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Method for preparing acetyenic ketone by coupling carboxylate triazinyl ester with terminal alkyne

A technology of carboxylate triazine ester and terminal alkyne, which is applied in the field of synthesis of acetylenic compounds, can solve the problems of difficult substrates, etc., and achieve the effects of improving electrophilicity, using less catalyst, and simple operation

Inactive Publication Date: 2015-04-01
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although these methods are very novel, the substrates used are very special and not easy to obtain, and the reactions often require the participation of specific ligands, which makes the application of such reactions very limited.

Method used

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  • Method for preparing acetyenic ketone by coupling carboxylate triazinyl ester with terminal alkyne
  • Method for preparing acetyenic ketone by coupling carboxylate triazinyl ester with terminal alkyne
  • Method for preparing acetyenic ketone by coupling carboxylate triazinyl ester with terminal alkyne

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] Taking the preparation of 1,3-diphenyl-2-ethynyl-1-one with the following structural formula as an example, the raw materials used and the preparation method are:

[0016]

[0017] Under the protection of nitrogen, add 0.0011g (0.005mmol) of palladium acetate and 0.1305g (0.5mmol) of triazine benzoate into the Shrek tube, vacuum three times with nitrogen, then add 55μL (0.6mmol) of phenylacetylene, 3mL of acetonitrile , stirred at 50°C for 10 hours, stopped the reaction, cooled down to room temperature naturally, filtered and separated by column chromatography to obtain white solid 1,3-diphenyl-2-ethynyl-1-one with a yield of 90%. The resulting product was characterized by a Bruker Avance superconducting Fourier digital NMR spectrometer, and the characterization data were: 1 H NMR (400MHz, CDCl 3 )δ: 8.15(d, J=7.5Hz, 2H), 7.65-7.51(m, 3H), 7.42(dd, J=17.3, 10.5Hz, 3H), 7.34(t, J=7.0Hz, 2H); 13 C NMR (101MHz, CDCl 3 )δ: 178.11, 137.04, 134.23, 133.18, 130.91, 129.6...

Embodiment 2

[0019] Taking the preparation of 1-(4-methoxyphenyl)-3-phenyl-2-ethynyl-1-one with the following structural formula as an example, the raw materials used and the preparation method are:

[0020]

[0021] In Example 1, the triazine benzoate used was replaced with equimolar triazine p-methoxybenzoate, and the other steps were the same as in Example 1 to prepare light grayish yellow solid 1-(4-methoxy Phenyl)-3-phenyl-2-ethynyl-1-one, its productive rate is 98%, and characteristic data is: 1 H NMR (400MHz, CDCl 3 )δ: 8.19(d, J=8.7Hz, 2H), 7.67(d, J=7.1Hz, 2H), 7.49-7.38(m, 3H), 6.98(d, J=8.8Hz, 2H), 3.89( s, 3H); 13 C NMR (101MHz, CDCl 3 )δ: 176.75, 164.61, 133.06, 132.08, 130.69, 130.45, 128.76, 120.49, 114.01, 92.39, 87.06, 55.70.

Embodiment 3

[0023] Taking the preparation of 1-(4-methoxyphenyl)-3-(4-methylphenyl)-2-ethynyl-1-one as an example with the following structural formula, the raw materials used and the preparation method are:

[0024]

[0025] In Example 2, the phenylacetylene used was replaced with equimolar p-methylphenylacetylene, and the other steps were the same as in Example 2 to prepare a yellow solid 1-(4-methoxyphenyl)-3-(4- Methylphenyl)-2-ethynyl-1-one, its productive rate is 98%, characterization data is: 1 H NMR (400MHz, CDCl 3 )δ: 8.19(d, J=8.9Hz, 2H), 7.57(d, J=8.1Hz, 2H), 7.22(d, J=7.9Hz, 2H), 6.98(d, J=8.9Hz, 2H) , 3.90(s, 3H), 2.40(s, 3H); 13 C NMR (101MHz, CDCl 3 )δ: 176.87, 164.55, 141.41, 133.13, 132.07, 130.60, 129.58, 117.43, 114.00, 93.09, 86.93, 55.72, 21.87.

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Abstract

The invention discloses a method for preparing acetyenic ketone by coupling carboxylate triazinyl ester with terminal alkyne. According to the method, palladium acetate is taken as a catalyst, and a carboxylate triazinyl ester compound is taken as an electrophilic reagent to react with an electrophilic reagent terminal alkyne so as to generate an acetyenic ketone compound under a mild condition. The method disclosed by the invention is simple to operate; the used carboxylate triazinyl ester compound is simple to synthesize; the reaction needs no ligand or alkali; the amount of used catalyst is small; the cost is relatively low; substrates are wide in applicability; and product yield is high.

Description

technical field [0001] The invention belongs to the technical field of synthesizing acetylenic ketone compounds, and in particular relates to a triazine carboxylate compound as a reaction substrate, which can be formed with a terminal alkyne under the catalysis of palladium acetate under the condition that no ligand and alkali are added. Method for acetylenic compounds. Background technique [0002] Alkyne ketones are important intermediates in the construction of pharmaceutical molecules and natural substances, and are of great significance in organic synthesis. It can be used to synthesize some organic functional small molecules, such as pyrimidine, quinolone, furan, pyridine, flavone and so on. [0003] The traditional method of synthesizing acetylene ketones is to use transition metals to catalyze the cross-coupling reaction of acid chlorides and terminal alkynes, and to use lithium alkynes, Grignard reagents, and weinreb amino compounds or aldehydes to generate them. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/56C07C49/794C07C49/84C07C49/807C07C49/796C07C49/563C07D333/22C07F17/02
CPCC07C45/562C07C67/293C07C2601/04C07C2601/08C07C2603/74C07D333/22C07F17/02C07C49/796C07C49/84C07C49/813C07C49/563C07C69/157
Inventor 高子伟于波张伟强徐伟杨金斗张莹王振华高培森
Owner SHAANXI NORMAL UNIV
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