CN103508941B - 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 PDF

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CN103508941B
CN103508941B CN201310518992.2A CN201310518992A CN103508941B CN 103508941 B CN103508941 B CN 103508941B CN 201310518992 A CN201310518992 A CN 201310518992A CN 103508941 B CN103508941 B CN 103508941B
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adds
preparation
phenylbenzene
diphenyl
phenol
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CN103508941A (en
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于明明
乔钰茜
李占先
魏柳荷
郭永开
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Zhengzhou University
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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

2,4-phenylbenzene-5,6-bipyridyls-phenol and preparation method thereof
Technical field
The present invention relates to heterogeneous ring compound 2,4-phenylbenzene-5, a 6-bipyridyls-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.Usual 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.The at present diversified heterogeneous ring compound of synthetic, is 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, while Cheng Huan, seven-membered ring defines hydroxyl ( j. Am. Chem. Soc. 2000, 122,12169-12173).Its raw material is complicated, and synthesis obtains is seven-membered ring.
React close addition rearrangement reaction with the present invention, Zhu G. D. once reported similar reaction, be by furans and alkynes react ( org. Lett. 2000, 2, 3345-3348).
Nearest Wipf P. also report furans and alkynyl similar reaction ( j. Org. Chem. 2013, 78, 167 174).
Clearly the starting raw material of this kind of reaction is all furans, makes the phenyl ring of generation is not easy to modify other groups.
Summary of the invention
The object of the invention is a kind of new heterogeneous ring compound 2,4-phenylbenzene-5,6-bipyridyls-phenol (2,4-diphenyl-5,6-bis (2-pyridyl)-phenol) of preparation and provides its preparation method.
The chemical structural formula of heterogeneous ring compound 2,4-phenylbenzene-5,6-bipyridyls-phenol (2,4-diphenyl-5,6-bis (2-pyridyl)-phenol) of the present invention is:
Employing following methods synthesizes:
Step 1: add in the ethanolic soln of 1,3-diphenyl acetone by 2,2 '-two pyridones, drips saturated sodium hydroxide-ethanolic soln after all dissolving, is warming up to backflow, then room temperature is cooled to, through refrigeration, suction filtration, washing, vacuum-drying, obtains 2,5-phenylbenzene-3,4-pyridyl ring pentadienone.
Step 2: add in phenylacetylene by the o-xylene solution of glacial acetic acid, 2,5-phenylbenzene-3,4-pyridyl ring pentadienones, under argon shield, reflux, illumination reaction, except desolventizing.Cross post to purify, obtain solid powder sample.
In the present invention, product prepares the proton environments needing glacial acetic acid to provide, and needs illumination and control applicable temperature, needs addition reaction and rearrangement reaction occur in preparation process.
Preparation method of the present invention can by controlling to initial raw material the compound that synthesis has expection substituted radical, and synthesis step is simple, and reaction is easily carried out, and cost is lower.Heterogeneous ring compound of the present invention may be used for synthetic 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 hexanaphthene respectively, 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 describes the present invention in detail below, and described embodiment is for describing the present invention, instead of restriction the present invention.
Embodiment
Synthesis step: be dissolved in 6 mL ethanol by 1, the 3-diphenyl acetone of 635.9 mg, adds in the two-mouth bottle of 25 mL, then adds 2 of 638.4 mg, 2 '-two pyridone.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, stop after 5 min, put into refrigerator cold-storage 5 h after cooling, suction filtration, use distilled water and absolute ethanol washing three times respectively, yellow solid and intermediate product 855 mg is obtained, productive rate 74% after vacuum-drying. 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 and dissolves, then add 0.15 mL (1.36 mmol) phenylacetylene; under argon shield; take out inflation three times, be heated to backflow, 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。
Gained compound 2,4-phenylbenzene-5,6-bipyridyls-phenol is slowly volatilized in methyl alcohol, after the week, obtains the crystal of this compound.
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, therefore the not aobvious color of solution.From accompanying drawing 3 fluorescence spectrum can see this compound and under the optical excitation of 300 nm in compound methylene dichloride emmission spectrum be obviously better than other solvents, can send stronger hepatic fluorescence in methylene dichloride, in other solvents, luminescence is very weak and not in visible region.This compound can modify fields such as being applied to fluorescence sense, coordination, catalysis, organic synthesis further.
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's () 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 (1)

1. prepare the method for 2,4-phenylbenzene-5,6-bipyridyls-oxybenzene compound, it is characterized in that, adopt following methods synthesis:
(1) 1, the 3-diphenyl acetone of 635.9 mg is dissolved in 6 mL ethanol, adds in the two-mouth bottle of 25 mL, then add 2 of 638.4 mg, 2 '-two pyridone; After all dissolving, drip saturated sodium hydroxide-ethanolic soln i.e. 93.9 mg KOH solids and be dissolved in 2 mL ethanol, be warming up to backflow, stop after 5 min, put into refrigerator cold-storage 5 h after cooling, suction filtration, use distilled water and absolute ethanol washing three times respectively, yellow solid and intermediate product 855 mg is obtained, productive rate 74% after vacuum-drying;
(2) by 0.15 mL glacial acetic acid, 0.1932 g i.e. 0.5 mmol 2,5-phenylbenzene-3,4-pyridyl ring pentadienone adds in 25 mL two-mouth bottles, adds 15 mL o-Xylols and dissolves, then add 0.15 mL i.e. 1.36 mmol phenylacetylenes, under argon shield, take out inflation three times, be heated to backflow, 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%.
CN201310518992.2A 2013-10-29 2013-10-29 2,4-diphenyl-5,6-bis(2-pyridyl)-phenol and preparation method thereof Expired - Fee Related CN103508941B (en)

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* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
Highly sensitive and selective fluorescent sensor for Zn2+/Cu2+ and new approach for sensing Cu2+ by central metal displacement;Zhanxian Li，等;《Chemical Communications》;20110329;第47卷(第20期);第5798页右栏图1、第5799页左栏第2段第1-2行、图3 *
几种荧光分子探针的设计、合成及离子识别性质研究;张利峰;《郑州大学硕士学位论文》;20111031;全文 *

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