CN102702083B - Synthetic method of 4,4'-dihydroxymethyl-2,2'-bipyridyl - Google Patents
Synthetic method of 4,4'-dihydroxymethyl-2,2'-bipyridyl Download PDFInfo
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Abstract
The invention relates to a synthetic method of 4,4'-dihydroxymethyl-2,2'-bipyridyl. The synthetic method comprises the following steps of 1) N-oxidization: 4,4'-dimethyl-2,2'-bipyridyl and glacial acetic acid are mixed, then, hydrogen peroxide aqueous solution is added at 65 to 85 DEG C, next, the backflow is carried out for 5 to 10 hours, the materials are cooled to the room temperature, and products 1 are obtained through reduced pressure distillation; 2) rearrangement acetylization: the products 1 and acetic anhydride with the temperature being 90 to 100 DEG C are mixed, then, the backflow is carried out for 2 to 3 hours, the materials are cooled to the room temperature, water is added for dilution, next, alkali liquor is used for regulating the pH value to be 8 to 9, organic solvents are used for extraction, organic phases are collected and are subjected to drying, concentration and chromatography column separation, and products 2 are obtained; and 3) hydrolysis: the products 2, the water and solid alkali are mixed, then, the backflow is carried out for 2 to 3 hours, the materials are cooled to the room temperature after the backflow completion, organic solvents are used for extraction, organic phases are collected and are subjected to drying and concentration, and target products are obtained. The synthetic method has the advantages that the operation is simple and convenient, the use of easy-to-cause-pollution substances such as sulfuric acid, chromium oxides and the like is avoided in the reaction process, and the pollution is little.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of 4,4'-dihydroxymethyl-2, the synthetic method of 2'-dipyridyl.
background technology
Bipyridyliums derivative is the important dye well midbody compound of a class, can form the title complex with conjugated electrons system with the various metals such as ruthenium, has significant opto-electronic conversion effect.This compounds, as energy converslon materials-dye sensitizing agent, plays an important role in dye sensitization solar battery research and application.4,4'-dihydroxymethyl-2,2'-dipyridyl is the important one in this compounds, itself can be used as dyestuff or prepares other dyestuff intermediate.Ciana etc. propose a kind of 4,4'-dihydroxymethyl-2, synthetic method (the Journal of Heterocyclic Chemistry of 2'-dipyridyl, 1990,27 (2): 163-5), it is with 4,4'-dimethyl-2,2'-dipyridyl is raw material, obtains 2,2'-dipyridyl-4 through oxidation, 4'-dioctyl phthalate, then obtain 4,4'-dihydroxymethyl-2,2'-dipyridyl through esterification, reduction.This synthetic method needs a large amount of materials such as sulfuric acid, chromated oxide that use in the time of oxidation, produces problem of environmental pollution.
Summary of the invention
The object of the invention is to provide a kind of 4,4'-dihydroxymethyl-2, the synthetic method of 2'-dipyridyl, the method is with 4,4'-dimethyl-2, and 2'-dipyridyl is raw material, in reaction process, avoiding the material that has used sulfuric acid and chromated oxide etc. easily to pollute, is a kind of comparatively green synthetic method.
For achieving the above object, the present invention adopts following technical scheme:
A kind of 4,4'-dihydroxymethyl-2, the synthetic method of 2'-dipyridyl, it comprises the steps:
1) N-oxidation: by 4,4'-dimethyl-2, after 2'-dipyridyl mixes with Glacial acetic acid, under agitation condition, in 65～85 DEG C of aqueous hydrogen peroxide solutions that add mass concentration 30%, 5～10h then refluxes, after finishing, backflow is cooled to room temperature, underpressure distillation (water etc. generating in order to remove remaining Glacial acetic acid and reaction) product 1, wherein, feed ratio is by every 1g 4,4'-dimethyl-2,2'-dipyridyl adds 6.5～15ml Glacial acetic acid, 3～7.5ml aqueous hydrogen peroxide solution meter;
2) reset acetylize: the diacetyl oxide that is 90～100 DEG C by product 1 and temperature mixes, then stirring and refluxing 2～3h, after finishing, backflow is cooled to room temperature, thin up (adding 10～20ml water with 1g solid 1 is advisable), then regulate pH value to 8～9 with alkali lye, with organic solvent extraction and collect organic phase, after organic phase drying, concentrated, chromatography column separate product 2, feed ratio adds 3～4.5ml diacetyl oxide by every 1g product 1;
3) hydrolysis: 2～3h refluxes after product 2, water and solid alkali are mixed, after finishing, backflow is cooled to room temperature, with organic solvent extraction and collect organic phase, organic phase drying, concentratedly obtain target product 3, feed ratio adds 10～18ml water, 0.5～0.6g solid alkali by every 1g product 2.
Concrete, extracting organic solvent used is chloroform, methylene dichloride or ethyl acetate etc.
Step 2) in alkali lye used be sodium hydroxide or the potassium hydroxide aqueous solution etc. of mass concentration 20～40%; In step 3), solid alkali used is NaOH or KOH etc.
Step 2) in organic phase dry siccative used can be the common agents of this area, as anhydrous sodium sulphate, anhydrous magnesium sulfate, anhydrous calciumsulphate, Calcium Chloride Powder Anhydrous etc.In step 3), the dry siccative used of organic phase can be anhydrous sodium sulphate, anhydrous magnesium sulfate, anhydrous calciumsulphate etc.
The synthetic route of the inventive method is as follows:
The inventive method is with 4,4'-dimethyl-2, and 2'-dipyridyl is raw material, through N-be oxidized dipyridyl N-oxide compound, obtain target product 4,4'-dihydroxymethyl-2,2'-dipyridyl (171～174 DEG C of fusing points) through resetting acetylize, hydrolysis reaction again.This synthetic method is easy and simple to handle, avoids the material that uses sulfuric acid and chromated oxide etc. easily to pollute in reaction process, and less pollution, is a kind of comparatively green synthetic method.
Brief description of the drawings
Fig. 1 is the product mass spectrum result that adopts synthetic method of the present invention to make.Mass spectrograph model QP-5000, Japanese Shimadzu company produces, and can find out that by mass spectrum the molecular weight product making is 216, in conjunction with 171～174 DEG C of fusing points, confirms that product is 4,4'-dihydroxymethyl-2,2'-dipyridyl.
embodiment
By several preferred embodiments, synthetic method of the present invention is described in further detail below, but protection scope of the present invention is not limited to this.
embodiment 1
A kind of 4,4'-dihydroxymethyl-2, the synthetic method of 2'-dipyridyl, it comprises the steps:
1) N-oxidation: by 2 g 4,4'-dimethyl-2, after 2'-dipyridyl mixes with 24 ml Glacial acetic acid, under agitation condition in 75 DEG C of aqueous hydrogen peroxide solutions that add 10 ml mass concentrations 30%, then 8h refluxes, after finishing, backflow is cooled to room temperature, and concentrated through rotary evaporation, obtain 2.1 g faint yellow solid products 1;
2) reset acetylize: get 8 ml diacetyl oxides and be heated to 95 DEG C, then add 2g product 1, stirring and refluxing 2.5h, after finishing, backflow is cooled to room temperature, add the dilution of 30ml water, then regulate pH value to 8.5 with the aqueous sodium hydroxide solution of mass concentration 40%, be extracted with ethyl acetate (24 ml × 3 time) and collect organic phase, organic phase is concentrated through anhydrous sodium sulfate drying, rotary evaporation, chromatography column obtains 1.4 g yellow solid product 2 after separating;
3) hydrolysis: backflow 2.5h after 2g product 2,30ml water and 1g potassium hydroxide are mixed, thin-layer chromatographic analysis is cooled to room temperature after refluxing and finishing, with chloroform extraction (18 ml × 3 time) and collect organic phase, organic phase obtains 1.1g white solid through anhydrous magnesium sulfate drying, concentrated evaporate to dryness, it is target product 4,4'-dihydroxymethyl-2,2'-dipyridyl.
embodiment 2
A kind of 4,4'-dihydroxymethyl-2, the synthetic method of 2'-dipyridyl, it comprises the steps:
1) N-oxidation: by 2 g 4,4'-dimethyl-2, after 2'-dipyridyl mixes with 14 ml Glacial acetic acid, under agitation condition in 65 DEG C of aqueous hydrogen peroxide solutions that add 6 ml mass concentrations 30%, then 10h refluxes, after finishing, backflow is cooled to room temperature, and concentrated through rotary evaporation, obtain 1.9 g faint yellow solid products 1;
2) reset acetylize: get 6 ml diacetyl oxides and be heated to 90 DEG C, then add 2g product 1, stirring and refluxing 3h, after finishing, backflow is cooled to room temperature, add 20 ml water dilutions, then regulate pH value to 8 with the potassium hydroxide aqueous solution of mass concentration 40%, be extracted with ethyl acetate (24 ml × 3 time) and collect organic phase, organic phase is concentrated through anhydrous sodium sulfate drying, rotary evaporation, chromatography column obtains 1.2 g yellow solid product 2 after separating;
3) hydrolysis: backflow 2h after 2g product 2,20ml water and 1g potassium hydroxide are mixed, thin-layer chromatographic analysis is cooled to room temperature after refluxing and finishing, with chloroform extraction (18 ml × 3 time) and collect organic phase, organic phase obtains 1.0 g white solids through anhydrous magnesium sulfate drying, concentrated evaporate to dryness, it is target product 4,4'-dihydroxymethyl-2,2'-dipyridyl.
embodiment 3
A kind of 4,4'-dihydroxymethyl-2, the synthetic method of 2'-dipyridyl, it comprises the steps:
1) N-oxidation: by 2 g 4,4'-dimethyl-2, after 2'-dipyridyl mixes with 30 ml Glacial acetic acid, under agitation condition in 85 DEG C of aqueous hydrogen peroxide solutions that add 15ml mass concentration 30%, then 6h refluxes, after finishing, backflow is cooled to room temperature, and concentrated through rotary evaporation, obtain 2.2 g faint yellow solid products 1;
2) reset acetylize: get 9 ml diacetyl oxides and be heated to 98 DEG C, then add 2g product 1, stirring and refluxing 2h, after finishing, backflow is cooled to room temperature, add the dilution of 40ml water, then regulate pH value to 9 with the potassium hydroxide aqueous solution of mass concentration 40%, be extracted with ethyl acetate (30 ml × 3 time) and collect organic phase, organic phase is concentrated through anhydrous sodium sulfate drying, rotary evaporation, chromatography column obtains 1.6 g yellow solid product 2 after separating;
3) hydrolysis: backflow 3h after 2 g products 2,36ml water and 1.2g potassium hydroxide are mixed, thin-layer chromatographic analysis is cooled to room temperature after refluxing and finishing, with chloroform extraction (24 ml × 3 time) and collect organic phase, organic phase obtains 1.2 g white solids through anhydrous magnesium sulfate drying, concentrated evaporate to dryness, it is target product 4,4'-dihydroxymethyl-2,2'-dipyridyl.
Claims (1)
1. one kind 4,4'-dihydroxymethyl-2, the synthetic method of 2'-dipyridyl, is characterized in that, comprises the steps:
1) N-oxidation: by 2 g 4,4'-dimethyl-2, after 2'-dipyridyl mixes with 30 ml Glacial acetic acid, under agitation condition in 85 DEG C of aqueous hydrogen peroxide solutions that add 15ml mass concentration 30%, then 6h refluxes, after finishing, backflow is cooled to room temperature, and concentrated through rotary evaporation, obtain 2.2 g faint yellow solid products 1;
2) reset acetylize: get 9 ml diacetyl oxides and be heated to 98 DEG C, then add 2g product 1, stirring and refluxing 2h, after finishing, backflow is cooled to room temperature, add the dilution of 40ml water, then regulate pH value to 9 with the potassium hydroxide aqueous solution of mass concentration 40%, be extracted with ethyl acetate and collect organic phase, organic phase is concentrated through anhydrous sodium sulfate drying, rotary evaporation, chromatography column obtains 1.6 g yellow solid product 2 after separating;
3) hydrolysis: backflow 3h after 2 g products 2,36ml water and 1.2g potassium hydroxide are mixed, thin-layer chromatographic analysis is cooled to room temperature after refluxing and finishing, with chloroform extraction and collect organic phase, organic phase obtains 1.2 g white solids through anhydrous magnesium sulfate drying, concentrated evaporate to dryness, it is target product 4,4'-dihydroxymethyl-2,2'-dipyridyl.
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| CN106000386B (en) * | 2016-05-31 | 2018-08-14 | 河南省商业科学研究所有限责任公司 | A kind of catalyst and the method using catalyst preparation 2,2 '-bipyridyl-the 4,4 '-diacrylate |
| CN115010654A (en) * | 2022-06-14 | 2022-09-06 | 南京红太阳生物化学有限责任公司 | Green synthesis process of 2,2' -bipyridine |
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Non-Patent Citations (4)
| Title |
|---|
| ColinP.Horwitz et al..Oxidative Electropolymerization of Iron and Ruthenium Complexes Containing Aniline-Substituted 2 |
| Oxidative Electropolymerization of Iron and Ruthenium Complexes Containing Aniline-Substituted 2,2’-Bipyridine Ligands;Colin P. Horwitz, et al.;《Inorg. Chem.》;19921231;第31卷(第9期);1607-1613 * |
| RobertS.Ward et al..SYNTHESIS OF C2 SYMMETRIC 2 |
| SYNTHESIS OF C2 SYMMETRIC 2,2’-BIPYRIDYL IMIDAZOLIDINONE AND OXAZABOROLIDINE DERIVATIVES;Robert S. Ward, et al.;《HETEROCYCLES》;20021231;第56卷;157-169 * |
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