Preparation method of asymmetric 1,3-diyne compound

An alkyne compound and asymmetric technology, which is applied in the field of preparation of asymmetric 1,3-diyne compounds, can solve the problems of long reaction route, reduced yield, and increased difficulty of reaction, etc., and achieves simple operation and high reaction efficiency. The effect of fewer steps and mild reaction conditions

Inactive Publication Date: 2018-03-23
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the reaction route of asymmetric 1,3-diyne compounds is longer, the difficulty of the reaction becomes greater, and the yield will decrease accordingly

Method used

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  • Preparation method of asymmetric 1,3-diyne compound
  • Preparation method of asymmetric 1,3-diyne compound
  • Preparation method of asymmetric 1,3-diyne compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Synthesis of 1-chloro-4-(1,3-octadiynyl)benzene

[0029] Take a 25mL dry Schlenk bottle, add a stirring bar, and mix bromoalkene 1a (0.2mmol), DMSO (1mL, preliminarily dried through activated molecular sieves), cuprous iodide (CuI, 0.04mmol), sarcosine (Creatine ,0.08mmol), cesium carbonate (Cs 2 CO 3 , 0.8 mmol) were successively added into the Schlenk bottle under the protection of nitrogen, the temperature of the oil bath was 60°C, and the reaction was stirred for 4h. After the reaction, petroleum ether was extracted (3×10 mL), the organic layers were combined, rotary evaporated, and purified by preparative TLC to obtain the product (developer: petroleum ether, 60-90° C.), with a yield of 72%.

[0030]

[0031] 1-Chloro-4-(1,3-octadiynyl)benzene

[0032] 1 H NMR (500MHz, CDCl3) δ7.40(d, J=8.4Hz, 2H), 7.28(d, J=8.4Hz, 2H), 2.37(t, J=7.0Hz, 2H), 1.61–1.51(m ,2H),1.45(m,2H),0.93(t,3H).

[0033] 13 C NMR (500MHz, CDCl3) δ134.85, 133.63, 128.69, 85.45, 75.29, 73...

Embodiment 2

[0037] Synthesis of 1-chloro-4-(1,3-heptadynyl)benzene

[0038] Take a 25 mL dry Schlenk bottle, add a stirring bar, and mix bromoalkene 2a (0.2 mmol), DMSO (1 mL, preliminarily dried through activated molecular sieves), cuprous iodide (CuI, 0.04 mmol), sarcosine (Creatine ,0.08mmol), cesium carbonate (Cs 2 CO 3 , 0.8 mmol) were successively added into the Schlenk bottle under the protection of nitrogen, the temperature of the oil bath was 60°C, and the reaction was stirred for 4h. After the reaction, petroleum ether was extracted (3×10 mL), the organic layers were combined, rotary evaporated, and purified by preparative TLC to obtain the product (developing solvent: petroleum ether, 60-90° C.), with a yield of 69%.

[0039]

[0040] 1-Chloro-4-(1,3-heptadiynyl)benzene

[0041] 1 H NMR (500MHz, CDCl 3 )δ7.32(d, J=8.6Hz, 2H), 7.20(d, J=8.6Hz, 2H), 2.27 (t, J=7.0Hz, 2H), 1.58–1.47(m, 3H), 0.96( t,3H).

Embodiment 3

[0043] Synthesis of 4-bromo-2-fluoro-1-(1,3-heptadiynyl)benzene

[0044] Take a 25 mL dry Schlenk bottle, add a stirring bar, and mix bromoalkene 3a (0.2 mmol), DMSO (1 mL, preliminarily dried through activated molecular sieves), cuprous iodide (CuI, 0.04 mmol), sarcosine (Creatine ,0.08mmol), cesium carbonate (Cs 2 CO 3 , 0.8 mmol) were successively added into the Schlenk bottle under the protection of nitrogen, the temperature of the oil bath was 60°C, and the reaction was stirred for 4h. After the reaction, petroleum ether was extracted (3×10 mL), the organic layers were combined, rotary evaporated, and purified by preparative TLC to obtain the product (developing solvent: petroleum ether, 60-90° C.), with a yield of 47%.

[0045]

[0046] 4-Bromo-2-fluoro-1-(1,3-heptadiynyl)benzene

[0047] 1 H NMR (500MHz, CDCl3) δ7.27–7.23(m,1H),7.21–7.17(m,2H),2.28(t,J=7.0Hz,2H),1.60–1.49(m,2H),0.96( t,3H).

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Abstract

The invention belongs to the field of medicine, pesticide intermediates and related chemical technologies, and relates to a preparation method of an asymmetric 1,3-diyne compound. The invention uses brominated allene as a raw material, and can obtain unsymmetrical 1,3-diyne compounds under the catalysis of cuprous iodide / amino acid. The method is easy to operate, has fewer reaction steps, mild reaction conditions, medium yield, low raw material price, and some products have not been reported in literature. Moreover, the obtained product has high yield and high purity, fully meets the quality requirements as a pharmaceutical intermediate, and provides favorable conditions for its industrial production. The asymmetric 1,3-diyne compound obtained by the method can be used to prepare heterocyclic compounds, and its derivatives widely exist in biologically active natural macromolecules.

Description

technical field [0001] The invention belongs to the field of medicine, pesticide intermediates and related chemical technologies, and relates to a preparation method of an asymmetric 1,3-diyne compound. Background technique [0002] Asymmetric 1,3-diyne compounds are not only important intermediates or raw materials in organic synthesis, widely used in the synthesis of medicines and pesticides, but also the basic skeleton of natural medicines and many substances with physiological activities, and have a broad market Therefore, the development of efficient synthesis methods and technologies of conjugated diynes has always been a research hotspot. [0003] Currently the most extensive and effective synthetic method for asymmetric 1,3-diynes, Cadiot-Chodkiewicz coupling to prepare asymmetric 1,3-diynes with terminal alkyne and 1-bromoalkyne in Cu(I) salt and a suitable organic amine as a ligand catalyst to prepare asymmetric 1,3-diyne compounds (Shi W, Lei A.1,3-Diynechemistry...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/00C07C17/25C07C25/02C07B53/00
CPCC07C17/00C07B53/00C07B2200/07C07B2200/09C07C17/25C07C25/02
Inventor 杜欣姜文凤邵冠花赵晓俊
Owner DALIAN UNIV OF TECH
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