Phenylacetic acid type aryne preparation method

A technology of phenylacetic acid and type, applied in directions such as silicon organic compounds, can solve the problems of complicated preparation process of aryl alkynes, difficult to obtain raw materials, and high production cost, and achieve the effects of easy industrial large-scale production, easy acquisition, and reduction of reaction steps.

Inactive Publication Date: 2019-04-02
HUBEI UNIV
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Problems solved by technology

[0004] In view of this, the present application provides a new method for preparing aryne of different substituted phenylacetic acid types, which solves the problem that the existing aryne preparation process is complex, raw materials are not easy to obtain, exogenous directing groups must be introduced, the production cost is high, and the steps are cumbersome lack of

Method used

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  • Phenylacetic acid type aryne preparation method
  • Phenylacetic acid type aryne preparation method
  • Phenylacetic acid type aryne preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] (S)-2-(6-methoxy-3-((triisopropylsilyl)ethynyl)naphthalen-2-yl)propanoicacid

[0020]

[0021] Add 0.69 g (S)-(+)-2-(6-methoxy-2-naphthyl)propionic acid, silver acetate 1 g, palladium acetate 69mg, and N-acetyl-L-phenylalanine into the reactor Acid 126 mg, sodium acetate 0.5 g, dichloroethane 5 ml, triisopropylsilylethynyl bromide 1 ml, and reacted at 60 ℃ for 16 h. After the reaction is completed, add acetic acid to acidify, extract three times with ethyl acetate, combine the organic phases, wash the organic phases with dilute hydrochloric acid and saturated brine, add an appropriate amount of anhydrous sodium sulfate to dry, filter to remove anhydrous sodium sulfate, petroleum ether: acetic acid Ethyl ester=10:1 was purified by column chromatography and distilled under reduced pressure to obtain 0.99g of product with a yield of 83.42%. 1 H NMR (501 MHz, CDCl 3 ) δ7.95 (s, 1H), 7.69 (s, 1H), 7.66 (d, J = 9.0 Hz, 1H), 7.13 (dd, J = 9.0, 2.5Hz, 1H), 7.06 (d, J = 2.5 Hz, ...

Embodiment 2

[0025] Example 2 Preparation of (S)-2-(4-isobutyl-2-((triisopropylsilyl)ethynyl)phenyl)propanoic acid

[0026]

[0027] Add 0.62 g of Levoprofen, 1 g of silver acetate, 69 mg of palladium acetate, 126 mg of N-acetyl-L-phenylalanine, 0.5 g of sodium acetate, 5 ml of dichloroethane, and triisopropyl in the reactor. 1 ml of silylethynyl bromide, react at 60 ℃ for 16 h. The other operation steps are the same as those in Example 1-1 to obtain 0.89 g of product (P1) with a yield of 76.72%. 1 H NMR (501 MHz, CDCl 3 ) δ 7.27(s, 1H), 7.23 (d, J = 8.0 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.39 (q, J = 7.0Hz, 1H), 2.42 (d, J = 7.0 Hz, 2H), 1.86 (dt, J = 13.5, 7.0 Hz, 1H), 1.50 (d, J = 7.0 Hz, 3H), 1.13 (s, 21H), 0.90 (d, J = 7.0 Hz, 6H); 13 C NMR (126 MHz, CDCl 3 ) δ 179.8, 140.4, 139.4, 133.3, 129.7, 126.2, 122.7, 104.9, 94.9, 44.7, 42.6, 29.9, 22.3, 18.6, 18.0, 11.3.

Embodiment 3

[0029] Preparation of (S)-8-((triisopropylsilyl)ethynyl)-1,2,3,4-tetrahydronaphthalene-1-carboxylic acid

[0030]

[0031] Add 0.53 g (S)-(-)-1,2,3,4-tetrahydro-1-naphthoic acid, silver acetate 1 g, palladium acetate 69 mg, and N-tert-butoxycarbonyl-L- Phenylalanine 140 mg, sodium acetate 0.5 g, dichloroethane 5 ml, triisopropylsilyl ethynyl bromide 1 ml, and reacted at 60 ℃ for 16 h. The other operation steps are the same as those in Example 1-1 to obtain 0.88 g of product with a yield of 82.24%. 1 H NMR(501 MHz, CDCl 3 ) δ 7.33 (d, J = 7.5 Hz, 1H), 7.12 (t, J = 7.5 Hz, 1H), 7.07(d, J = 8.0 Hz, 1H), 4.20 (d, J = 6.5 Hz, 1H), 2.83 (d, J = 17.0 Hz, 1H), 2.74 (m, 1H), 2.35 (d, J = 13.5 Hz, 1H), 2.05 – 1.94 (m, 1H), 1.80 (d, J =26.0 Hz, 2H), 1.12 (d, J = 2.0 Hz, 21H); 13 C NMR (126 MHz, CDCl 3 ) δ 180.4, 137.4, 135.0, 130.3, 129.4, 126.5, 124.3, 104.8, 95.9, 43.4, 29.1, 27.1, 19.5, 18.5, 11.2.

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Abstract

The invention discloses a phenylacetic acid type aryne preparation method, wherein compounds represented by a structural formula I and a structural formula II are used as raw materials, the ortho-alkynylation reaction of the compound represented by the structural formula I is achieved in an organic solvent by adding a ligand and a palladium catalyst in the presence of an alkali and an oxidizing agent so as to obtain phenylacetic acid type aryne represented by a structural formula III. According to the present invention, the introducing of the external guiding group is not required during the synthesis so as to reduce the reaction steps; and the preparation method has advantages of simple and convenient process operation, easily-available raw materials, mild conditions, cost reducing and reduced requirements on equipment, and is suitable for industrial mass production. The formulas I, II and III are defined in the specification.

Description

Technical field [0001] The invention relates to a preparation method of phenylacetic acid type arylacetylene, belonging to the technical field of organic synthesis and drug modification. Background technique [0002] As an important building block for organic synthesis, arylalkynes have a wide range of applications in materials, medicines and natural products. It can participate in oxidation, addition and polymerization reactions. The development of efficient synthesis methods for aromatic acetylenes has always been a hot topic for chemists. [0003] The synthesis of phenylacetic acid type aromatic acetylenes has been reported in some literatures, mainly involving the activation of CH bond to introduce the core alkynyl group. The synthesis process is relatively difficult, often requiring the introduction of exogenous guiding groups, and the steps are cumbersome. . Literature (Org. Lett., 2016, 18, 2970–2973; Org. Chem. Front. , 2017, 4 , 1931-1934) used triazolamide and glycine...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/08
Inventor 刘悦进周郑鑫曾明华
Owner HUBEI UNIV
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