Method for synthesizing olefin and fluoroolefin
By using ferrous acetate catalysis and oxygen as an oxidant to synthesize olefins and fluoroolefins with acrylic acid or fluoroacrylic acid and dihydroquinazolinone derivatives, the problems of complex synthesis and high cost in existing technologies are solved, and high-selectivity and high-purity synthesis effects are achieved.
Patent Information
- Application Number
- CN202411426576.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-28
- Publication Date
- 2025-01-14
AI Technical Summary
Existing technologies are difficult to synthesize olefins and fluoroolefins efficiently and cheaply, especially when using inexpensive catalysts and oxidants, and the synthesis process is complex and costly.
Olefins and fluoroolefins are synthesized by reacting acrylic acid or fluoroacrylic acid with dihydroquinazolinone derivatives under ferrous acetate catalysis, using oxygen as the oxidant and chlorobenzene as the solvent.
This provides a low-cost, highly selective, and simple synthetic method that produces high-purity products suitable for organic chemistry, medicinal chemistry, and materials science.
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Figure CN119306689A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to compound preparation, belonging to the field of organic compound synthesis, and specifically to a method for preparing olefins and fluoroolefins. Background Art
[0002] As an important basic chemical raw material, olefins are widely used in the production of plastics, synthetic rubber and other chemical products. Their chemical properties enable olefins to participate in a variety of chemical reactions, promoting the development and application of new materials. With the advancement of modern science and technology, the application of olefins in the fields of medicine, electronics, energy, etc. is becoming increasingly important, promoting the process of green chemistry and sustainable development.
[0003] In addition, as a class of organic compounds with great application prospects, fluoroolefins have shown extensive and far-reaching application value in the fields of medicinal chemistry and synthetic chemistry. Their unique physical and chemical properties play a vital role in molecular design and organic synthesis strategies. Specifically, the clever introduction of fluoroolefins can finely regulate the spatial conformation, stability and reactivity of molecules, thereby significantly improving the biological activity or selectivity of chemical reactions of compounds, opening up new avenues for optimizing drug efficacy and innovating synthetic pathways. Not only that, fluoroolefins also show the ability to significantly improve the pharmacokinetic properties of compounds, including enhancing oral bioavailability and prolonging the half-life of drugs in the body. These properties are of great significance for improving drug efficacy, reducing the frequency of administration and reducing side effects. Therefore, fluoroolefins have become an indispensable key tool in the fields of drug research and development and organic synthesis, and continue to promote the development of these two fields to a higher level, which has brought unprecedented opportunities and also proposed new challenges and research directions. Summary of the invention
[0004] In view of the unique properties of olefins and fluoroolefins and their important value in the fields of materials and medicine, the present invention provides a highly efficient method for synthesizing olefins and fluoroolefins using cheap ketone compound derivatives and acrylic compounds as reaction raw materials, clean oxygen as oxidant, and under cheap iron catalysis.
[0005] In order to solve the above technical problems, the present invention adopts the following technical scheme: a method for synthesizing olefins and fluoroolefins, characterized in that acrylic acid or fluoroacrylic acid is reacted with a dihydroquinazolinone derivative, oxygen is used as an oxidant, chlorobenzene is used as a solvent, and under the catalysis of ferrous acetate, a reaction is carried out according to the following reaction formula to obtain a class of olefins and fluoroolefin compounds having the general formula:
[0006]
[0007] Preferably, the amount of the dihydroquinazolinone derivative is twice the amount of acrylic acid.
[0008] Preferably, the amount of ferrous acetate is 10% of the amount of acrylic acid.
[0009] Preferably, the reaction temperature is 100° C. and the reaction time is 10 hours.
[0010] The method is cheap, has high product selectivity, is easy to operate, and uses clean oxygen as an oxidant. The synthesized compounds have high application value in organic chemistry, medicinal chemistry, and material science. It provides an efficient and clean synthesis method for olefins and fluoroolefin compounds.
[0011] Ketone compounds play an important role in nature and industrial production, and are cheap raw materials for chemical industry synthesis. The method provides a method for synthesizing olefins and fluoroolefins using dihydroquinazolinone compounds, which are derivatives of ketone compounds, and the reaction system is cheap. Clean oxygen or air is used as an oxidant, which overcomes the disadvantages of other external oxidants being expensive and cumbersome to synthesize, and has great industrial synthesis value. It can produce beneficial value and has significant improvement over some existing methods. DETAILED DESCRIPTION
[0012] The technical solution of the present invention is further described below through specific implementation modes:
[0013] Example 1
[0014] The reaction formula of this embodiment is as follows:
[0015]
[0016] (1) Cinnamic acid (0.2 mmol, 1.0 equiv), derivatized dihydroquinazolinone (0.4 mmol, 2.0 equiv) and ferrous acetate (10 mol%) were added to a sealed reaction tube with a branch tube and a magnetic pole under air. The reaction tube was evacuated and filled with oxygen. 1 mL of chlorobenzene was added to the reaction tube and reacted at 100 degrees Celsius for 10 hours.
[0017] (2) The solvent in the organic phase obtained in step (1) is dried by spin drying to obtain a crude product, which is then purified using a silica gel column. The separation yield is 75% and the product purity is >98%.
[0018] Example 2
[0019] The reaction formula of this embodiment is as follows:
[0020]
[0021] (1) 4-Acetoxycinnamic acid (0.2 mmol, 1.0 equiv), derivatized dihydroquinazolinone (0.4 mmol, 2.0 equiv) and ferrous acetate (10 mol%) were added to a sealed reaction tube with a branch tube and a magnetic pole under air. The reaction tube was evacuated and filled with oxygen. 1 mL of chlorobenzene was added to the reaction tube and reacted at 100 degrees Celsius for 10 hours.
[0022] (2) The solvent in the organic phase obtained in step (1) was dried by spin drying to obtain a crude product, which was then purified using a silica gel column. The separation yield was 72% and the product purity was >98%.
[0023] Example 3
[0024] The reaction formula of this embodiment is as follows:
[0025]
[0026] (1) 3-Bromocinnamic acid (0.2 mmol, 1.0 equiv), derivatized dihydroquinazolinone (0.4 mmol, 2.0 equiv) and ferrous acetate (10 mol%) were added to a sealed reaction tube with a branch tube and a magnetic pole under air. The reaction tube was evacuated and filled with oxygen. 1 mL of chlorobenzene was added to the reaction tube and reacted at 100 degrees Celsius for 10 hours.
[0027] (2) The solvent in the organic phase obtained in step (1) was dried by spin drying to obtain a crude product, which was then purified using a silica gel column. The separation yield was 73% and the product purity was >98%.
[0028] Example 4
[0029] The reaction formula of this embodiment is as follows:
[0030]
[0031] (1) 4-Chlorofluorocinnamic acid (0.2 mmol, 1.0 equiv), derivatized dihydroquinazolinone (0.4 mmol, 2.0 equiv) and ferrous acetate (10 mol%) were added to a sealed reaction tube with a branch tube and a magnetic bar under air. 1 mL of chlorobenzene was added to the reaction tube and reacted at 100 °C for 10 hours.
[0032] (2) The solvent in the organic phase obtained in step (1) was dried by spin drying to obtain a crude product, which was then purified using a silica gel column. The separation yield was 73% and the product purity was >98%.
[0033] Example 5
[0034] The reaction formula of this embodiment is as follows:
[0035]
[0036] (1) 4-Fluoro-(fluorocinnamic acid) (0.2 mmol, 1.0 equiv), derivatized dihydroquinazolinone (0.4 mmol, 2.0 equiv) and ferrous acetate (10 mol%) were added to a sealed reaction tube with a branch tube and a magnetic bar under air. 1 mL of chlorobenzene was added to the reaction tube and reacted at 100 degrees Celsius for 10 hours.
[0037] (2) The solvent in the organic phase obtained in step (1) was dried by spin drying to obtain a crude product, which was then purified using a silica gel column. The separation yield was 72% and the product purity was >98%.
[0038] Example 6
[0039] The reaction formula of this embodiment is as follows:
[0040]
[0041] (1) Substituted fluorocinnamic acid (0.2 mmol, 1.0 equiv), derivatized dihydroquinazolinone (0.4 mmol, 2.0 equiv) and ferrous acetate (10 mol%) were added to a sealed reaction tube with a branch tube and a magnetic bar under air. 1 mL of chlorobenzene was added to the reaction tube and reacted at 100 degrees Celsius for 10 hours.
[0042] (2) The solvent in the organic phase obtained in step (1) was dried by spin drying to obtain a crude product, which was then purified using a silica gel column. The separation yield was 63% and the product purity was >98%.
[0043] The amounts of the substances used and the reaction conditions were extended experimentally with those in the examples to illustrate that the technical solution of the present invention has good functional group compatibility.
[0044] The present invention has been described in detail above. The above descriptions are only embodiments of the present invention and should not limit the scope of implementation of the present application. That is, all equivalent changes and modifications made within the scope of the present application should still fall within the scope of the present invention.
[0045] BRIEF DESCRIPTION OF THE DRAWINGS
[0046] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the product 1 prepared in the present invention;
[0047] Figure 2 The carbon NMR spectrum of the product 1 prepared by the present invention;
[0048] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the product 2 prepared by the present invention;
[0049] Figure 4 The carbon NMR spectrum of the product 2 prepared by the present invention;
[0050] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the product 3 prepared by the present invention;
[0051] Figure 6 The carbon NMR spectrum of the product 3 prepared by the present invention;
[0052] Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of the product 7 prepared by the present invention;
[0053] Figure 8 The NMR fluorine spectrum of the product 7 prepared by the present invention;
[0054] Fig. 9 The carbon NMR spectrum of the product 7 prepared by the present invention;
[0055] Fig.10 This is the hydrogen nuclear magnetic resonance spectrum of the product 8 prepared in the present invention;
[0056] Fig.11 The NMR fluorine spectrum of the product 8 prepared by the present invention;
[0057] Fig.12 The carbon NMR spectrum of the product 8 prepared by the present invention;
[0058] Fig.13 This is the hydrogen nuclear magnetic resonance spectrum of the product 9 prepared by the present invention;
[0059] Fig.14 The NMR fluorine spectrum of the product 9 prepared by the present invention;
[0060] Fig.15 This is the carbon NMR spectrum of the product 9 prepared in the present invention.
Claims
1. A method for synthesizing olefins and fluoroolefins, characterized in that: Acrylic acid or fluoroacrylic acid and dihydroquinazolinone compounds are used as reactants, oxygen is used as an oxidant, ferrous acetate is used as a catalyst, and chlorobenzene is used as a solvent. The reaction is carried out at 100° C. according to the following reaction formula to obtain a class of olefins and fluoroolefin compounds.