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Method for preparing alkyne ketone by coupling triazine carboxylate 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 goal of improving electrophilicity, promoting oxidative addition, and high yield of reaction products Effect

Inactive Publication Date: 2016-06-29
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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 alkyne ketone by coupling triazine carboxylate with terminal alkyne
  • Method for preparing alkyne ketone by coupling triazine carboxylate with terminal alkyne
  • Method for preparing alkyne ketone by coupling triazine carboxylate 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 and preparation methods used 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 and pass nitrogen three times, and then add 55μL (0.6mmol) of phenylacetylene and 3mL of acetonitrile After stirring for 10 hours at 50° C., the reaction was stopped, and the reaction was naturally reduced to room temperature, filtered and separated by column chromatography to obtain 1,3-diphenyl-2-ethynyl-1-one as a white solid with a yield of 90%. The resulting product was characterized by a BrukerAvance superconducting Fourier digital nuclear magnetic resonance spectrometer. The characterization data are: 1 HNMR(400MHz, CDCl 3 )δ: 8.15 (d, J = 7.5 Hz, 2H), 7.65-7.51 (m, 3H), 7.42 (dd, J = 17.3, 10.5 Hz, 3H), 7.34 (t, J = 7.0 Hz, 2H); 13 CNMR(101MHz,...

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 and preparation methods used are:

[0020]

[0021] In Example 1, the triazine benzoate used was replaced with an equimolar triazine p-methoxybenzoate. The other steps were the same as in Example 1, and a light grayish yellow solid 1-(4-methoxy (Phenyl)-3-phenyl-2-ethynyl-1-one, the yield is 98%, and the characterization data are: 1 HNMR(400MHz, CDCl 3 )δ: 8.19 (d, J=8.7 Hz, 2H), 7.67 (d, J=7.1 Hz, 2H), 7.49-7.38 (m, 3H), 6.98 (d, J=8.8 Hz, 2H), 3.89 ( s, 3H); 13 CNMR(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 with the following structural formula as an example, the raw materials and preparation methods used are:

[0024]

[0025] In Example 2, the phenylacetylene used was replaced with an equimolar p-tolueneacetylene, and the other steps were the same as in Example 2. The yellow solid 1-(4-methoxyphenyl)-3-(4- The yield of methylphenyl)-2-ethynyl-1-one is 98%, and the characterization data are: 1 HNMR(400MHz, CDCl 3 )δ: 8.19 (d, J = 8.9 Hz, 2H), 7.57 (d, J = 8.1 Hz, 2H), 7.22 (d, J = 7.9 Hz, 2H), 6.98 (d, J = 8.9 Hz, 2H) , 3.90(s, 3H), 2.40(s, 3H); 13 CNMR(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 synthetic technical field of alkynone compounds, and specifically relates to a carboxylic acid triazine ester compound as a reaction substrate, and it is formed with a terminal alkyne under the catalysis of palladium acetate without adding a ligand and a base. The method of alkynone compounds. Background technique [0002] Alkynone is an important intermediate for the construction of medical molecules and natural substances, and is 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 alkynone is to use transition metal catalyzed cross-coupling reaction of acid chloride and terminal alkyne, and also use lithium alkyne, Grignard reagent and weinreb amino compound or aldehyde to generate. However, the common problem with these reactions is that acid chlorides...

Claims

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Application Information

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Patent Type & Authority Patents(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