CN102304080A - Method for preparing divinyl dipyridine compounds - Google Patents
Method for preparing divinyl dipyridine compounds Download PDFInfo
- Publication number
- CN102304080A CN102304080A CN201110123157A CN201110123157A CN102304080A CN 102304080 A CN102304080 A CN 102304080A CN 201110123157 A CN201110123157 A CN 201110123157A CN 201110123157 A CN201110123157 A CN 201110123157A CN 102304080 A CN102304080 A CN 102304080A
- Authority
- CN
- China
- Prior art keywords
- dipyridyl
- divinyl
- diethylmethyl
- acid esters
- phosphorous acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a method for preparing 4,4'-divinyl-2,2'-dipyridine. The method comprises: reacting 4,4'- dibromomethyl-2,2'-dipyridine with triethyl phosphate to obtain triethyl phosphate to obtain 4,4'-bis(diethylmethylphosphite)-2,2'-dipyridine (Wittig-Horner reagent); and performing the Horner-Emmons-Wadsworth reaction of the 4,4'-bis(diethylmethylphosphite)-2,2'-dipyridine and 37-percent formaldehyde solution to obtain4,4'-diethyl-2,2'-dipyridine. Compared with the prior art, the method has the characteristics of low raw material price, mild reaction conditions, easy product separation, simple and convenient operation, high yield and the like.
Description
Technical field
The present invention relates to a kind of Chemicals and technology of preparing thereof, be specially a kind of preparation method of divinyl bipyridyliums compound.
Background technology
Metal complex often forms film through polyreaction attached to electrode surface, carries out oxidation or reduction reaction, studies the film forming new ligand molecular of new reaction and polymerizable and always is hot fields.Reported 4-methyl-4 '-divinyl-2 for the first time from Spiro and Ghosh; Since the preparation of 2 '-dipyridyl; This material just becomes frequent thickness and the stabilizing layer that uses aspect preparation solid-phase catalyst and electroactive polymer film; In order to obtain enough thickness and stabilizing layer, be necessary to add and contain two monomeric compounds of electric polymerizable vinyl and central metal ion composition title complex at least.In addition, this compounds also can be used for making the fluorescence chemical sensing material of highly sensitive and high sensing capability; After can forming part with ruthenium, manufacturing property is optoelectronic equipment preferably; Can form part with iron, be used for electrochemical oxidation and reduction reaction or the like.Therefore, such material is with a wide range of applications, it typically represents, also be use more promptly 4,4 '-divinyl-2,2 '-dipyridyl, study this material safely and efficiently the preparation method have certain realistic meaning.
Leopoldo Della Ciana etc. once reported the preparation method (J.Heterocyclic.Chem.1990 of this material; 27; 163-165); But this method steps is comparatively loaded down with trivial details; Bigger and the adventurous reagent of toxicity such as tin anhydride, chloroform, sodium amide in preparation, have been used; And reaction requires anhydrous condition, and is comparatively harsh.Sharon Gould etc. has reported a kind of more succinct preparation 4,4 '-two brooethyls-2, the method for 2 '-dipyridyl (Inorg.Chem.1991; 30; 2942-2949), with 4,4 '-dimethyl-2; 2 '-dipyridyl is a reactant; With N-bromo-succinimide (NBS) reaction, a step obtains 4,4 '-two brooethyls-2 under the initiator effect; 2 '-dipyridyl, productive rate are about 30-40%.Advantages such as the shortcoming of this method is that productive rate is on the low side, but it is short to have synthetic route, and is easy to operate, and aftertreatment is simple.The present invention carries out subsequent reactions based on this, prepared purity higher 4,4 '-divinyl-2,2 '-dipyridyl.
Summary of the invention
To the synthesis step more complicated of divinyl dipyridyl, aftertreatment is loaded down with trivial details and productive rate is not high at present.The purpose of this invention is to provide a kind of preparation 4,4 '-divinyl-2, the method for 2 '-dipyridyl.Preparation 4 provided by the invention; 4 '-divinyl-2; 2 '-dipyridyl method compares with existing method that to have a cost of material cheap, and reaction conditions is gentle, and product is easily separated; Easy and simple to handle; Productive rate is than characteristics such as height, to 4, and 4 '-divinyl-2; This suitability for industrialized production at widely used products of numerous areas such as basic science and study on the industrialization of 2 '-dipyridyl provides a route that operability is stronger, has important practical significance and economic worth.A kind of preparation 4 provided by the invention, 4 '-divinyl-2, the method for 2 '-dipyridyl, its concrete steps are following, and wherein (2) (3) two step is crucial innovative step:
(1) 4,4 '-two brooethyls-2,2 '-dipyridyl synthetic: with commercially available 4; 4 '-dimethyl-2,2 '-dipyridyl are initial reactant, in the presence of initiator Diisopropyl azodicarboxylate (AIBN); With N-bromo-succinimide (NBS) in tetracol phenixin back flow reaction 2-20 hour; Reduce to room temperature, suction filtration reactant, the insoluble material of elimination; Revolve to steam to remove and desolvate; Can obtain 4,4 '-two brooethyls-2,2 '-dipyridyl.
(2) 4; 4 '-two (diethylmethyl phosphorous acid esters)-2,2 '-dipyridyl (Wittig-Horner reagent) synthetic: with 4,4 '-two brooethyls-2; 2 '-dipyridyl mixes with a certain amount of triethyl-phosphite; At room temperature to the temperature range internal reaction that refluxes 4-24 hour, reduce to room temperature, unnecessary triethyl-phosphite underpressure distillation is removed; Vacuum-drying; Get 4,4 '-two (diethylmethyl phosphorous acid esters)-2,2 '-dipyridyl;
(3) 4; 4 '-divinyl-2; Synthetic (the Horner-Emmons-Wadsworth reaction) of 2 '-dipyridyl: with 4; 4 '-two (diethylmethyl phosphorous acid esters)-2; 2 '-dipyridyl and methylene dichloride, 37% formalin mix stirring; Obtaining the outstanding absurd creature of white, under the nitrogen protection, cryosel bathes and to be cooled to-8--2 degree centigrade; In 10-180 minute, drip in 1%-15% sodium hydroxide solution to the above-mentioned reaction system, dropwise back insulation 30-60 minute, remove cryosel and bathe; Stirring at normal temperature is spent the night; Stopped reaction, the water layer dichloromethane extraction merges organic phase; With carrying out drying with anhydrous sodium sulphate after the saturated common salt water washing; Revolve and boil off, obtain 4,4 '-divinyl-2 except that methylene dichloride; 2 '-dipyridyl, productive rate 60%-90%.
Provided by the present invention 4,4 '-divinyl-2, the synthesis method of 2 '-dipyridyl; Its crucial innovative step compared with prior art; Employedly be common organic reaction, reaction conditions is relatively gentleer, has avoided the harsh waterless operation of condition and the use of hypertoxic hazardous chemicals as far as possible; And has productive rate preferably; Final product is easy to separate, in laboratory and industry, all carries out easily, and be 4; 4 '-divinyl-2, the extensive magnitude production at 2 '-Lian pyrrole place provides a practical way.
Embodiment
With embodiment the present invention is made below and further specifying.
Embodiment 1
(1) 4,4 '-two brooethyls-2,2 '-dipyridyl synthetic: in 300 milliliters of tetracol phenixin, add 8 grams 4,4 '-dimethyl-2,2 '-dipyridyl and 24 gram N-bromo-succinimides (NBS), and 1 restrain Diisopropyl azodicarboxylate.Reflux 3 hours, the frozen water cooling removes by filter insolubles.Revolve and desolvate, obtain product 4,4 '-two brooethyls-2 of light brown, 2 '-dipyridyl, 5.2 grams, productive rate 35%
(2) 4,4 '-two (diethylmethyl phosphorous acid esters)-2,2 '-dipyridyl (Wittig-Horner reagent) synthetic: with 6.8 grams, 4,4 '-two brooethyls-2,2 '-dipyridyl mixes stirring with the 60ml triethyl-phosphite, and back flow reaction was reduced to room temperature after 4.5 hours.Unreacted triethyl-phosphite is removed in underpressure distillation, and residuum places refrigerator and cooled to hide after 1 hour and takes out, and is cured as dark brown solid; With 100 milliliters of ether washings, 50 degrees centigrade of following vacuum-dryings get 4; 4 '-two (diethylmethyl phosphorous acid esters)-2,2 '-dipyridyl, 8.2 grams, productive rate 90%;
(3) 4; 4 '-divinyl-2; Synthesizing of 2 '-dipyridyl: with 2.3 grams 4; 4 '-two (diethylmethyl phosphorous acid esters)-2; 2 '-dipyridyl and 40 milliliters of methylene dichloride, 12 milliliter of 37% formalin mix stirring; Obtain the outstanding absurd creature of white, under the nitrogen protection, cryosel is bathed and is cooled to-8 degrees centigrade; In 30 minutes, drip in 20 milliliter of 10% sodium hydroxide solution to the above-mentioned reaction system, dropwise the back and be incubated half an hour, remove cryosel and bathe; Stir overnight under the normal temperature, stopped reaction, water layer dichloromethane extraction; Merge organic phase; Behind saturated common salt water washing dichloromethane layer, carry out drying with anhydrous sodium sulphate, filter; Revolve to boil off except that methylene dichloride and get light yellow solid 4; 4 '-divinyl-2,2 '-dipyridyl, 0.8 gram, productive rate 77%.
Embodiment 2
(1) 4,4 '-two brooethyls-2,2 '-dipyridyl synthetic: in 400 milliliters of tetracol phenixin, add 18.4 grams 4,4 '-dimethyl-2,2 '-dipyridyl and 48 gram N-bromo-succinimides (NBS), and 1 restrain Diisopropyl azodicarboxylate.Reflux 8 hours, the frozen water cooling removes by filter insolubles.Revolve and desolvate, obtain brown product 4,4 '-two brooethyls-2,2 '-dipyridyl, 12.6 grams, productive rate 37%
(2) 4; 4 '-two (diethylmethyl phosphorous acid esters)-2; Synthesizing of 2 '-dipyridyl (Wittig-Horner reagent): with 17.1 grams 4; 4 '-two brooethyls-2; 2 '-dipyridyl and 90 milliliters of triethyl-phosphites stir; Be heated to backflow, react and reduce to room temperature after 8 hours, unreacted triethyl-phosphite is removed in underpressure distillation; Residuum places refrigerator and cooled to hide after 1 hour; Be cured as dark brown solid, with 150 milliliters of ether washings, 50 degrees centigrade of following vacuum-dryings; Get 4; 4 '-two (diethylmethyl phosphorous acid esters)-2,2 '-dipyridyl, 19.4 grams, productive rate 85%;
(3) 4; 4 '-divinyl-2; Synthesizing of 2 '-dipyridyl: with 9.1 grams 4; 4 '-two (diethylmethyl phosphorous acid esters)-2; 2 '-dipyridyl and 80 milliliters of methylene dichloride, 20 milliliter of 37% formalin mix stirring; Obtain the outstanding absurd creature of white, under the nitrogen protection, cryosel is bathed and is cooled to-5 degrees centigrade; In 50 minutes, drip in 60 milliliter of 10% sodium hydroxide solution to the above-mentioned reaction system; Dropwise back insulation 1 hour, remove cryosel and bathe stir overnight under the normal temperature; Stopped reaction; The water layer dichloromethane extraction merges organic phase, with carrying out drying with anhydrous sodium sulphate after the saturated common salt water washing; Revolve to boil off except that methylene dichloride and get light yellow solid 4; 4 '-divinyl-2,2 '-dipyridyl, 3.5 grams, productive rate 85%.
Spectral data
1H nuclear magnetic resonance spectrum (300MHz)
4,4 '-two brooethyls-2,2 '-dipyridyl (CDCl
3) δ (ppm): 4.47 (unimodal, 4H), 7.35 (bimodal, bimodal, 2H), 8.42 (bimodal, 2H), 8.65 (bimodal, 2H).
4,4 '-divinyl-2,2 '-dipyridyl (CDCl
3) δ (ppm): 5.51 (bimodal, 2H), 6.08 (bimodal, 2H), 6.75 (bimodal, bimodal, 2H), 7.32 (bimodal, bimodal, 2H), 8.39 (bimodal, 2H), 8.61 (bimodal, 2H),
Ultimate analysis
4,4 '-two brooethyls-2,2 '-dipyridyl (molecular formula C
12H
10N
2Br
2): calculated value C, 42.14; H, 2.95; N, 8.19. analytical value: C, 42.03; H, 3.09; N, 8.38.
4,4 '-divinyl-2,2 '-dipyridyl (molecular formula C
11H
12N
2): calculated value C, 80.74; H, 5.81; N, 13.45. analytical value: C, 80.59; H, 5.90; N, 13.40.
Claims (3)
1. one kind prepares 4,4 '-divinyl-2, and the method for 2 '-dipyridyl, this method are by 4, and 4 '-dimethyl-2,2 '-dipyridyl are initial feed, through generating 4,4 '-two brooethyls-2,2 '-dipyridyl with N-bromo-succinimide (NBS) reaction; It is characterized in that comprising following subsequent step:
(1) 4; 4 '-two (diethylmethyl phosphorous acid esters)-2, synthetic (the Wittig-Horner reagent) of 2 '-dipyridyl: with 4,4 '-two brooethyls-2; 2 '-dipyridyl mixes with a certain amount of triethyl-phosphite; Control is reacted and is reduced to room temperature after 4-24 hour at a certain temperature, removes unnecessary triethyl-phosphite; The suction filtration reactant; Seasoning gets 4,4 '-two (diethylmethyl phosphorous acid esters)-2,2 '-dipyridyl; (2) 4; 4 '-divinyl-2; Synthetic (the Horner-Emmons-Wadsworth reaction) of 2 '-dipyridyl: with 4; 4 '-two (diethylmethyl phosphorous acid esters)-2; 2 '-dipyridyl and methylene dichloride, 37% formalin mix stirring; Obtaining the outstanding absurd creature of white or xanchromatic, under the nitrogen protection, cryosel or ice-water bath be cooled to-10--2 degree centigrade; In 10-180 minute, drip in 1%-15% sodium hydroxide solution to the above-mentioned reaction system, dropwise back insulation 30-60 minute, remove cryosel and bathe; Stirring at normal temperature is spent the night; Stopped reaction, the water layer dichloromethane extraction merges organic phase; After the saturated common salt water washing; Carry out drying with anhydrous sodium sulphate, revolve to steam and remove methylene dichloride, get 4; 4 '-divinyl-2,2 '-dipyridyl.
2. a kind of preparation 4 according to claim 1,4 '-divinyl-2, the method for 2 '-dipyridyl is characterized in that, described 4,4 '-two brooethyls-2,2 '-dipyridyl is 1 with the ratio of the amount of triethyl-phosphite: 2.5-1: 30.
3. a kind of preparation 4 according to claim 1; 4 '-divinyl-2; The method of 2 '-dipyridyl; It is characterized in that described 4,4 '-two (diethylmethyl phosphorous acid esters)-2; The ratio of each amount is in 2 '-dipyridyl, sodium hydroxide, the formaldehyde solution system: 4; 4 '-two (diethylmethyl phosphorous acid esters)-2,2 '-dipyridyl: sodium hydroxide=1: 5-1: 20, sodium hydroxide: formaldehyde solution=1: 3-1: 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110123157A CN102304080A (en) | 2011-05-13 | 2011-05-13 | Method for preparing divinyl dipyridine compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110123157A CN102304080A (en) | 2011-05-13 | 2011-05-13 | Method for preparing divinyl dipyridine compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102304080A true CN102304080A (en) | 2012-01-04 |
Family
ID=45378019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110123157A Pending CN102304080A (en) | 2011-05-13 | 2011-05-13 | Method for preparing divinyl dipyridine compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102304080A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114569612A (en) * | 2022-03-15 | 2022-06-03 | 江苏科技大学 | Application of bipyridine in prevention and treatment of silkworm myiasis |
| CN115417809A (en) * | 2022-09-05 | 2022-12-02 | 天津药明康德新药开发有限公司 | Preparation method of 4, 4-dipyrrole-2, 2-bipyridine |
-
2011
- 2011-05-13 CN CN201110123157A patent/CN102304080A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114569612A (en) * | 2022-03-15 | 2022-06-03 | 江苏科技大学 | Application of bipyridine in prevention and treatment of silkworm myiasis |
| CN114569612B (en) * | 2022-03-15 | 2024-02-27 | 江苏科技大学 | Application of bipyridine in preventing and treating silkworm maggot disease |
| CN115417809A (en) * | 2022-09-05 | 2022-12-02 | 天津药明康德新药开发有限公司 | Preparation method of 4, 4-dipyrrole-2, 2-bipyridine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ramya et al. | Highly luminescent and thermally stable lanthanide coordination polymers designed from 4-(dipyridin-2-yl) aminobenzoate: efficient energy transfer from Tb3+ to Eu3+ in a mixed lanthanide coordination compound | |
| Fei et al. | Metal− Organic Frameworks Derived from Imidazolium Dicarboxylates and Group I and II Salts | |
| Zhang et al. | Coordination-induced syntheses of two hybrid framework iodides: A thermochromic luminescent thermometer | |
| Sindhuja et al. | Palladium (ii) thiocarboxamide complexes: synthesis, characterisation and application to catalytic Suzuki coupling reactions | |
| CN103242300B (en) | N-heterocyclic carbene metal complex based on quinoxaline as well as preparation method and application thereof | |
| Tschan et al. | Zinc and cobalt complexes based on tripodal ligands: synthesis, structure and reactivity toward lactide | |
| Li et al. | Calix [4] arene containing thiourea and coumarin functionality as highly selective fluorescent and colorimetric chemosensor for fluoride ion | |
| Amatori et al. | Modulating the sensor response to halide using NBD-based azamacrocycles | |
| Pandiarajan et al. | Suzuki–Miyaura cross-coupling reaction of aryl bromides catalyzed by palladium (II) pyridoxal hydrazone complexes | |
| CN101402644A (en) | Production method for metal aza ring carbene complex | |
| Ernst et al. | Structural characterization of Cp* Ru‐intermediates of phenylacetylene cyclotrimerization | |
| CN102219797A (en) | N-heterocyclic carbene annular metal complexes, preparation method and purpose thereof | |
| Kumar et al. | Sterically hindered selenoether ligands: Palladium (II) complexes as catalytic activators for Suzuki–Miyaura coupling | |
| CN103664769A (en) | Synthesis method of dipyridyl derivative or analogue | |
| Priyarega et al. | Novel binuclear palladium (II) complexes of 2-oxoquinoline-3-carbaldehyde Schiff bases: Synthesis, structure and catalytic applications | |
| Liu et al. | C 2-Symmetric Hindered “Sandwich” Chiral N-Heterocyclic Carbene Precursors and Their Transition Metal Complexes: Expedient Syntheses, Structural Authentication, and Catalytic Properties | |
| CN103724270A (en) | Alkyl chain chaining-based N-heterocyclic carbene metal complex as well as preparation method and application thereof | |
| Šebová et al. | Structure and magnetism of Co (II) complexes with bidentate heterocyclic ligand Hsalbim derived from benzimidazole | |
| Konar | Dicynamide bridged two new zig-zag 1-D Zn (II) coordination polymers of pyrimidine derived Schiff base ligands: Synthesis, crystal structures and fluorescence studies | |
| Holwerda et al. | Crystal structure, physical properties, and hydrolysis kinetics of [(O)(tmpa) VIV (μ-O) VV (tmpa)(O)] 3+ | |
| CN102304080A (en) | Method for preparing divinyl dipyridine compounds | |
| CN105566358A (en) | Application of cyclic N-heterocyclic carbene metal complex in selective recognition of aromatic compounds | |
| Vicente et al. | New Palladacycles Containing Terdentate [C, N, O] n−(n= 0, 1, 2) or Tetradentate [N, C, O, N′] n−(n= 1, 2) Ligands. The First 1, 2-Dihydroquinazoline-4-yl Complexes | |
| Dickie et al. | Structure of organic and metal− organic networks based on a bifunctional m-terphenyl carboxylic acid | |
| Zhong et al. | Effect of counterions and central cores of tripodal imidazolium salts on palladium-catalyzed Suzuki–Miyaura cross-coupling reactions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120104 |