CN110407677A - The preparation method and application of benzil class compound - Google Patents
The preparation method and application of benzil class compound Download PDFInfo
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- CN110407677A CN110407677A CN201910520854.5A CN201910520854A CN110407677A CN 110407677 A CN110407677 A CN 110407677A CN 201910520854 A CN201910520854 A CN 201910520854A CN 110407677 A CN110407677 A CN 110407677A
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- benzyl alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation methods for synthesizing dibenzoyl class compound, benzyl alcohol class compound is in the case where cuprous bromide, sodium nitrite, DDQ, Bronsted acid are total to catalytic action, it is oxidized by oxygen, benzil class compound is made in one-step method, suitable by catalyst, reaction condition etc. is selected and is cooperateed with, realize the purpose product of high yield, and it is high-efficient in preparation process, it is at low cost, there is very significant technical meaning and application value, wide market in medicine intermediate synthesis field.
Description
Technical field
The invention belongs to synthesize dibenzoyl class compound field, in particular to a kind of synthesis dibenzoyl class compound
Preparation method and application.
Background technique
Aryl-linking compound, especially biphenyl compound are to be widely present in medical compounds, pesticide, functional material etc.
In important structural unit, the synthesis of this kind of structure chunking is most important for the production of drug, material etc..In the prior art
Although disclosing the method for many synthesis biphenyl compounds, these methods are not able to satisfy still general in current medicine synthesis
All over demand, therefore it is particularly significant and urgently to be resolved to develop a kind of high efficiency, the synthesis technology of low energy consumption.
Summary of the invention
A kind of high efficiency, the synthesis work of low energy consumption how are developed in the prior art the purpose of the present invention is to solve above-mentioned
The technical issues of skill, the present invention provides a kind of preparation method for synthesizing dibenzoyl class compound, benzyl alcohol class compound exists
Cuprous bromide, sodium nitrite, DDQ, Bronsted acid are total under catalytic action, are oxidized by oxygen, and benzil class is made in one-step method
Object is closed, reaction equation is as follows:
Wherein catalyst is cuprous bromide, sodium nitrite, DDQ, Bronsted acid, is reacted under the conditions of dioxygen oxidation.
As an improvement, benzyl alcohol class compound, protobromide ketone, sodium nitrite, Bronsted acid, DDQ described in above-mentioned reaction
Usage ratio is 10:1:1:1:1 when reaction.
As an improvement, in above-mentioned reaction the reaction time be 65-75 degrees Celsius, reaction time 10-14h.
As an improvement, the group on the benzyl alcohol class compound phenyl ring can be halogen, and cyano, amide, nitro, three
It is any in methyl fluoride.
As an improvement, the solvent usage of above-mentioned reaction is 3-6mL, be acetonitrile when solvent, it is a kind of in DMF, dioxane or
More than one；Or solvent is not selected to react.
As an improvement, the Bronsted acid is acetic acid.
As an improvement, the benzyl alcohol class compound is benzyl alcohol, 2- methylbenzyl alcohol, 3- methylbenzyl alcohol, 4- methyl
Benzyl alcohol, 2- trifluoromethyl benzyl alcohol, 3- trifluoromethyl benzyl alcohol.
The utility model has the advantages that the preparation method of benzil class compound provided by the invention, passes through catalyst, reaction condition
Deng it is suitable selection and cooperate with, realize the purpose product of high yield, and high-efficient in preparation process, it is at low cost, in medicine
There is very significant technical meaning and application value, wide market in mesosome synthesis field.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention, detailed description is as follows below.
Specific embodiment
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is not intended to limit the scope of the invention.
Embodiment 1:
Benzyl alcohol (20mmol, 2.163g), protobromide ketone (2mmol, 0.287g), Asia are sequentially added in 50mL eggplant-shape bottle
Sodium nitrate (2mmol, 0.138g), acetic acid (2mmol, 0.120g), DDQ (2mmol, 0.454g), vacuumize, are oxygenated gas shielded,
4mL acetonitrile is added, 65 degrees Celsius of reaction 10h are answered after stopping.It is cooling, the dilution of 50mL ethyl acetate is added, it is full with 50mL respectively
Three times with aqueous ammonium chloride solution, 50mL sodium bicarbonate aqueous solution, 50mL water washing, organic layer is obtained, anhydrous sodium sulfate is dry
40min, evaporated under reduced pressure obtain crude product, with petroleum ether: ethyl acetate=25:1 carry out column chromatograph 1.985g product, yield are
94.5%.
mp 94.5–95.5℃；1H NMR(400MHz,CDCl3) δ 7.99-7.97 (m, 4H), 7.66 (t, J=7.4Hz,
2H), 7.51 (t, J=7.8Hz, 4H)；13C NMR(100MHz,CDCl3)δ194.7,135.0,133.2,130.0,129.2；
HRMS(ESI):m/z[M+Na]+calcd.for C14H10NaO2 +:233.0573,found 233.0570.
Embodiment 2
Sequentially added in 50mL eggplant-shape bottle to methylbenzyl alcohol (20mmol, 2.443g), protobromide ketone (2mmol,
0.287g), sodium nitrite (2mmol, 0.138g), acetic acid (2mmol, 0.120g), DDQ (2mmol, 0.454 g), vacuumize,
It is oxygenated gas shielded, 4mL acetonitrile is added, 70 degrees Celsius of reaction 10.5h are answered after stopping.It is cooling, the dilution of 50mL ethyl acetate is added,
Respectively three times with 50mL saturated aqueous ammonium chloride, 50mL sodium bicarbonate aqueous solution, 50mL water washing, organic layer, anhydrous sulphur are obtained
The dry 40min of sour sodium, evaporated under reduced pressure obtains crude product, with petroleum ether: ethyl acetate=30:1 carries out column and chromatographs to obtain 2.229g product,
Yield is 93.6%.
mp:102.5-103.5℃；1H NMR(400MHz,CDCl3): δ=7.84-7.86 (d, J=6.5Hz, 4H),
7.28-7.29 (d, J=8.0Hz, 4H), 2.41 (s, 6H)；13C NMR(100MHz,CDCl3):δ194.4,146.0,130.5,
129.88, 129.31,21.79；HRMS(ESI):m/z[M+H]+calcd.for C16H15O2 +:239.1067found
239.1050.
Embodiment 3
Sequentially added in 50mL eggplant-shape bottle to trifluoromethyl benzyl alcohol (20mmol, 3.523g), protobromide ketone (2mmol,
0.287g), sodium nitrite (2mmol, 0.138g), acetic acid (2mmol, 0.120g), DDQ (2mmol, 0.454 g), vacuumize,
It is oxygenated gas shielded, 4mL acetonitrile is added, 75 degrees Celsius of reaction 14h are answered after stopping.It is cooling, the dilution of 50mL ethyl acetate is added, point
Not three times with 50mL saturated aqueous ammonium chloride, 50mL sodium bicarbonate aqueous solution, 50 mL water washings, organic layer, anhydrous slufuric acid are obtained
Sodium dries 40min, and evaporated under reduced pressure obtains crude product, with petroleum ether: ethyl acetate=30:1 carries out column and chromatographs to obtain 3.092g product, receives
Rate is 89.4%.
m.p.142.5-143.5℃；1H NMR(400MHz,CDCl3): 7.81 (d, J=8Hz, 4H), 8.12 (d, J=
8Hz, 4H)；13C NMR(100MHz,CDCl3):119.99,122.16,124.33,126.11,126.14,126.17,
126.20, 126.27,126.51,130.07,130.24,130.33,135.21,135.22,135.79,136.05,
136.32,136.58, 191.87；HRMS(ESI):m/z[M+H]+calcd.for C16H9F6O2 +:347.0501found
345.0516.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (6)
1. a kind of preparation method of benzil class compound, it is characterised in that: benzyl alcohol class compound is in cuprous bromide, Asia
Sodium nitrate, DDQ, Bronsted acid are total under catalytic action, are oxidized by oxygen, and benzil class compound, reaction side is made in one-step method
Formula is as follows:
Wherein, R1、R2、R3、R4、R5It is independently H, halogen, cyano, amide, nitro, any in trifluoromethyl.
2. preparation method according to claim 1, it is characterised in that: in reaction system, the benzyl alcohol class compound, bromine
Changing sub- ketone, sodium nitrite, Bronsted acid, DDQ amount ratio is 10:1:1:1:1.
3. preparation method according to claim 1, it is characterised in that: the reaction time is 65-75 DEG C, reaction time 10-
14h。
4. preparation method according to claim 1, it is characterised in that: in reaction system, solvent can be selected, solvent usage is
3-6mL, solvent is acetonitrile, DMF, one or more kinds of in dioxane；Or solvent is not selected to react.
5. preparation method according to claim 1, it is characterised in that: the Bronsted acid is acetic acid.
6. preparation method according to claim 1, it is characterised in that: the benzyl alcohol class compound is benzyl alcohol, 2- first
Base benzyl alcohol, 3- methylbenzyl alcohol, 4- methylbenzyl alcohol, 2- trifluoromethyl benzyl alcohol, 3- trifluoromethyl benzyl alcohol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910520854.5A CN110407677B (en) | 2019-06-17 | 2019-06-17 | Preparation method and application of diphenylethanedione compound |
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| CN201910520854.5A CN110407677B (en) | 2019-06-17 | 2019-06-17 | Preparation method and application of diphenylethanedione compound |
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| CN110407677A true CN110407677A (en) | 2019-11-05 |
| CN110407677B CN110407677B (en) | 2022-10-11 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090042891A1 (en) * | 2005-07-29 | 2009-02-12 | Bernat Vidal Juan | Pyrazine Derivatives Useful as Adenosine Receptor Antagonists |
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- 2019-06-17 CN CN201910520854.5A patent/CN110407677B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090042891A1 (en) * | 2005-07-29 | 2009-02-12 | Bernat Vidal Juan | Pyrazine Derivatives Useful as Adenosine Receptor Antagonists |
Non-Patent Citations (1)
| Title |
|---|
| KEVIN P. MCCLELLAND等: "Selective Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde or C−C Coupled Products by Visible-Light-Absorbing Quantum Dots", 《ACS APPLIED ENERGY MATERIALS》 * |
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