Electrochemical synthesis method of 1, 1 '-binaphthalene compound

A synthesis method and compound technology, applied in the field of electrochemical organic synthesis, can solve the problems of complex reaction system and operation, unfriendly environmental protection, low atomic efficiency, etc., and achieve the effect of simple and safe reaction system, environmental friendliness and high reaction yield

Pending Publication Date: 2022-01-21
QILU UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] In view of the deficiencies of the prior art, especially the problems of high cost, complex reaction system and operation, narrow application range, low atomic efficiency, and unfriendly environmental protection in the existing preparation method, the present invention provides a more green, environmentally friendly and applicable A wide range of methods for the synthesis of 1,1'-binaphthyl compounds

Method used

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  • Electrochemical synthesis method of 1, 1 '-binaphthalene compound
  • Electrochemical synthesis method of 1, 1 '-binaphthalene compound
  • Electrochemical synthesis method of 1, 1 '-binaphthalene compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Example 1: Preparation of 4,4'-diethyl-1,1'-binaphthalene

[0056]

[0057] Add 0.4mmol of 1-ethylnaphthalene, 0.2mmol of lithium perchlorate, and 5mL of acetonitrile into a 10mL three-necked flask in sequence, use a carbon rod as an anode, and a platinum sheet electrode as a cathode, react at 25°C with a constant current of 5mA for 5h, TLC Tracking and monitoring; after the reaction was completed, the solvent was removed with a rotary evaporator, and the residue was purified by flash silica gel column chromatography (petroleum ether as mobile phase) to obtain the product with a yield of 76%.

[0058] 1 H NMR (400MHz, Chloroform-d) δ8.19 (d, J = 8.5Hz, 2H), 7.55-7.40 (m, 8H), 7.30 (t, J = 7.6Hz, 2H), 3.25 (q, J = 7.5Hz, 4H), 1.52(t, J=7.5Hz, 6H);

[0059] 13 C NMR (101MHz, Chloroform-d) δ139.9, 137.1, 133.3, 131.8, 127.8, 127.6, 125.5, 125.4, 124.4, 123.9, 26.0, 15.1;

[0060] MS for C 24 h 22 calcd 310, found 310.

Embodiment 2

[0061] Example 2: Preparation of 4,4'-dimethyl-1,1'-binaphthalene

[0062]

[0063] Add 0.4mmol of 1-methylnaphthalene, 0.2mmol of lithium perchlorate, and 5mL of acetonitrile into a 10mL three-necked flask in sequence, use a carbon rod as the anode, and a platinum sheet electrode as the cathode, react at 25°C with a constant current of 5mA for 5h, TLC Tracking and monitoring; after the reaction was completed, the solvent was removed with a rotary evaporator, and the residue was purified by flash silica gel column chromatography (petroleum ether as mobile phase) to obtain the product with a yield of 78%.

[0064] 1 H NMR (600MHz, Chloroform-d) δ8.11 (d, J = 8.4Hz, 2H), 7.52 (t, J = 7.6Hz, 2H), 7.47-7.43 (m, 4H), 7.40 (d, J = 7.0Hz, 2H), 7.30(t, J=7.4Hz, 2H), 2.81(s, 6H);

[0065] 13 C NMR (151MHz, Chloroform-d) δ137.0, 133.9, 133.0, 132.5, 127.6, 127.3, 126.1, 125.5, 124.2, 19.6;

[0066] MS for C 22 h 18 calcd 282, found 282.

Embodiment 3

[0067] Example 3: Preparation of 4,4'-diisopropyl-1,1'-binaphthalene

[0068]

[0069] Add 0.4mmol of 1-isopropylnaphthalene, 0.2mmol of lithium perchlorate, and 5mL of acetonitrile to a 10mL three-necked flask in sequence, use a carbon rod as an anode, and a platinum sheet electrode as a cathode, and react at a constant current of 5mA for 5h at 25°C. TLC tracking and monitoring; after the reaction was completed, the solvent was removed with a rotary evaporator, and the residue was purified by flash silica gel column chromatography (petroleum ether as mobile phase) to obtain the product with a yield of 73%.

[0070] 1 H NMR (400MHz, Chloroform-d) δ8.22 (dd, J = 8.6, 1.1Hz, 2H), 7.54-7.42 (m, 8H), 7.25 (td, J = 6.8, 1.2Hz, 2H), 3.86 ( p,J=6.8Hz,2H),1.49(dd,J=9.3,6.9Hz,12H);

[0071] 13 C NMR (151MHz, Chloroform-d) δ144.2, 136.9, 133.4, 131.4, 127.8, 127.7, 125.5, 125.2, 123.4, 121.3, 28.7, 23.8;

[0072] MS for C 26 h 26 calcd 338, found 338.

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Abstract

The invention relates to an electrochemical synthesis method of a 1, 1 '-binaphthalene compound, which comprises the following steps: sequentially adding a solvent, an electrolyte, a naphthalene compound, a positive electrode and a negative electrode into a diaphragm-free electrolytic tank, stirring at room temperature, and reacting under a constant current condition; and after the reaction is completed, concentrating the reaction liquid, and separating and purifying the organic phase to obtain the product 1, 1 '-binaphthalene compound. The method has the advantages of easily available raw materials, no transition metal or oxidant, no safety problem and heavy metal residue problem, simple operation, considerable yield, environmental protection, and good application prospect. The electrode used in the method is a common inert electrode, electrode modification is not needed, an oxidizing agent and a toxic and expensive catalyst are not used, the reaction yield is high, and a reaction system is simple and safe.

Description

technical field [0001] The invention belongs to the technical field of electrochemical organic synthesis, and relates to a synthesis method of 1,1'-binaphthyl, in particular to an electrochemical preparation method of 1,1'-binaphthyl compounds. Background technique [0002] 1,1'-binaphthyl is the core structure of various functional material molecules such as bioactive molecules, dyes, supramolecules, and sensors. 1,1'- Binaphthalene compounds have been widely used as chiral ligands and chiral catalysts in the field of organic asymmetric synthesis due to their chiral axis characteristics. [0003] The traditional methods for preparing 1,1'-binaphthyl compounds include two categories: reductive coupling and oxidative coupling. Reductive coupling is mainly realized through Kumada, Negishi, Stille, Hiyama and Suzuki coupling reactions; oxidative coupling is through the dehydrogenation between two naphthalene and its derivatives to directly construct a 1,1'-binaphthyl skeleton....

Claims

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Application Information

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Patent Type & AuthorityApplications(China)
IPC IPC(8): C25B3/03C25B3/07C25B3/23
CPCC25B3/03C25B3/07C25B3/23
Inventor刘思远陈建宾
OwnerQILU UNIV OF TECH