CN102532005A - One-step synthesis method of 2,2'-dipyridyl-4,4'-diformaldehyde - Google Patents
One-step synthesis method of 2,2'-dipyridyl-4,4'-diformaldehyde Download PDFInfo
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- CN102532005A CN102532005A CN2011104046246A CN201110404624A CN102532005A CN 102532005 A CN102532005 A CN 102532005A CN 2011104046246 A CN2011104046246 A CN 2011104046246A CN 201110404624 A CN201110404624 A CN 201110404624A CN 102532005 A CN102532005 A CN 102532005A
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Abstract
The invention relates to a one-step synthesis method of 2,2'-dipyridyl-4,4'-diformaldehyde. The method comprises the following steps of: dissolving 4,4'-dimethyl-2,2'-dipyridyl and iodine into dimethyl sulfoxide to obtain a solution A; adding the solution A into hot dimethyl sulfoxide of which the temperature is 120-140 DEG C under a stirring condition; raising the temperature to 150-180 DEG C and reacting for 0.5-3 hours; cooling to the room temperature; neutralizing a reaction product with an alkaline liquor till the pH is 7-8; and filtering, extracting a filtrate, drying and concentrating to obtain a target product. The method has the advantages of short reaction steps, easiness and convenience for operating, and the like.
Description
Technical field
The invention belongs to the organic synthesis field, specifically relate to 2,2'-dipyridyl-4, the one-step method for synthesizing of 4'-dicarbaldehyde.
Background technology
2,2'-dipyridyl-4,4'-dicarbaldehyde, molecular formula C
12H
8N
2O
2, molecular weight 212 is a kind of important chemical, medicinal intermediates and part.2,2'-dipyridyl-4, the 4'-dicarbaldehyde can form the title complex with conjugated electrons system with multiple metal such as ruthenium, has significant opto-electronic conversion effect.2,2'-dipyridyl-4, the ruthenium complexe of 4'-dicarbaldehyde is used for dye sensitization solar battery, is one type of important photosensitizer.(Journal of Heterocyclic Chemistry, 1990,27 (2): such as Ciana 163-5) with 4; 4'-dimethyl--2; The 2'-dipyridyl is a raw material, through oxidation, esterification, reduce and reoxidize four-step reaction and obtain the purpose product, exists reaction time longer; Defectives such as energy consumption is big, and use strong oxidizers such as sulfuric acid, chromium and oxide compound can produce serious sewage discharge problem in a large number.The inventive method is with 4, and 4'-dimethyl--2,2'-dipyridyl are raw material, can arrive 2,2'-dipyridyl-4,4'-dicarbaldehyde through single step reaction.
Summary of the invention
It is a kind of 2 that the object of the invention is to provide, 2'-dipyridyl-4, and the one-step method for synthesizing of 4'-dicarbaldehyde, this method is by 4, and 4'-dimethyl--2 directly obtains target product behind 2'-dipyridyl and the iodine single step reaction, and reactions step is few, and is easy and simple to handle.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
2,2 '-dipyridyl-4, the one-step synthesis of 4 '-dicarbaldehyde comprises the steps:
With 4,4'-dimethyl--2,2'-dipyridyl and iodine are dissolved in and get solution A in the methyl-sulphoxide; Under agitation condition, adding solution A (can slowly adding with the mode that drips preferably) is in 120～140 ℃ the hot methyl-sulphoxide, to be warming up to 150～180 ℃ of reaction 0.5～3h then to temperature; Be cooled to room temperature, it is 7～8 that reaction product uses alkali lye to be neutralized to pH, warp filtration then, filtrating extraction, dry and concentrated; Obtain title product 2,2'-dipyridyl-4,4'-dicarbaldehyde.
Concrete, in the said solution A 4,4'-dimethyl--2, the weight ratio of 2'-dipyridyl, iodine and methyl-sulphoxide is 1:2.76～3.31:5～10; Temperature is that 120～140 ℃ hot methyl-sulphoxide consumption is 4,4'-dimethyl--2,15～25 times of 2'-dipyridyl weight.
The used alkali lye that neutralizes is preferably saturated yellow soda ash, sodium hydrogencarbonate, salt of wormwood or potassium bicarbonate aqueous solution etc.Filtrating extraction solvent for use is preferably chloroform, methylene dichloride or 1,2-ethylene dichloride etc.Used siccative is preferably SODIUM SULPHATE ANHYDROUS 99PCT, anhydrous magnesium sulfate or Calcium Chloride Powder Anhydrous etc. when dry.
The reaction process of compound method of the present invention is following:
When the preparation solution A, can suitably heat to promote dissolving.Every gram 4,4'-dimethyl--2, the theoretical consumption of the iodine that 2'-dipyridyl raw material is corresponding is 2.76g.In the building-up process of reality, it is complete that iodine need slightly excessively just be beneficial to raw material reaction.But if the iodine consumption is too much, not only can cause waste, also bring unnecessary trouble simultaneously, influence degree of purity of production to subsequent purification.Therefore, be treated to preferably: the gained reaction product can be removed excessive iodine through adding a small amount of reductive agent (like saturated S-WAT, sodium sulfite anhy 96 or sodium thiosulfate solution) if be brown after being cooled to room temperature.The reduced liquid consumption is too much unsuitable, is advisable so that system is become colorless.
Compound method of the present invention is with 4, and 4'-dimethyl--2,2'-dipyridyl are raw material; With the iodine single step reaction; Directly obtain target product 2 after the purified processing, 2'-dipyridyl-4,4'-dicarbaldehyde (194.0～196.3 ℃ of fusing points); This compound method has been avoided the sewage discharge problem of using a large amount of strong oxidizers to cause, has advantages such as reactions step is short, easy and simple to handle.
Description of drawings
The product mass spectrum result of Fig. 1 for adopting compound method of the present invention to make, mass spectrograph model QP-5000, day island proper Tianjin company produces, and can find out that by mass spectrum the molecular weight product that makes is 212.0, confirms that thus product is 2,2'-dipyridyl-4,4'-dicarbaldehyde.
Embodiment
Below through several preferred embodiments compound method of the present invention is done further explain, but protection scope of the present invention is not limited thereto.
Embodiment 1
2,2 '-dipyridyl-4, the one-step synthesis of 4 '-dicarbaldehyde comprises the steps:
1. with 1 g 4,4'-dimethyl--2,2'-dipyridyl and 2.8g iodine are dissolved in and get solution A in the 8g methyl-sulphoxide, and be subsequent use.
2. in having the flask of device for absorbing tail gas, add the 20g methyl-sulphoxide, be preheating to 130 ℃; Then under agitation condition, slowly splash into solution A, be warming up to 160 ℃ of reaction 1.5h then, be cooled to room temperature.
3. to use saturated aqueous sodium carbonate to be neutralized to pH be 7 to reaction product, and decompress filter is removed insolubles, and filtrating is used chloroform extraction; Extraction gained organic phase is used anhydrous sodium sulfate drying; Obtain 0.29g through filtration, Rotary Evaporators concentrating under reduced pressure then and be close to colourless pressed powder, be title product 2,2'-dipyridyl-4; The 4'-dicarbaldehyde, yield 25.4 %.
Embodiment 2
2,2 '-dipyridyl-4, the one-step synthesis of 4 '-dicarbaldehyde comprises the steps:
1. with 1 g 4,4'-dimethyl--2,2'-dipyridyl and 3.3g iodine are dissolved in and get solution A in the 10g methyl-sulphoxide, and be subsequent use.
2. in having the flask of device for absorbing tail gas, add the 18g methyl-sulphoxide, be preheating to 140 ℃; Then under agitation condition, slowly splash into solution A, be warming up to 150 ℃ of reaction 3h then, be cooled to room temperature.
3. reaction product adds an amount of saturated sodium bisulfite solution, so that system is faded for colourless, using saturated sodium bicarbonate aqueous solution to be neutralized to pH then is 8; Decompress filter is removed insolubles, and filtrating is used dichloromethane extraction, and extraction gained organic phase is dry with Calcium Chloride Powder Anhydrous; Obtain 0.32g faint yellow solid powder through filtration, concentrating under reduced pressure then, be title product 2,2'-dipyridyl-4; The 4'-dicarbaldehyde, yield 27.8%.
Embodiment 3
2,2 '-dipyridyl-4, the one-step synthesis of 4 '-dicarbaldehyde comprises the steps:
1. with 1 g 4,4'-dimethyl--2,2'-dipyridyl and 3.0g iodine are dissolved in and get solution A in the 6g methyl-sulphoxide, and be subsequent use.
2. in having the flask of device for absorbing tail gas, add the 25g methyl-sulphoxide, be preheating to 120 ℃; Then under agitation condition, slowly splash into solution A, be warming up to 180 ℃ of reaction 0.5h then, be cooled to room temperature.
3. reaction product adds an amount of saturated sodium bisulfite solution, so that system is faded for colourless, using the saturated potassium hydrogen carbonate aqueous solution to be neutralized to pH then is 7; Decompress filter is removed insolubles, and filtrating is used chloroform extraction, and extraction gained organic phase is used anhydrous magnesium sulfate drying; Obtain 0.36g faint yellow solid powder through filtration, concentrating under reduced pressure then, be title product 2,2'-dipyridyl-4; The 4'-dicarbaldehyde, yield 31.3%.
Claims (5)
1.2,2 '-dipyridyl-4, the one-step synthesis of 4 '-dicarbaldehyde is characterized in that, comprises the steps:
With 4,4'-dimethyl--2,2'-dipyridyl and iodine are dissolved in and get solution A in the methyl-sulphoxide; Under agitation condition, joining temperature to solution A is in 120～140 ℃ the hot methyl-sulphoxide, is warming up to 150～180 ℃ of reaction 0.5～3h then; Be cooled to room temperature, it is 7～8 that reaction product uses alkali lye to be neutralized to pH, warp filtration then, filtrating extraction, dry and concentrated; Obtain title product 2,2'-dipyridyl-4,4'-dicarbaldehyde.
2. according to claim 12,2 '-dipyridyl-4, the one-step synthesis of 4 '-dicarbaldehyde is characterized in that, in the said solution A 4,4'-dimethyl--2, the weight ratio of 2'-dipyridyl, iodine and methyl-sulphoxide is 1:2.76～3.31:5～10; Temperature is that 120～140 ℃ hot methyl-sulphoxide consumption is 4,4'-dimethyl--2,15～25 times of 2'-dipyridyl weight.
3. according to claim 12,2 '-dipyridyl-4, the one-step synthesis of 4 '-dicarbaldehyde is characterized in that, said alkali lye is saturated yellow soda ash, sodium hydrogencarbonate, salt of wormwood or potassium bicarbonate aqueous solution.
4. according to claim 12,2 '-dipyridyl-4, the one-step synthesis of 4 '-dicarbaldehyde is characterized in that, filtrating extraction solvent for use is chloroform, methylene dichloride or 1, the 2-ethylene dichloride.
5. according to claim 12,2 '-dipyridyl-4, the one-step synthesis of 4 '-dicarbaldehyde is characterized in that, used siccative is SODIUM SULPHATE ANHYDROUS 99PCT, anhydrous magnesium sulfate or Calcium Chloride Powder Anhydrous when dry.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988008419A1 (en) * | 1987-04-30 | 1988-11-03 | Compagnie Oris Industrie S.A. | Oligobipyridine ligands, process for obtaining them and application as complexing agents |
| TW200728409A (en) * | 2005-10-19 | 2007-08-01 | Jsr Corp | A pigment and pigment-sensitized solar battery |
| US20100317858A1 (en) * | 2006-12-08 | 2010-12-16 | National Institute Of Advance Industrial Science And Technology | Metal coordination compound and light-emitting material containing the same |
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2011
- 2011-12-08 CN CN2011104046246A patent/CN102532005A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988008419A1 (en) * | 1987-04-30 | 1988-11-03 | Compagnie Oris Industrie S.A. | Oligobipyridine ligands, process for obtaining them and application as complexing agents |
| TW200728409A (en) * | 2005-10-19 | 2007-08-01 | Jsr Corp | A pigment and pigment-sensitized solar battery |
| US20100317858A1 (en) * | 2006-12-08 | 2010-12-16 | National Institute Of Advance Industrial Science And Technology | Metal coordination compound and light-emitting material containing the same |
Non-Patent Citations (4)
| Title |
|---|
| 《New Journal of Chemistry》 20011207 Olivier Maury,等 Design and synthesis of 4,4'-pi-conjugated[2,2']-bipyridines: a versatile class of tunable chromophores and fluorophores 第1553-1566页 1-5 第25卷, 第12期 * |
| ARIANE ANGELOFF,等: "The Ligand 1,10-Phenanthroline-2,9-dicarbaldehyde Dioxime can Act Both as a Tridentate and as a Tetradentate Ligand - Synthesis, Characterization and Crystal Structures of its Transition Metal Complexes", 《EUR. J. INORG. CHEM.》 * |
| OLIVIER MAURY,等: "Design and synthesis of 4,4’-π-conjugated[2,2’]-bipyridines: a versatile class of tunable chromophores and fluorophores", 《NEW JOURNAL OF CHEMISTRY》 * |
| 徐建明,等: "2-吡啶甲醛和2,4-吡啶二甲醛的简便合成", 《中国医药工业杂志》 * |
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