CN-117720506-B - Cyclic ether compound containing indenone structure and preparation method thereof

Abstract

The invention belongs to the technical field of compound preparation, and discloses a preparation method of a cyclic ether compound containing an indenone structure, which comprises the following steps: the indene dione diazonium compound and the cyclic ether compound shown in the formula I are used as raw materials, and the cyclic ether compound containing the indene ketone structure shown in the formula II is synthesized by heating reaction in an argon atmosphere under the action of a copper salt catalyst. According to the invention, copper salt is used as a catalyst, namely copper carbene is inserted into a diazonium compound to form oxygen Weng Sheli De, then the oxygen Weng Sheli De and cyclic ether are subjected to ring expansion reaction, so that the cyclic ether compound containing the indenone structure is efficiently synthesized, and the product yield is high.

Inventors

• ZHANG GUANGWU
• Xiong Hengying
• ZHOU YUFENG

Assignees

• 河南大学

Dates

Publication Date

20260505

Application Date

20231204

Claims (4)

1. 1. The preparation method of the cyclic ether compound containing the indenone structure is characterized by comprising the following steps of taking an indenodione diazo compound shown in a formula I and a cyclic ether compound as raw materials, and heating and reacting in an argon atmosphere under the action of a copper salt catalyst to synthesize the cyclic ether compound containing the indenone structure shown in a formula II, wherein the copper salt catalyst is selected from cuprous cyanide, cupric hydroxide, cuprous bromide or cuprous chloride, the cyclic ether compound is selected from trimethoxy ester, tetrahydrofuran, tetrahydropyran, dioxane, cyclohexane, 15-crown ether-5 or 18-crown ether-6, and the synthetic route is as follows: , wherein R is selected from H or halogen, n is 1-7, and m is 1-9.
2. 2. The method according to claim 1, wherein the reaction temperature is 90 to 120 ℃.
3. 3. The preparation method according to claim 1, wherein the copper salt catalyst is added in an amount of 10% of the molar amount of the indenodiketone diazonium compound.
4. 4. The preparation method according to claim 1, wherein the dosage ratio of the cyclic ether compound to the indenodiketone diazonium compound is 1ml to 0.1 mmol.

Description

Cyclic ether compound containing indenone structure and preparation method thereof Technical Field The invention belongs to the technical field of compound preparation, and relates to a cyclic ether compound containing an indenone structure and a preparation method thereof. Background Macrocyclic molecules are an important class of compounds in nature, being the core backbone of many natural products and active molecules. Polycyclic ethers are a specific subclass of macrocyclic molecules, and can be used as effective binding acceptors for cations or small molecules, with a variety of uses and applications in the fields of chemistry, materials, medicine, and the like. For example, lysine ether has inhibitory effects on Escherichia coli and Bacillus subtilis, and 5-fluorouracil is a common and effective chemotherapeutic agent against various tumor types. Because the polycyclic ether has potential biological and pharmacological activities, the development of an efficient synthesis method for constructing the compounds has important significance. In 2010, the group of lacours group-induced topics developed rhodium-catalyzed regioselective condensation of two molecules of a-diazo- β -ketoesters and two molecule cyclic ethers, enabling synthesis of 18-membered polyether rings in one pot (eghida w., besnard c., lacour j., angel. Chem. Int. Ed.,2010,49,7253-7256). At present, the reported method for synthesizing the polycyclic ether has the defects of poor substrate universality, poor substrate universality and the like. Therefore, the development of a new method for synthesizing the polycyclic ether is of great significance. Disclosure of Invention Aiming at the technical problems, the invention provides the cyclic ether compound containing the indenone structure and the preparation method thereof, wherein copper salt is used as a catalyst, namely copper carbene is inserted into a diazonium compound to form oxygen Weng Sheli De, then the oxygen Weng Sheli De and the cyclic ether are subjected to ring expansion reaction, so that the cyclic ether compound containing the indenone structure is efficiently synthesized, and the product yield is high. In order to achieve the above purpose, the present invention adopts the following technical scheme: The invention provides a cyclic ether compound containing an indenone structure, which has the following chemical structural formula: Wherein R is selected from H or halogen, n is 1-7, and m is 1-9. The invention also provides a preparation method of the cyclic ether compound containing the indenone structure, which comprises the following steps of taking the indendione diazonium compound shown in the formula I and the cyclic ether compound as raw materials, and heating and reacting in an argon atmosphere under the action of a copper salt catalyst to synthesize the cyclic ether compound containing the indenone structure shown in the formula II, wherein the synthetic route is as follows: wherein R is selected from H or halogen, n is 1-7, and m is 1-9. The copper salt catalyst in the technical scheme of the invention is selected from cuprous cyanide, cupric hydroxide, cuprous bromide or cuprous chloride. The cyclic ether compound in the technical scheme is selected from trimethoxy ester, tetrahydrofuran, tetrahydropyran, dioxane, cyclohexane, 15-crown ether-5 or 18-crown ether-6. According to the technical scheme, the reaction temperature is 90-120 ℃. The addition amount of the copper salt catalyst in the technical scheme of the invention is 10 percent of the molar amount of the indenodiketone diazo compound. According to the technical scheme, the dosage ratio of the cyclic ether compound to the indenodiketone diazonium compound is 1ml to 0.1mmol. Compared with the prior art, the invention has the beneficial effects that: the invention uses copper salt as catalyst, namely copper carbene is inserted into diazonium compound to form oxygen Weng Sheli De, then the oxygen Weng Sheli De and cyclic ether are subjected to ring expansion reaction, the cyclic ether compound containing indenone structure is synthesized efficiently, and the product yield is high. The reaction scheme for example twelve is shown below. The synthesis method has the advantages of wide sources of raw materials, low price of the used metal copper catalyst, environmental protection, simple and convenient operation, excellent product yield, suitability for large-scale preparation and wide application prospect. Drawings FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 3,4,7,8,11,12-hexahydro-2H, 6H,10H, 18H-indeno [1,2-b ] [1,4,8,12] tetraoxacyclopentadecen-18-one in example 1 of the present invention. FIG. 2 is a nuclear magnetic resonance carbon spectrum of 3,4,7,8,11,12-hexahydro-2H, 6H,10H, 18H-indeno [1,2-b ] [1,4,8,12] tetraoxacyclopentadecen-18-one of example 1 of the present invention. FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of 3,4,5,6,9,10,11,12-octahydro 2H,8H, 18H-indeno [1,2-