Poly-substituted tetrahydrofuran and tetrahydropyrane diene compound and preparation method thereof

A technology of tetrahydropyrandiene and tetrahydrofuran, which is applied in the directions of organic chemistry, drug combination, antipyretic and the like, and achieves the effects of simple synthesis method, good yield, and cheap and easy-to-obtain catalysts

Pending Publication Date: 2020-12-29
CHENGDU ORGANIC CHEM CO LTD CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] At present, there are few reports on the synthesis of tetrahydrofuran and tetrahydropyran diene ((a) J.Chem.Soc., Chem.Commun., 1986, 1230-1232. (b) Org.Lett.2018,20, 4709-4712. (c) Ange

Method used

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  • Poly-substituted tetrahydrofuran and tetrahydropyrane diene compound and preparation method thereof
  • Poly-substituted tetrahydrofuran and tetrahydropyrane diene compound and preparation method thereof
  • Poly-substituted tetrahydrofuran and tetrahydropyrane diene compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] Target compound:

[0051]

[0052] Preparation:

[0053] Step 1: Dissolve 2.0g (E)-2-benzylidene-3,3-dimethylbutyrolactone in 10ml 1,4-dioxane to form an allyl lactone solution; weigh it into the reaction bottle 1.3g malononitrile, add 10ml 1,4-dioxane, cool down to 0-5°C; weigh 2.2g potassium tert-butoxide into the reaction flask; drop the alkenyl lactone solution into the reaction system, 0- React at 5°C for 10 h; after the reaction, add water to quench, extract with ethyl acetate, evaporate the solvent under reduced pressure to obtain 2.3 g of oily hemiacetal, yield 85%.

[0054] Step 2: Dissolve the hemiacetal obtained in the previous step in 10ml chloroform, add 2g Cu(OTf) 2 , and then heated up to 45° C. for 4 h; after the reaction, quenched with water, extracted with chloroform, and distilled off the solvent under reduced pressure to obtain 2 g of oil, with a yield of 95%.

[0055] Product characterization:

[0056] Colorless liquid. 1 H NMR (400MHz, CDCl...

Embodiment 2

[0058] Target compound:

[0059]

[0060] Preparation:

[0061] Step 1: Dissolve 2.0g (E)-2-benzylidene-3,3-dimethylbutyrolactone in 10ml tetrahydrofuran to form an allyl lactone solution; weigh 0.5g acetonitrile into the reaction bottle, add 10ml tetrahydrofuran ; Weigh n-butyllithium into the reaction flask (the molar ratio of n-butyllithium to (E)-2-benzylidene-3,3-dimethylbutyrolactone is 0.4:1); The ester solution was dripped into the reaction system, and reacted at 10°C for 20 hours; after the reaction was completed, it was quenched with water, extracted with ethyl acetate, and separated by column chromatography to obtain hemiacetal as an oily product with a yield of 83%.

[0062] Step 2: Dissolve the hemiacetal obtained in the previous step in 10ml of dichloromethane, add Zn(OAc) 2 2H 2 O(Zn(OAc) 2 2H 2 The molar ratio of O to hemiacetal is 0.1:1), and then the temperature was raised to 20°C for 48 hours; after the reaction, quenched with water, extracted with e...

Embodiment 3

[0066] Target compound:

[0067]

[0068] Preparation:

[0069] Step 1: Dissolve 2.2g (E)-2-benzylidene-3,3-dimethylvalerolactone in 12ml of ether to form an allyl lactone solution; weigh 2.6g of dimethyl malonate into the reaction bottle ester, add 10ml ether; add sodium hydride into the reaction flask (the molar ratio of sodium hydride to (E)-2-benzylidene-3,3-dimethylvalerolactone is 0.8:1); The lactone solution was dripped into the reaction system, and reacted at 20°C for 12 hours; after the reaction was completed, it was quenched with water, extracted with ethyl acetate, and separated by column chromatography to obtain hemiacetal as an oil with a yield of 84%.

[0070] Step 2: Dissolve the hemiacetal obtained in the previous step in 12ml of n-hexane, add CuSO 4 ·5H 2 O(CuSO 4 ·5H 2 The molar ratio of O to hemiacetal is 0.2:1), and then the temperature was raised to 30°C for 24 hours; after the reaction, quenched with water, extracted with ethyl acetate, and the so...

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Abstract

The invention belongs to the field of organic synthesis, and provides a poly-substituted tetrahydrofuran and tetrahydropyrane diene compound as shown in a formula I. In the formula I, R1 is selected from aryl or hetero-aryl; R2 and R3 are selected from hydrogen or C1-C6 alkyl; R4 and R5 are each independently selected from aryl, hetero-aryl, C1-C6 alkyl or hydrogen; and R6 and R7 are selected fromcyano, nitro, C1-C6 alkyl, an ester group or hydrogen. A target product is synthesized through two steps of reaction, and the method comprises the following steps: (1) reacting alpha-alkenyl lactonewith a nucleophilic reagent (nitrile, nitroalkane or ester and the like) for 1-48 hours at -78 to 60 DEG C under the action of alkali to obtain a hemiacetal intermediate; and (2) dehydrating the hemiacetal intermediate under the catalytic action of Lewis acid or Bronsted acid to form the compound shown in the formula I. The method is simple in process equipment, easy to operate, environment-friendly, low in cost and good in yield.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a multi-substituted tetrahydrofuran and tetrahydropyran diene compound and a preparation method thereof. Background technique [0002] Multi-substituted tetrahydrofuran and tetrahydropyran diene are very important synthons, which are widely used in the synthesis of various natural products and drug molecules. This kind of compound can be prepared by D-A / oxidation reaction to prepare multi-substituted benzofuran and Benzopyran compounds. Benzofuran is a typical representative of a class of oxygen-containing heterocyclic compounds. Benzofuran derivatives and their analogs are widely found in natural products. Many compounds containing benzofuran structure have anti-HIV, anti-tumor, anti-fungal and anti-inflammatory properties The role of cardiovascular aging, so far, more than 30 kinds of natural benzofuran compounds have been used clinically, and humans have also foun...

Claims

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Application Information

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IPC IPC(8): C07D307/54C07D309/32C07D307/94C07D307/93C07D407/06C07D307/79C07D409/06A61P31/10A61P29/00A61P35/00A61P31/12
CPCA61P29/00A61P31/10A61P31/12A61P35/00C07D307/54C07D307/79C07D307/93C07D307/94C07D309/32C07D407/06C07D409/06
Inventor 王继宇张华李福裕张远康张淑青
Owner CHENGDU ORGANIC CHEM CO LTD CHINESE ACAD OF SCI
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