,2 '-dipyridyl, is dissolved in the mixed system of 200mL water and 20mL nitric acid, 80 DEG C are heated under stirring, and keep this temperature to divide adding for five times potassium permanganate solid (altogether 12.6g, 0.08mol), until before the potassium permanganate reaction that once adds to molten clear after, add the potassium permanganate of next batch again, react after 6 hours and stop heating.After being cooled to room temperature, by reaction solution decompress filter, after elimination insoluble substance, in filtrate, add concentrated hydrochloric acid, adjust ph is 1.Leave standstill crystallization, adularescent crystal is separated out.Until crystallization completely after, carry out decompress filter, and with the white crystal of deionized water wash gained.Finally that product vacuum is dry, obtain target product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 4.00g, productive rate is 82%.
Embodiment 10
2, the synthesis of 2 '-dipyridyl-4,4 '-dioctyl phthalate
In the four-hole bottle that thermometer, magneton and reflux condensing tube are housed, add 3.7g (0.02mol) analytically pure 4,4 '-dimethyl-2,2 '-dipyridyl, is dissolved in the mixed system of 400mL water and 40mL nitric acid, 80 DEG C are heated under stirring, and keep this temperature to divide adding for five times potassium permanganate solid (altogether 12.6g, 0.08mol), until before the potassium permanganate reaction that once adds to molten clear after, add the potassium permanganate of next batch again, react after 6 hours and stop heating.After being cooled to room temperature, by reaction solution decompress filter, after elimination insoluble substance, in filtrate, add concentrated hydrochloric acid, adjust ph is 1.Leave standstill crystallization, adularescent crystal is separated out.Until crystallization completely after, carry out decompress filter, and with the white crystal of deionized water wash gained.Finally that product vacuum is dry, obtain target product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 4.00g, productive rate is 82%.
Spectral data:
Target product 2, the structure of 2 '-dipyridyl-4,4 '-dioctyl phthalate is:
FT-IR (cm
-1) KBr: ν 3440(is strong), 2446(is strong), 1730(is strong), 1605(is strong), 1463(is strong), 1365(is strong), 1290(is strong), 1269(is strong).
Ultimate analysis:
2,2 '-dipyridyl-4,4 '-dioctyl phthalate (molecular formula C
12h
8n
2o
4) calculated value: C 59.02, H 3.30, N 11.50, O 26.18; Analytical value: C 59.09, H 3.55, N 11.53.
Embodiment above describes ultimate principle of the present invention, principal character and advantage; the technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; under the scope not departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.
Claims (4)
1. one kind 2,2'-dipyridyl-4, the preparation method of 4'-dioctyl phthalate, it is characterized in that: by 4,4'-dimethyl-2, in the mixed system of the water-soluble and nitric acid of 2'-dipyridyl and by obtained 2,2'-dipyridyl-4, the 4'-dioctyl phthalate of potassium permanganate oxidation, specifically comprise the following steps: (1) is by 4,4'-dimethyl-2,2 '-dipyridyl is water-soluble with in the mixed system of nitric acid, stirs and is heated to 80 DEG C, add potassium permanganate in batches, until the last batch of potassium permanganate reaction added to clarification, then add the potassium permanganate of next batch, maintain the temperature at 80 DEG C of reaction 6h; (2) reaction solution is cooled to room temperature, decompress filter, elimination insoluble substance, then the pH value adding concentrated hydrochloric acid adjustment filtrate in filtrate is 1, leave standstill crystallization, after crystallization is complete, decompress filter, filter cake deionized water wash, products therefrom obtains 2,2'-dipyridyl-4,4'-dioctyl phthalate after drying.
2. the preparation method of 2,2'-dipyridyl-4,4'-dioctyl phthalate according to claim 1, is characterized in that: 1g 4 in preparation process, water 10-100mL in the corresponding mixed system of 4 '-dimethyl-2,2 '-dipyridyl.
3. the preparation method of 2,2'-dipyridyl-4,4'-dioctyl phthalate according to claim 1, is characterized in that: in described mixed system, the volume ratio of nitric acid and water is 1-30:100.
4. the preparation method of 2,2'-dipyridyl-4,4'-dioctyl phthalate according to claim 1, is characterized in that: in preparation process, the mol ratio of 4,4'-dimethyl-2,2'-dipyridyls and potassium permanganate is 1:2-8.
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| CN201510291480.6A CN104892503B (en) | 2015-06-01 | 2015-06-01 | A kind of preparation method of the ＇ dioctyl phthalate of 2,2 ＇ bipyridyls 4,4 |
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| CN201510291480.6A CN104892503B (en) | 2015-06-01 | 2015-06-01 | A kind of preparation method of the ＇ dioctyl phthalate of 2,2 ＇ bipyridyls 4,4 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5585279A (en) * | 1986-01-23 | 1996-12-17 | Davidson; Robert S. | Time-resolved luminescence binding assays using a fluorescent transition metal label other than ruthenium |
| JP2005082511A (en) * | 2003-09-05 | 2005-03-31 | Ube Ind Ltd | Method for producing carboxy compound |
| JP2006193444A (en) * | 2005-01-12 | 2006-07-27 | Koei Chem Co Ltd | Method for producing 4,4'-dicarboxy-2,2'-bipyridine |
| CN102321017A (en) * | 2011-07-08 | 2012-01-18 | 天津工业大学 | Method for preparing 2, 2'-bipyridyl-4, 4'-dioctyl phthalate |
-
2015
- 2015-06-01 CN CN201510291480.6A patent/CN104892503B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5585279A (en) * | 1986-01-23 | 1996-12-17 | Davidson; Robert S. | Time-resolved luminescence binding assays using a fluorescent transition metal label other than ruthenium |
| JP2005082511A (en) * | 2003-09-05 | 2005-03-31 | Ube Ind Ltd | Method for producing carboxy compound |
| JP2006193444A (en) * | 2005-01-12 | 2006-07-27 | Koei Chem Co Ltd | Method for producing 4,4'-dicarboxy-2,2'-bipyridine |
| CN102321017A (en) * | 2011-07-08 | 2012-01-18 | 天津工业大学 | Method for preparing 2, 2'-bipyridyl-4, 4'-dioctyl phthalate |
Non-Patent Citations (2)
| Title |
|---|
| GERHARD SPRINTSCHNIK，等: "Preparation and Photochemical Reactivity of Surfactant Ruthenium( 11) Complexes in Monolayer Assemblies and at Water-Solid Interfaces", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 田铁牛，等: "《有机合成单元过程》", 31 July 2010 * |
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