CN110078608A - A kind of method of fatty aldehyde β derivatization reactions synthesis 2- benzyl -2- ethyl valeral - Google Patents
A kind of method of fatty aldehyde β derivatization reactions synthesis 2- benzyl -2- ethyl valeral Download PDFInfo
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- CN110078608A CN110078608A CN201910455324.7A CN201910455324A CN110078608A CN 110078608 A CN110078608 A CN 110078608A CN 201910455324 A CN201910455324 A CN 201910455324A CN 110078608 A CN110078608 A CN 110078608A
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- ethyl valeral
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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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The present invention relates to technical field of fine, a kind of method for disclosing fatty aldehyde β derivatization reactions synthesis 2- benzyl -2- ethyl valeral.Specific steps: using 2- methyl -2- ethyl valeral and iodobenzene as raw material, palladium acetate is catalyst, silver trifluoroacetate and acethydrazide are additive, react 36 hours in methylene chloride with 90 degrees Celsius in acetic acid mixed reaction solvent, target product 2- benzyl -2- ethyl valeral can be obtained.The method is easy to operate, uses 2- methyl -2- ethyl valeral and iodobenzene as reaction raw materials, and a step is efficiently synthesized target product, has potential industrial value, is worthy of popularization.
Description
Technical field
The invention belongs to field of fine chemical, are related to a kind of fatty aldehyde β derivatization reactions synthesis 2- benzyl -2- ethyl valeral
Method.
Background technique
Aldehyde compound, especially fatty aldehyde are one of structural units common in natural products and drug, but also are
The key intermediate of organic synthesis.Therefore, how directly and efficiently synthctic fat aldehyde compound or to aliphatic aldehyde compound into
Row derivative reaction has caused the highest attention of chemist.
Currently, aldehyde compound synthetic method is mainly the following, comprising: hydroformylation reaction, alcohol oxidation reaction with
And Wacker reaction.And reaction is performed the derivatization for aliphatic aldehyde compound, presently relevant work reported in the literature is mainly concentrated
Priming reaction at fatty aldehyde aldehyde radical or aldehyde radical ortho position, only several example texts, which are offered, reports the direct remote site position of fatty aldehyde
Derivative reaction.MacMillan seminar once using organic catalyst and visible light catalyst realize fatty aldehyde β it is hydrocarbon
The direct functionalization of key.In addition, Wang Wei and Li Jian seminar reports depositing in chiral amine catalyst and anaerobic agent IBX
In the chiral derivatizing reaction of lower simple fatty aldehyde β C-H bonds, which relates to enamine and is formed, oxidation and nucleophilic addition
Journey, there are yield is relatively low and the restricted defect of substrate spectrum.Therefore, it explores and develops novel fatty aldehyde β derivative reactions
It is one of the vital task of chemist.There are no document report 2- benzyl -2- ethyl valeral synthetic methods so far.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of novel fatty aldehyde β derivatization reactions to close
At the new method of 2- benzyl -2- ethyl valeral.
Steps are as follows for synthesis 2- benzyl -2- ethyl valeral according to the present invention: by 2- methyl -2- ethyl valeral, iodobenzene,
Palladium acetate, silver trifluoroacetate, acethydrazide are sequentially added containing methylene chloride and acetic acid mixed reaction solvent (volume ratio 3:1)
In pressure pipe, 90 degrees Celsius with vigorous are stirred 36 hours, after reaction, successively carry out reaction solution concentration and column chromatography for separation, i.e.,
It can get target product 2- benzyl -2- ethyl valeral.
The reaction dissolvent of system is methylene chloride and acetic acid (volume ratio 3:1) in the present invention.
The concentration of reaction system is 0.25 mol/L in the present invention.
2- methyl -2- ethyl valeral in invention, iodobenzene, palladium acetate, silver trifluoroacetate, acethydrazide used in molar ratio be 1:
2:0.1:1.5:0.4.
Heretofore described reaction temperature is 90 degrees Celsius.
The heretofore described reaction time is 36 hours.
Specific embodiment
The following examples will be helpful to illustrate the present invention, but not limit to its range.
Specific embodiment:
Methylene chloride and acetic acid (volume ratio 3:1,4.0mL), 2- methyl -2- second are sequentially added in the pressure pipe of 50mL
Base valeral (1mmol, 0.128g), iodobenzene (2mmol, 0.41g), palladium acetate (0.1mmol, 0.023g), silver trifluoroacetate
(2.5mmol, 0.552g) and acethydrazide (0.4mmol, 0.03g), anti-temperature control are vigorously stirred anti-at 90 degrees Celsius
It answers 36 hours.After reaction, it is cooled to room temperature, successively carries out reaction solution concentration and column chromatography for separation, can be obtained target production
Object 2- benzyl -2- ethyl valeral (0.106g, 52%).
It is as follows to react the equation being related to:
The nuclear magnetic data of target product 2- benzyl -2- ethyl valeral is as follows:
1H NMR(500MHz,CDCl3) δ 9.55 (s, 1H), 7.27-7.20 (m, 3H), 7.07 (d, J=7.4Hz, 2H),
2.82(s,2H),1.58–1.39(m,4H),1.30–1.25(m,2H),0.92–0.86(m,6H).13C NMR(126MHz,
CDCl3)δ207.10,137.09,130.02,128.24,126.44,53.72,38.59,33.80,24.33,16.92,
14.65,8.07.
The foregoing describe optional embodiments of the invention, to instruct how those skilled in the art implement and reproduce this hair
It is bright.In order to instruct the present invention program, some routine techniques aspects are simplified and saved.Those skilled in the art answer
The understanding is originated from the modification of this respect, within the scope of the present invention.
Claims (7)
1. a kind of method of fatty aldehyde β derivatization reactions synthesis 2- benzyl -2- ethyl valeral follows the steps below: organic
2- methyl -2- ethyl valeral, iodobenzene, palladium acetate, silver trifluoroacetate and acethydrazide are added in solvent, heating is vigorously stirred and can obtain
To target product 2- benzyl -2- ethyl valeral.
2. the method according to claim 1, wherein the decompression steaming that the method also includes carrying out after reaction
It evaporates, column chromatography for separation and collection target product.
3. the method as described in claim 1, it is characterised in that: reaction temperature is at 90 degrees Celsius.
4. the method as described in claim 1, it is characterised in that: the reaction time is 36 hours.
5. the method as described in claim 1, it is characterised in that: 2- methyl -2- ethyl valeral, iodobenzene, palladium acetate, trifluoroacetic acid
The Standard entertion that silver and acethydrazide are 1:2:0.1:1.5:0.4 according to molar ratio.
6. the method as described in claim 1, it is characterised in that: organic solvent used in reacting is methylene chloride and acetic acid
(volume ratio 3:1).
7. the method as described in claim 1, it is characterised in that: the concentration of reaction system is 0.25 mol/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910455324.7A CN110078608B (en) | 2019-05-29 | 2019-05-29 | Method for synthesizing 2-benzyl-2-ethyl pentanal through beta-position derivatization reaction of aliphatic aldehyde |
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| CN201910455324.7A CN110078608B (en) | 2019-05-29 | 2019-05-29 | Method for synthesizing 2-benzyl-2-ethyl pentanal through beta-position derivatization reaction of aliphatic aldehyde |
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| CN110078608A true CN110078608A (en) | 2019-08-02 |
| CN110078608B CN110078608B (en) | 2021-11-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731506A (en) * | 2021-09-28 | 2021-12-03 | 常州大学 | Method for assisting palladium-catalyzed C-H arylation reaction of aliphatic aldehyde by calix [4] arene amide compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129249A (en) * | 2017-12-30 | 2018-06-08 | 武汉理工大学 | The synthetic method of pentacene and its derivative |
| CN109438205A (en) * | 2018-10-12 | 2019-03-08 | 西北大学 | A kind of synthetic method of 2- methyl -2,3- diaryl propionic aldehyde derivative |
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2019
- 2019-05-29 CN CN201910455324.7A patent/CN110078608B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129249A (en) * | 2017-12-30 | 2018-06-08 | 武汉理工大学 | The synthetic method of pentacene and its derivative |
| CN109438205A (en) * | 2018-10-12 | 2019-03-08 | 西北大学 | A kind of synthetic method of 2- methyl -2,3- diaryl propionic aldehyde derivative |
Non-Patent Citations (2)
| Title |
|---|
| FEI MA等: "Acetohydrazone: A Transient Directing Group for Arylation of Unactivated C(sp3)-H Bonds", 《ORGANIC LETTERS》 * |
| KE YANG等: "Catalytic C-H Arylation of Aliphatic Aldehydes Enabled by a Transient Ligand", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731506A (en) * | 2021-09-28 | 2021-12-03 | 常州大学 | Method for assisting palladium-catalyzed C-H arylation reaction of aliphatic aldehyde by calix [4] arene amide compound |
| CN113731506B (en) * | 2021-09-28 | 2023-05-26 | 常州大学 | Method for assisting palladium-catalyzed fatty aldehyde C-H arylation reaction by calix [4] arene amide compound |
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