CN109970703A - The preparation method and application of 1,3- heterocyclic substituted aromatic ketone - Google Patents
The preparation method and application of 1,3- heterocyclic substituted aromatic ketone Download PDFInfo
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- CN109970703A CN109970703A CN201910380476.5A CN201910380476A CN109970703A CN 109970703 A CN109970703 A CN 109970703A CN 201910380476 A CN201910380476 A CN 201910380476A CN 109970703 A CN109970703 A CN 109970703A
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- heterocyclic substituted
- preparation
- aromatic ketone
- fragrant
- substituted aromatic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The preparation method and application of 1,3- heterocyclic substituted aromatic ketone, belongs to medical science and field of photovoltaic materials.The present invention reacts to obtain compound in dichloromethane system by raw material and DCC and DMAP of the fragrant phenylacetic acid of heterocyclic substituted, and chemicals obtain final products using column Chromatographic purification, which can be used in the preparation of antidiabetic drug and photoelectricity crystallization conductor material.The present invention prepares 1,3- heterocyclic substituted aromatic ketone using the fragrant phenylacetic acid reaction of heterocyclic substituted；Operation is simple and easy, carries out under mild reaction conditions.Synthetic method provided by the invention is simple and easy, scientific and reasonable, environmentally protective, economical and practical, is suitble to large-scale production.
Description
Technical field
The present invention relates to medical science and field of photovoltaic materials, relate generally to the preparation method of 1,3- heterocyclic substituted aromatic ketone
And application.
Background technique
1,3- heterocyclic substituted aromatic ketone due to its unique molecular structure, photoelectric characteristic and they on p- electronic material
Application, make its poromerics, crystallization photoconductor, synthesizing graphite alkene in terms of using more and more extensive.Meanwhile
1,3- heterocyclic substituted aromatic ketone can be used as a kind of cheap precursor, fast and effeciently prepare relative complex structure, so
Also there is important application in terms of pharmaceutical synthesis.Based on this, this field needs easier, green, economic method to synthesize 1,3-
Heterocyclic substituted aromatic ketone.The present invention prepares 1,3- heterocyclic substituted aromatic ketone using the reaction of the fragrant phenylacetic acid of heterocyclic substituted.Instead
It answers that operation is simple, carries out under mild reaction conditions.Synthetic method provided by the invention is simple and easy, scientific and reasonable, green
Colour circle is protected, is economical and practical, and large-scale production is suitble to.
Summary of the invention
To make up the deficiencies in the prior art, the present invention provides operation is simple, 1,3- heterocycle is synthesized under temperate condition
The method of substituted aroma ketone.
The present invention adopts the following technical scheme: 1,3- heterocyclic substituted aromatic ketone, has the structure as shown in formula I:
The purpose of the present invention is the preparation method of above-mentioned 1,3- heterocyclic substituted aromatic ketone is claimed, it may be assumed that by DCC (N, N'-
Dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) according to molar ratio be 1~10:1~2 be added to round-bottomed flask
In, and dry methylene chloride (1mmol:(2~5mL) is added) to stirring evenly.By the fragrant phenylacetic acid of heterocyclic substituted (mole
Number it is equal with DCC) be dissolved in (1mmol:(4~8mL)) and dry dichloromethane solution in, be added dropwise to using constant pressure funnel
It is 20~30 DEG C of reaction 24-72h in temperature, the color with the progress solution of reaction becomes orange, and it is heavy to filter out in reaction solution
It forms sediment, is rotated later.Use column chromatography for separation to obtain compound (eluant, eluent is ethyl acetate: petroleum ether=1:5).
The volume number of the methylene chloride is using the mole of the fragrant phenylacetic acid of heterocyclic substituted as standard.
Preferably, the fragrant phenylacetic acid of the heterocyclic substituted are as follows:
Above-mentioned 1,3- heterocyclic substituted aromatic ketone is claimed in medicine preparation and field of photovoltaic materials in the present invention simultaneously
Using.
For example it is used for antidiabetic drug intermediateOr photoelectricity crystallizes conductor materialPreparation.
Compared with prior art, the beneficial effects of the present invention are:
The present invention prepares 1,3- heterocyclic substituted aromatic ketone using the fragrant phenylacetic acid reaction of heterocyclic substituted；Operation is simple
It is easy, it carries out under mild reaction conditions.Synthetic method provided by the invention is simple and easy, scientific and reasonable, environmentally protective, economical
It is practical, it is suitble to large-scale production.
Specific embodiment
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally
Experimental method used by inventing is conventional method, and experiment equipment used, material, reagent etc. can chemically company be bought.
Embodiment 1
A 100mL round-bottomed flask is taken, 10mL is added in DCC (1.0320g, 5mmol) and DMAP (0.1222g, 1mmol)
In dry methylene chloride, stirring to whole dissolutions.3- thiophene acetic acid (0.7109g, 5mmol) is dissolved to 20mL drying
In methylene chloride, then it is slowly added dropwise with constant pressure funnel into above-mentioned solution.Stir 24-72h.It is spin-dried for, then through column color
Spectrum separation (eluant, eluent is ethyl acetate: petroleum ether :=1:5) is to obtain target compound.It is characterized as below:
1,3- thiophene acetone: yield: 56%.1H NMR(500MHz,CDCl3) δ 7.19-7.13 (m, 2H), 6.94 (t, J=
6.4Hz, 2H), 6.80 (dd, J=4.9,0.9Hz, 2H), 3.63 (s, 4H)
Embodiment 2
The application of antidiabetic drug intermediate
The 1,3- thiophene acetone (0.350g, 1.57mmol) being dissolved in the anhydrous THF of 15mL is added drop-wise to cooling contain
In the solution of the THF (30mL, 0 DEG C) of hydrofining (0.5g, 12.2mmol).Iodomethane (0.4mL, 6.4mmol) is added dropwise
Into yellow suspension and stir to room temperature.Bleach to suspension, is then refluxed for until observing that suspension becomes orange, then
Suspension is cooled to 0 DEG C, the iodomethane (0.15mL, 2.4mmol) of additional quantity is added dropwise, is then extracted with water and ether.Ether layer
With magnesium sulfate drying and it is evaporated under reduced pressure.It is purified by column chromatography (silica, CH3COOC2H5=10%, hexane=90%) residual
Excess obtains white crystalline powder.It is characterized as below:
The amyl- 3- ketone of 2,4- dimethyl -2,4- two (thiene-3-yl): yield: 90%；Fusing point: 76-78 DEG C.1HNMR
(500MHz,CDCl3) δ 7.17 (dd, J=4.96Hz, 1H), 6.84 (d, J=2.9Hz, 1H), 6.76 (dd, J=4.96Hz,
1H),1.36(s,6H)。
Embodiment 3
The application of photoelectric material
It is molten that 10mL water/SDS is added at one time into acetone (2mL) solution of 1,3- thiophene acetone (0.04g, 0.14mmol)
Liquid (2.5mM).Air is blown in reaction bottle while agitating, until obtaining the air that total volume is 6mL.It is added additional
2mL water make total volume 8mL.Milk-white coloured suspension is placed in distance at the distance (~10cm) for pressing Hg Hanovia lamp and is stirred
It mixes, while keeping 4 steady temperatures (about 25 DEG C) in photolysis chamber.In irradiation process, a small amount of various kinds is taken out in different time
Product, and analyzed by GC, NMR and X-RPD.Irradiation stops after 12h, then filters yellow mercury oxide, obtains target chemical combination
Object.It is characterized as below:
3- (2,3- dimethyl -3- (thiene-3-yl) butyl- 2- yl) thiophene: yield: 70%；Fusing point: 125-128 DEG C.1H
NMR (500HMz, CDCl3) δ 7.14 (dd, J=3.0,4.98Hz, 1H), 6.79 (dd, J=3.0Hz, 1H), 6.77 (dd, J=
4.98Hz,1H)1.34(s,6H)。
The preferable specific embodiment of the above, only the invention, but the protection scope of the invention is not
It is confined to this, anyone skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection scope it
It is interior.
Claims (7)
1. one kind 1, the preparation method of 3- heterocyclic substituted aromatic ketone, which is characterized in that method includes the following steps:
S1. DCC and DMAP are added in round-bottomed flask, and dry methylene chloride is added and stirs evenly；
S2. the fragrant phenylacetic acid of heterocyclic substituted is dissolved in the reaction solution for being added dropwise to step S1 in dichloromethane solution, 20~
30 DEG C of reaction 24-72h；
S3. it is filtered to remove the precipitating of step S2, filtrate revolving obtains product using column chromatography for separation.
2. a kind of preparation method of 1,3- heterocyclic substituted aromatic ketone according to claim 1, which is characterized in that the step
The molar ratio of DCC and DMAP is 1~10:1~2 in S1.
3. the preparation method of 1,3- heterocyclic substituted aromatic ketone according to claim 1, which is characterized in that in the step S2
The fragrant phenylacetic acid molal quantity of heterocyclic substituted is equal with DCC.
4. the preparation method of 1,3- heterocyclic substituted aromatic ketone according to claim 1, which is characterized in that in the step S1
The proportionate relationship of methylene chloride and the fragrant phenylacetic acid of heterocyclic substituted is the fragrant phenylacetic acid of heterocyclic substituted: methylene chloride=
1mmol:2~5mL.
5. the preparation method of 1,3- heterocyclic substituted aromatic ketone according to claim 1, which is characterized in that in the step S2
The proportionate relationship of methylene chloride and the fragrant phenylacetic acid of heterocyclic substituted is the fragrant phenylacetic acid of heterocyclic substituted: methylene chloride=
1mmol:4~8mL.
6. a kind of preparation method of 1,3- heterocyclic substituted aromatic ketone according to claim 1, which is characterized in that in step S3
Eluant, eluent be ethyl acetate: petroleum ether=1:5.
7. the product that the method as described in claim 1 obtains answering in terms of antidiabetic drug and photoelectricity crystallization conductor material preparation
With.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426533A (en) * | 2021-12-23 | 2022-05-03 | 玉林师范学院 | Method for preparing polyaryl substituted benzothiophene through ruthenium catalysis and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153300A (en) * | 2010-08-11 | 2013-06-12 | 米伦纽姆医药公司 | Heteroaryls and uses thereof |
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2019
- 2019-05-08 CN CN201910380476.5A patent/CN109970703A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153300A (en) * | 2010-08-11 | 2013-06-12 | 米伦纽姆医药公司 | Heteroaryls and uses thereof |
Non-Patent Citations (5)
| Title |
|---|
| J. ARIAS-PARDILLA: "Reduction and Oxidation Doping Kinetics of an Electropolymerized Donor−Acceptor Low-Bandgap Conjugated Copolymer", 《J. PHYS. CHEM. B》 * |
| JESSE P. WALDO, ET AL.: "Efficient Synthesis of Fluoren-9-ones by the Palladium-Catalyzed, Annulation of Arynes by 2-Haloarenecarboxaldehydes", 《J. ORG. CHEM.》 * |
| MARINO J. E. RESENDIZ: "Photodecarbonylation of 1,3-Dithiophenyl Propanone: Using Nanocrystals to Overcome the Filtering Effect of Highly Absorbing Trace Impurities", 《ORG. LETT.》 * |
| MARINO J. E. RESENDIZ: "Unexpected Solid-State Photochemistry of an α-Thiophenyl-α‘-Thiophenyl-S,S-dioxo-Substituted Ketone", 《J. ORG. CHEM.》 * |
| 徐威: "《药学细胞生物学》", 31 August 2015, 中国医药科技出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426533A (en) * | 2021-12-23 | 2022-05-03 | 玉林师范学院 | Method for preparing polyaryl substituted benzothiophene through ruthenium catalysis and application |
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