CN103508941A - 2,4-diphenyl-5,6-bis(2-pyridyl)-phenol and preparation method thereof - Google Patents
2,4-diphenyl-5,6-bis(2-pyridyl)-phenol and preparation method thereof Download PDFInfo
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- CN103508941A CN103508941A CN201310518992.2A CN201310518992A CN103508941A CN 103508941 A CN103508941 A CN 103508941A CN 201310518992 A CN201310518992 A CN 201310518992A CN 103508941 A CN103508941 A CN 103508941A
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- phenylbenzene
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- bipyridyl
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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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
Abstract
The invention discloses a heterocyclic compound 2,4- diphenyl -5,6- bipyridyl-phenol and preparation method thereof belongs to organic chemical synthesis field. It has the following structure formula:
With 2,2 '-two pyridones, for raw material, object is prepared by addition reaction and rearrangement reaction in the present invention. The preparation method can have the compound of expected substituent group by the raw material control synthesis to starting, and synthesis step is simple, reacts and is easy to carry out, cost is relatively low. Heterocyclic compound of the present invention can be used for synthesizing chemistry or fluorescent material.
Description
Technical field
The present invention relates to a heterogeneous ring compound 2,4-phenylbenzene-5,6-bipyridyl-phenol (2,4-diphenyl-5,6-bis (2-pyridyl)-phenol), and its preparation method.Belong to organic chemical synthesis field.
Background technology
Heterogeneous ring compound is the hugest class organic compound of number.Conventionally heterogeneous ring compound is prevalent in drug molecular structure, and the important compound majority relevant with biology is heterogeneous ring compound, such as nucleic acid, some VITAMIN, microbiotic, hormone, pigment and alkaloid etc.At present synthetic diversified heterogeneous ring compound, be widely used in medicine, Insecticides (tech) & Herbicides (tech), dyestuff, plastics etc.
With intermediate product 2 of the present invention, 5-diphenyl-3, the correlative study of 4-bis (2-pyridyl)-cyclopentadienone comprises: fluorescent material (WSS:Spectral data were obtained from Wiley Subscription Services, Inc. (US); Li, Zhanxian; Chemical Communications (Cambridge, United Kingdom) 2011, V47 (20), P5798-5800), coordination chemistry (Siemeling, Ulrich; Zeitschrift fuer Anorganische und Allgemeine Chemie 2008, V634 (5), P895-900), catalyzed reaction (Siemeling, Ulrich; Chemistry-A European Journal 2004, V10 (22), P5661-5670), organic synthesis (Newkome, George R.; Journal of Organic Chemistry 1975, V40 (24), P3514-18) etc.Bogor D. L. reported the complete synthesis reaction of rubrolone aglycon, had wherein used cyclopropnone ketals, in Cheng Huan, on seven-membered ring, formed hydroxyl (
j. Am. Chem. Soc. 2000,
122,12169-12173).Its raw material is complicated, and synthetic what obtain is seven-membered ring.
React close addition rearrangement reaction with the present invention, Zhu G. D. once reported similarly reaction, be by furans react with alkynes (
org. Lett. 2000,
2, 3345-3348).
Recently Wipf P. also reported furans and alkynyl similar reaction (
j. Org. Chem. 2013,
78, 167 174).
Clearly the starting raw material of this class reaction is all furans, on the phenyl ring that makes to generate, is not easy to modify other groups.
Summary of the invention
The object of the invention is to prepare a kind of new heterogeneous ring compound 2,4-phenylbenzene-5, and 6-bipyridyl-phenol (2,4-diphenyl-5,6-bis (2-pyridyl)-phenol) also provides its preparation method.
Employing following methods is synthetic:
Step 1: 2,2 '-bis-pyridones are added in the ethanolic soln of 1,3-diphenyl acetone, drip saturated sodium hydroxide-ethanolic soln after all dissolving, be warming up to backflow, then be cooled to room temperature, through refrigeration, suction filtration, washing, vacuum-drying, obtains 2,5-phenylbenzene-3,4-pyridyl ring pentadienone.
Step 2: by glacial acetic acid, 2,5-phenylbenzene-3, the o-Xylol solution of 4-pyridyl ring pentadienone adds in phenylacetylene, under argon shield, reflux, illumination reaction, except desolventizing.Cross post and purify, obtain solid powder sample.
The proton environment that in the present invention, product preparation needs glacial acetic acid to provide, and need illumination and control applicable temperature, in preparation process, need to occur addition reaction and rearrangement reaction.
Preparation method of the present invention can control the synthetic compound with expection substituted radical by the raw material to initial, and synthesis step is simple, and reaction is easily carried out, and cost is lower.Heterogeneous ring compound of the present invention can be for the synthesis of chemistry or fluorescent material.
Accompanying drawing explanation
Fig. 1 is the x-diffractogram of the compounds of this invention;
Fig. 2 is the uv-absorbing spectrogram of the compounds of this invention; In figure, 1 represents methylene dichloride, and 2 represent normal hexane, and 7 represent ethanol, and other curve represents respectively hexanaphthene, toluene, ethyl acetate, tetrahydrofuran (THF), acetonitrile, methyl alcohol, chloroform;
Fig. 3 is the fluorescence spectrum figure of the compounds of this invention; In figure, 1 represents methylene dichloride, and 2 represent normal hexane, and 3 represent hexanaphthene, and 4 represent toluene, and 5 represent ethyl acetate, and 6 represent tetrahydrofuran (THF), and 7 represent ethanol, and 8 represent acetonitrile, and 9 represent methyl alcohol, and 10 represent chloroform.
Embodiment
Specific embodiment is described the present invention in detail below, and described embodiment is used for describing the present invention, rather than restriction the present invention.
Embodiment
Synthesis step: by 1 of 635.9 mg, 3-diphenyl acetone is dissolved in 6 mL ethanol, adds in the two-mouth bottle of 25 mL, then adds 2,2 of 638.4 mg '-bis-pyridones.After all dissolving, drip saturated sodium hydroxide-ethanolic soln (93.9 mg KOH solids are dissolved in 2 mL ethanol), be warming up to backflow, after 5 min, stop, after cooling, put into refrigerator cold-storage 5 h, suction filtration, uses respectively distilled water and absolute ethanol washing three times, after vacuum-drying, obtaining yellow solid is intermediate product 855 mg, productive rate 74%.
1H?NMR?(400MHz,?CDCl
3,?ppm):?8.45?(m,?1H),?8.32?(m,?1H),?7.72?(m,?2H),?7.64?(m,?5H),?7.39?(m,?3H),?7.27?(m,?1H),?7.10?(m,?4H),?6.65?(m,?1H).?
13C?NMR:?(100?MHz,?CDCl
3,?ppm):?205.82,?164.10,?163.59,?154.01,?148.86,?141.58,?136.43,?136.27,?134.60,?130.64,?129.89,?129.50,?128.78,?128.71,?128.50,?128.02,?127.55,?127.29,?125.80,?123.41,?121.80,?120.94.
By 0.15 mL glacial acetic acid; 0.1932 g (0.5 mmol) 2; 5-phenylbenzene-3; 4-pyridyl ring pentadienone adds in 25 mL two-mouth bottles, adds 15 mL o-Xylols to dissolve, and then adds 0.15 mL (1.36 mmol) phenylacetylene; under argon shield; take out inflation three times, be heated to reflux, stop after reacting 24 h.After cooling, revolve steaming, except desolventizing, sherwood oil: ethyl acetate=1:1 crosses post, obtains light yellow solid powder 85 mg, productive rate: 37%.
1HNMR?(400MHz,?DMSO,?ppm):?8.237-8.225?(d,?1H),?8.093?(s,?1H),?7.682-7.662?(m,?2H),?7.488-7.450?(m,?2H),?7.390-7.331?(m,?2H),?7.254?(s,?1H),?7.170-6.959?(m,?9H),?6.947-6.929?(m,?1H),?6.894-6.876?(t,?1H).?
13CNMR?(100MHz,?CDCl
3,?ppm):?158.12,?148.20,?141.33,?140.86,?139.33,?139.01,?138.32,?134.64,?131.86,?131.17,?129.80,?127.75,?120.38,?120.20。
By gained compound 2,4-phenylbenzene-5,6-bipyridyl-phenol is slowly volatilization in methyl alcohol, obtains the crystal of this compound after the week.
Crystalline structure is shown in accompanying drawing 1.From accompanying drawing 2 UV spectrum, we can see that it absorbs all at ultraviolet region different solvents, so the not aobvious color of solution.From accompanying drawing 3 fluorescence spectrums can see this compound and under the optical excitation of 300 nm in compound methylene dichloride emmission spectrum be obviously better than other solvents, in methylene dichloride, can send stronger hepatic fluorescence, luminous very Ruo Qiebu visible region in other solvents.This compound can further be modified fields such as being applied to fluorescence sense, coordination, catalysis, organic synthesis.
table one crystal data
| Empirical formula | C 29H 24N 2O 2 |
| Formula weight | 432.50 |
| Crystal size [mm] | 0.33×0.26×0.21 |
| Crystal system | triclinic |
| Space group | P-1 |
| a [?] | 9.3249(5) |
| b [?] | 10.9923(6) |
| c [?] | 11.9067(7) |
| α [deg] | 78.845(5) |
| β [deg] | 88.741(4) |
| γ [deg] | 86.513(4) |
| Volume [? 3], Z | 1195.12(12), 2 |
| Dcalcd. [g/cm 3] | 1.202 |
| μ [mm -1], F (000) | 0.076, 456.0 |
| Reflections collected | 5463 |
| Unique reflections | 2364 |
| Rint | 0.0437 |
| Final R indices | R1 = 0.0845 |
| [I>2σ(I)]a | wR2 =0.1927 |
the chemical bond distance of table two ()
| O1—C1 | 1.368(4) |
| C6—C1 | 1.401(5) |
| C6—C5 | 1.414(5) |
| C6—C24 | 1.496(5) |
| C5—C4 | 1.412(5) |
| C5—C19 | 1.494(5) |
| C1—C2 | 1.384(5) |
| C3—C4 | 1.380(5) |
| C3—C2 | 1.396(4) |
| C20—C19 | 1.318(4) |
| C20—C21 | 1.324(5) |
| C2—C7 | 1.494(5) |
| C4—C13 | 1.487(5) |
| C7—C8 | 1.382(5) |
| C7—C12 | 1.394(5) |
| C19—N1 | 1.408(5) |
| C13—C14 | 1.387(6) |
| C13—C18 | 1.387(5) |
| C24—C25 | 1.380(5) |
| C24—N2 | 1.397(5) |
| C25—C26 | 1.371(5) |
| N1—C23 | 1.394(5) |
| N2—C28 | 1.397(5) |
| C21—C22 | 1.356(6) |
| C11—C10 | 1.366(7) |
| C11—C12 | 1.389(6) |
| C26—C27 | 1.357(6) |
| C14—C15 | 1.402(6) |
| C28—C27 | 1.368(6) |
| C23—C22 | 1.356(6) |
| C18—C17 | 1.382(6) |
| C15—C16 | 1.361(8) |
| C8—C9 | 1.363(6) |
| C9—C10 | 1.388(6) |
| C16—C17 | 1.389(7) |
| O2—C29 | 1.350(5) |
Claims (2)
1. heterogeneous ring compound 2,4-phenylbenzene-5, and 6-bipyridyl-phenol, is characterized in that, has following structure:
。
2. preparation is claimed in claim 12,4-phenylbenzene-5, and the method for 6-bipyridyl-oxybenzene compound, is characterized in that, adopts following methods synthetic:
(1) 2,2 '-bis-pyridones are added in the ethanolic soln of 1,3-diphenyl acetone, after all dissolving, drip saturated sodium hydroxide-ethanolic soln, be warming up to backflow, then be cooled to room temperature, through refrigeration, suction filtration, washing, vacuum-drying, obtains 2,5-phenylbenzene-3,4-pyridyl ring pentadienone;
(2) by glacial acetic acid, 2,5-phenylbenzene-3, the o-Xylol solution of 4-pyridyl ring pentadienone adds in phenylacetylene, under argon shield, reflux, illumination reaction, except desolventizing, crosses post and purifies, and obtains target compound.
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| CN201310518992.2A CN103508941B (en) | 2013-10-29 | 2013-10-29 | 2,4-diphenyl-5,6-bis(2-pyridyl)-phenol and preparation method thereof |
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| CN103508941A true CN103508941A (en) | 2014-01-15 |
| CN103508941B CN103508941B (en) | 2015-07-22 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001057264A2 (en) * | 2000-02-07 | 2001-08-09 | Applera Corporation | Electron-deficient nitrogen heterocycle-substituted fluorescein dyes |
| US20070128658A1 (en) * | 2005-11-14 | 2007-06-07 | Blackwell Helen E | Fluorescent dyes, methods and uses thereof |
| CN102286279A (en) * | 2011-06-23 | 2011-12-21 | 郑州大学 | Benzene derivative metal ion fluorescent probe and use thereof |
-
2013
- 2013-10-29 CN CN201310518992.2A patent/CN103508941B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001057264A2 (en) * | 2000-02-07 | 2001-08-09 | Applera Corporation | Electron-deficient nitrogen heterocycle-substituted fluorescein dyes |
| US20070128658A1 (en) * | 2005-11-14 | 2007-06-07 | Blackwell Helen E | Fluorescent dyes, methods and uses thereof |
| CN102286279A (en) * | 2011-06-23 | 2011-12-21 | 郑州大学 | Benzene derivative metal ion fluorescent probe and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| ZHANXIAN LI，等: "Highly sensitive and selective fluorescent sensor for Zn2+/Cu2+ and new approach for sensing Cu2+ by central metal displacement", 《CHEMICAL COMMUNICATIONS》 * |
| 张利峰: "几种荧光分子探针的设计、合成及离子识别性质研究", 《郑州大学硕士学位论文》 * |
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