CN103102228A - Preparation method of aryl eneyne compound - Google Patents

Abstract

The invention discloses a preparation method of an aryl alkyne compound. Using an aryl alkyne compound and a propargyl alcohol or a propargyl amine compound as raw materials, under the condition of an organic solvent, [Rh(COD)Cl] ₂ and a compound The rhodium complex compound that body action generates is catalyst, and reaction preparation obtains the aryl alkyne compound shown in formula (I). The preparation method of the invention has easy-to-obtain raw materials, low catalyst consumption, high efficiency and easy operation, good regioselectivity, good reaction yield and strong practicability, and the prepared aryl alkyne compound is a class of important chemical synthesis intermediates.

Description

A kind of preparation method of aryl alkyne compound

technical field

The invention relates to the technical field of compound synthesis, in particular to a preparation method of an aryl alkyne compound.

Background technique

Conjugated alkyne compounds are a very important class of synthetic intermediates, which are important structural units and synthetic building blocks of many natural products and pharmaceutical intermediates. At present, the synthesis of acetylenic compounds has been reported in the literature, for example: literature (1) Helio A, Stefani; Marlito Gomes, Jr.Tetrahedron Lett.2005, 46, 563; (2) K, Sonogashira; Y, Tohda; N, Hagihara.Tetrahedron Lett.1975, 16, 4467; (3) Hong Mei Peng; Jing Zhao; Xingwei Li. Adv. Synth. Catal.2009, 351, 1371; (4) H, Katayama; H, Yari; F, Ozawa 2005, 34, 4336(5) M, Nishiura; Z, Hou; T, Miyamoto. J. Am. Chem. Soc. 2003, 125, 1184. The synthesis methods reported in the above literatures of the prior art use metal catalysis to dimerize alkynes or couple alkynes to alkenes to obtain aryl alkyne compounds. Few literatures or reports have proposed an atom-economical synthesis of aryl alkyne compounds via the direct cross-hydrokylation of two terminal alkynes.

Contents of the invention

The present invention overcomes the above-mentioned defects of the prior art, and provides a preparation method of an important chemical synthesis intermediate aryl alkyne compound.

The present invention proposes a kind of preparation method of aryl alkyne compound, take aryl alkyne compound and propargyl alcohol or propargyl amine compound as raw material, use [Rh(COD)Cl] ₂ and the rhodium complexation that ligand action generates The compound is a catalyst, and in an organic solvent, the reaction obtains the described aryl alkyne compound shown in formula (I);

The reaction scheme of described preparation method is shown in following reaction formula (A):

Wherein, _R is hydrogen, methoxy, formaldehyde, nitro, bromine, amino or -NHAc;

R ₂ is -OH or -NHTs.

The product obtained by the preparation method of the present invention is an aryl alkyne compound shown in formula (I),

In formula (I), R ₁ is hydrogen, methoxy, formaldehyde, nitro, bromine, amino or -NHAc; R ₂ is -OH or -NHTs.

R₁为：氢，甲氧基，甲醛基，硝基，溴，氨基或-NHAc。原料炔丙醇或炔丙胺类化合物结构为：R₂为：-OH或-NHTs。In the present invention, the raw material aryl alkyne compound structure is:

R ₁ is: hydrogen, methoxy, formaldehyde, nitro, bromo, amino or -NHAc. The structure of the raw material propargyl alcohol or propargyl amine compound is: R ₂ is: -OH or -NHTs.

In the present invention, the molar ratio of the aryl alkyne compound, propargyl alcohol or propargylamine compound, [Rh(COD)Cl] ₂ , and ligand is 1:1-1.5:0.05:0.2-0.3. Preferably, the molar ratio of aryl alkyne compound, propargyl alcohol or propargylamine compound, [Rh(COD)Cl] ₂ , and ligand is 1:1.5:0.05:0.2.

In the present invention, the ligand is:

Preferably, the ligand is

In the present invention, the organic solvent is dichloromethane, chloroform, tetrahydrofuran, 1,2-dichloroethane. The organic solvent can be a polar or non-polar solvent.

In the present invention, the reaction time is 10-12 hours. For example, react overnight.

In the present invention, the reaction temperature is from 25°C to 40°C. Preferably, the reaction temperature is 40°C.

The preparation method of the present invention uses aryl alkyne compounds and propargyl alcohol or propargyl amine compounds as raw materials, under the condition of the presence of an organic solvent, complexes the rhodium generated by [Rh(COD)Cl] ₂ and the ligand L The compound is used as a catalyst, and the aryl alkyne compound is obtained by reacting overnight. The product obtained by adopting the method of the present invention is separated through column chromatography. The developing agent used for column chromatography separation is a mixed solvent of polar solvent and non-polar solvent. Preferably, the solvent can be mixed solvents such as ethyl acetate-petroleum ether, ethyl acetate-n-hexane, etc., and its volume ratio can be respectively : polar solvent: non-polar solvent = 1: 2-10. For example: ethyl acetate:petroleum ether=1:2-10.

The present invention found that a variety of gem-2-alkynyl alkenes can be synthesized with high gem-selectivity by using the cross-hydroalkynylation reaction catalyzed by the rhodium complex generated by [Rh(COD)Cl] ₂ and the ligand L. Propanol and gem 2-alkynyl allylamines.

In the prior art, a certain alkyne compound is self-dimerized to form an alkyne compound, or a certain type of alkyne compound is head-to-head coupled to form an alkyne compound. And the synthetic method of aryl alkynene compound of the present invention is to adopt metal rhodium complex to catalyze, innovatively propose to use Rh(COD)Cl] ₂ and the rhodium complex that ligand L reacts to generate as catalyzer, make two as raw material Alkyne-like compounds generate new alkyne-alkenes in a head-to-tail manner, achieving high regioselectivity. The present invention adopts atom economical reaction to prepare aryl alkyne compound, which has the advantages of low catalyst consumption, easy to obtain raw materials, high efficiency and easy operation, good regioselectivity, high product yield, strong practicability, efficient atom economy, high selectivity, etc. . The product provided by the preparation method of the invention is a class of important intermediate aryl alkyne compounds.

Detailed ways

The present invention will be further described below in conjunction with embodiment. The process, conditions, experimental methods, etc. for implementing the present invention, except for the content specifically mentioned below, are common knowledge and common knowledge in this field, and the present invention has no special limitation content.

A kind of preparation method of aryl alkyne compound of the present invention, with aryl alkyne compound and propargyl alcohol or propargyl amine compound as raw material, with [Rh (COD) Cl] ₂ and the rhodium complex compound that ligand action generates As a catalyst, in an organic solvent, the reaction obtains the aryl alkyne compound shown in formula (I); the reaction scheme of the preparation method is shown in the following formula (A), wherein, _R is hydrogen, methoxy Base, formaldehyde, nitro, bromine, amino or -NHAc; R ₂ is -OH or -NHTs.

Reaction formula (A)

优选的配体是

The preferred ligand is

Example 1:

With [Rh (COD) Cl] ₂ and the metal rhodium complex that ligand forms to catalyze the reaction that prepares aryl alkynene compound, add [Rh (COD) Cl] ₂ and Ligand, followed by adding anhydrous dichloromethane and raw material compound (1), and finally injecting raw material compound (2) with a peristaltic pump, reacting overnight at 40°C or room temperature. After the reaction, the reaction liquid was concentrated by filtration and separated by column chromatography to obtain the product (ethyl acetate:petroleum ether=1:2-10, V/V). The reaction scheme, reaction raw materials, experimental conditions and products are listed below.

Among them, the ligands L are respectively:

Example 2:

The metal rhodium complex formed by [Rh(COD)Cl] ₂ and the ligand is used to catalyze the reaction of preparing aryl alkyne compounds, and 5mol% [Rh(COD)Cl] is added to the dry reaction tube under an argon atmosphere ₂ and 20mol% PPh ₃ , then add the solvent and the raw material compound (1) sequentially, and finally inject the raw material compound (2) with a peristaltic pump, and react overnight at 40° C. or room temperature. After the reaction, the reaction liquid was concentrated by filtration and separated by column chromatography to obtain the product (ethyl acetate:petroleum ether=1:2-10, V/V). The reaction scheme, reaction raw materials, optimized conditions and products are listed below.

Wherein, DCM is dichloromethane, THF is tetrahydrofuran, and DCE is 1,2-dichloroethane.

Embodiment 3: Arylacetylene and propargyl alcohol prepare 2-alkynyl allyl alcohol under metal rhodium complex catalysis

[Rh(COD)Cl] ₂ (5 mol%) and PPh ₃ (30 mol%) were added to the dry reaction tube under argon atmosphere, followed by 1 ml of anhydrous dichloromethane and 0.5 mmol of aryl acetylene. Finally, 0.75 mmol of propargyl alcohol was injected with a peristaltic pump, and reacted overnight at 40°C. After the reaction, the reaction solution was concentrated by filtration and separated by column chromatography to obtain the product (ethyl acetate:petroleum ether=1:2-10, V/V).

中，R₁分别为：氢、甲氧基、甲醛基、硝基、溴、氨基或-NHAc，相应制备得到的产物式(I)芳基炔烯化合物为P1-P10，详见以下所示。Raw material aryl alkynes

Among them, _R1 are respectively: hydrogen, methoxyl group, formaldehyde group, nitro group, bromine, amino group or-NHAc, and the product formula (I) aryl alkynene compound prepared accordingly is P1-P10, see the following for details .

Yield: 70%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 7.47-7.45(m, 2H), 7.33-7.32(m, 3H), 5.61(d, J=1.2Hz, 1H), 5.58(s , 1H), 4.25 (d, J=3.1Hz, 2H), 1.90 (bs, 1H); ¹³ C NMR (100MHz, CDCl ₃ ): δppm 131.7, 131.2, 128.5, 128.4, 122.8, 120.2, 90.8, 87.0, and 65.3; HRMS (ESI): Calcd. for C ₁₁ H ₁₀ O [M+Na] ⁺ : 181.0624; Found: 181.0623.

Yield: 55%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 7.41(d, J=8.7Hz, 2H), 6.87(d, J=8.7Hz, 2H), 5.58(d, J=1.2Hz, 1H), 5.55(s, 1H), 4.24(s, 2H), 3.83(s, 3H), 1.90(bs, 1H); ¹³ C NMR (100MHz, CDCl ₃ ): δppm 159.8, 133.2, 119.7, 118.4, 114.9, 114.0, 90.6, _85.5 , 65.4, 55.2; HRMS (ESI ₎ : Calcd. for _C12H12O2 [M+Na] ⁺ : 211.0733, found: 211.0730.

Yield: 52%. ¹ H NMR (400MHz, CDCl ₃ ): δppm 8.20(d, J=8.4Hz, 2H), 7.60(d, J=8.8Hz, 2H), 5.73(s, 1H), 5.68( s, 1H), 4.27 (s, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δppm 152.4, 132.4, 129.7, 123.6, 122.7, 92.2, 88.8, 65.1. HRMS (ESI): Calculated for C ₁₁ H ₉ NO ₃ [M+Na] ⁺ : 226.0475, detected value: 226.0474.

Yield: 65%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 10.0(s, 1H), 7.85(d, J=7.5Hz, 2H), 7.61(d, J=7.5Hz, 2H), 5.70( s, 1H), 5.66 (s, 1H), 4.27 (s, 2H), 1.86 (bs, 1H). ¹³ C NMR (125MHz, CDCl ₃ ): δppm 191.5, 135.5, 132.2, 130.8, 129.5, 129.1, 122.0 , 91.0, 89.8, 65.1. HRMS ( _ESI ): Calcd. for _C12H10O2 [M+Na] ⁺ : _209.0573 , found: 209.0571.

Yield: 88%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 7.59 (d, J=7.9Hz, 1H), 7.49 (d, J=1.3Hz, 1H), 7.28 (m, 1H), 7.18( m, 1H), 5.64(s, 2H), 4.27(s, 2H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 133.3, 132.4, 131.1, 129.7, 127.1, 125.7, 124.9, 121.1, 91.6, 89.6, 65.2. HRMS (ESI): Calcd. for _C11H9BrO [M+Na] ₊ ^: 258.9729, found: 258.9730.

Yield: 87%. ¹ H NMR (400MHz, CDCl ₃ ): δppm 7.32-7.28(m, 1H), 7.17-7.13(m, 1H), 6.77-6.71(m, 2H), 5.57(m, 2H) , 4.27(s, 2H), 3.77(br, 2H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 147.9, 132.0, 131.3, 129.9, 120.1, 118.0, 114.5, 107.6, 92.7, 87.6, 65.4. HRMS (ESI): Calcd. for _C11H11NO [M+Na] ⁺ : _196.0733 , found: 196.0728.

Yield: 65%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 7.46-7.44(m, 2H), 7.32-7.30(m, 2H), 5.63(s, 1H), 5.59(s, 1H), 4.23 (s, 2H), 1.80 (br, 1H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 133.1, 131.6, 131.0, 122.7, 121.8, 121.0, 89.4, 88.1, 65.2. HRMS (ESI): Calculated C ₁₁ H ₉ BrO [M+Na] ⁺ 258.9729, found: 258.9729.

Yield: 73%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 8.41(d, J=8.4Hz, 1H), 8.23(bs, 1H), 7.42(d, J=7.6Hz, 1H), 7.36- 7.33(m, 1H), 7.06-7.03(m, 1H), 5.60(s, 1H), 5.59(s, 1H), 4.31(d, J=3.6Hz, 2H), 2.35(bs, 1H), 2.23 (s, 3H). ¹³ C NMR (125MHz, CDCl ₃ ): δppm 169.0, 139.4, 131.2, 130.9, 123.3, 120.9, 119.4, 111.6, 94.5, 86.4, 65.5, 24.6. HRMS (ESI): Calculated for C ₁₃ H ₁₃ NO ₂ [M+Na] ⁺ : 238.0838, detected value: 238.0842.

Yield: 64%. ¹ H NMR (400MHz, CDCl ₃ ): δppm 7.60(t, J=1.6Hz, 1H), 7.46-7.43(m, 1H), 7.38(d, J=7.7Hz, 1H), 7.18(t, J=7.9Hz, 1H), 5.64(d, J=1.4Hz, 1H), 5.59(d, J=1.4Hz, 1H), 4.23(s, 2H), 2.04(bs, 1H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 134.4, 131.6, 130.9, 130.2, 129.8, 124.8, 122.1, 121.3, 89.2, 88.3, 76.7, 65.2. HRMS (ESI): Calculated for C ₁₃ H ₁₃ NO ₂ [M +Na] ⁺ : 258.9729, detected value: 258.9727.

Yield: 42%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 8.15(d, J=7.1Hz, 1H), 7.78(s, 1H), 7.67(d, J=7.7Hz, 1H), 7.38- 7.35(m, 1H), 7.32-7.29(m, 1H), 5.62(s, 2H), 4.30(s, 2H), 1.67(s, 9H). ¹³ CNMR(125MHz, CDCl ₃ ): δppm 149.0, 131.3 , 130.2, 128.9, 125.2, 123.2, 120.1, 119.9, 115.2, 102.9, 90.5, 84.4, 82.8, 65.4, 53.4, 28.1. HRMS (ESI): calculated 320.1257, detected: 320.1293.

Embodiment 4: Arylacetylene and propargylamine prepare 2-alkynyl allylamine under the catalysis of metal rhodium complex

Wherein Ts is p-toluenesulfonyl, DCM is dichloromethane.

[Rh(COD)Cl] ₂ (5 mol%) and PPh ₃ (30 mol%) were added to the dry reaction tube under argon atmosphere, followed by 1 ml of anhydrous dichloromethane and 0.5 mmol of aryl acetylene. Finally, 0.75 mmol propargylamine was injected with a peristaltic pump, and reacted overnight at 40°C. After the reaction, the reaction solution was concentrated by filtration and separated by column chromatography to obtain the product (ethyl acetate:petroleum ether=1:2-10, V/V).

Raw material aryl alkynes Among them, R ₁ are respectively: hydrogen, methoxy group, formaldehyde group, nitro group, bromine, amino group or-NHAc, and the product formula (I) aryl alkynene compound prepared accordingly is respectively P11-P20, see the following for details Show.

Yield: 84%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 7.79(d, J=5.4Hz, 2H), 7.38-7.36(m, 2H), 7.31-7.29(m, 3H), 7.25(d , J=8.0Hz, 2H), 5.46(m, 2H), 5.27(br, 1H), 3.74(d, J=6.4Hz, 2H), 2.37(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 143.4, 137.3, 131.7, 129.7, 128.6, 128.3, 127.2, 127.1, 122.7, 122.5, 90.9, 87.0, 47.6, 21.4. HRMS (ESI): calculated for C ₁₈ H ₁₇ NO ₂ S [M+Na] ⁺ : 334.0872, detection value: 334.0910..

Yield: 92%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 7.78 (d, J=8.2Hz, 2H), 7.31 (d, J=8.7Hz, 2H), 7.24 (dJ=8.1Hz, 2H) , 6.82(d, J=8.6Hz, 2H), 5.40(s, 1H), 5.39(s, 1H), 5.27(br, 1H), 3.78(s, 3H), 3.72(d, J=6.4Hz, 2H), 2.36(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 160.0, 143.5, 137.3, 133.2, 132.1, 129.7, 127.2, 121.9, 114.6, 114.0, 91.2, 85.8, 55.2, 47.8, 21.4 .HRMS (ESI): Calcd. for _C19H19NO3S [M+Na] ₊ ^: 364.0978, _found : 364.1000.

Yield: 77%. ¹ H NMR (400MHz, CDCl ₃ ): δppm 8.10(d, J=8.4Hz, 2H), 7.71(d, J=8.0Hz, 2H), 7.46(d, J=8.0Hz, 2H), 7.22(d, J=8.0Hz, 2H), 5.50(s, 2H), 5.07(t, J=6.0Hz, 1H), 3.7(d, J=6.4Hz, 2H), 2.33(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 147.2, 143.6, 137.2, 132.4, 129.7, 129.4, 127.1, 126.6, 124.8, 123.6, 91.9, 89.1, 47.5, 21.5. HRMS (ESI): Calculated C ₁₈ H ₁₆ N ₂ O ₄ S[M+Na] ⁺ : 379.0723, detected value: 379.0741.

Yield: 70%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 9.97(s, 1H), 7.79-7.75(m, 4H), 7.51(d, J=7.9Hz, 2H), 7.25(d, J =7.9Hz, 2H), 5.54(s, 1H), 5.52(s, 1H), 5.46(br, 1H), 3.75(d, J=6.4Hz, 2H), 2.37(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 191.7, 143.6, 137.3, 135.7, 132.3, 129.8, 129.6, 128.9, 127.2, 126.9, 124.3, 90.9, 90.0, 47.5, 21.4. HRMS (ESI): calculated for C ₁₉ H ₁₇ NO ₃ S[M+Na] ⁺ : 362.0861, detected value: 362.0864.

Yield: 95%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 7.78(d, J=8.2Hz, 2H), 7.56(d, J=8.1Hz, 1H), 7.39(d, J=6.9Hz, 1H), 7.23-7.22(m, 3H), 7.17-7.14(m, 1H), 5.48(s, 2H), 5.27(br, 1H), 3.78(d, J=6.0Hz, 2H), 2.35(s , 3H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 143.6, 137.2, 133.4, 132.5, 130.0, 129.7, 127.4, 127.2, 126.8, 125.7, 124.6, 123.6, 91.3, 90.0, 47.8, 21.6. HRMS (ESI ): Calcd. for C ₁₉ H ₁₇ NO ₃ S[M+Na] ⁺ : 411.9977, found: 412.0017.

Yield: 65%. ¹ H NMR (400MHz, CDCl ₃ ): δppm 7.69(d, J=8.0Hz, 2H), 7.17(d, J=8.4Hz, 2H), 7.13(d, J=8.0Hz, 1H), 7.05(t, J=7.7Hz, 1H), 6.61-6.56(m, 2H), 5.35(s, 1H), 5.32(s, 1H), 5.26(br, 1H), 3.86(s, 2H ), 3.65 (d, J=6.4Hz, 2H), 2.30 (s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 147.9, 143.5, 137.1, 132.1, 130.1, 129.7, 127.3, 127.1, 122.4, 117.9, 114.6 _, 107.3, _92.3 , _88.1 , 48.1, 21.5. HRMS (ESI): Calcd. for _C18H18N2O2S [M+Na] ⁺ : 349.0981, found: 349.1026.

Yield: 90%, ¹ H NMR (500MHz, CDCl ₃ ): δppm 7.76 (d, J=8.0Hz, 2H), 7.42 (d, J=6.8Hz, 2H), 7.26-7.21 (m, 4H), 5.47(s, 1H), 5.46(s, 1H), 5.32(br, 1H), 3.73(d, J=6.5Hz, 2H), 2.37(s, 3H). ¹³ CNMR(100MHz, CDCl ₃ ): δppm 143.4, 137.2, 133.1, 132.0, 131.6, 129.7, 127.2, 126.9, 123.2, 122.9, 121.5, 89.9, 88.1, 47.6, 21.5. HRMS (ESI): Calculated for C ₁₈ H ₁₆ BrNO ₂ S [M+Na] ⁺ : 411.9977, detected value: 412.0024.

Yield: 89%. ¹ H NMR (400MHz, CDCl ₃ ): δppm 8.21(d, J=8Hz, 1H), 7.91(s, 1H), 7.65(d, J=8.4Hz, 2H), 7.25-7.18 (m, 2H), 7.16-7.14(m, 2H), 5.42(d, J=0.4Hz, 1H), 5.37(d, J=1.2Hz, 1H), 5.18(br, 1H), 3.62(d, J=6.4Hz, 2H), 2.29(s, 3H), 2.13(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 169.0, 143.7, 139.1, 136.9, 132.1, 129.9, 129.8, 127.2, 127.0, 124.0, 123.2, 120.0, 111.8 _, 93.6, 86.5, 48.2 _{, 24.8} , 21.5. HRMS (ESI): Calcd. for _C20H20N2O3S [M+Na] ⁺ : 391.1087, found: 391.1105.

Yield: 72%. ¹ H NMR (400MHz, CDCl ₃ ): δppm 7.78(d, J=8.4Hz, 1H), 7.49(s, 1H), 7.45(d, J=8.0Hz, 1H), 7.30- 7.26(m, 3H), 7.16(t, J=7.9Hz, 1H), 5.50(s, 1H), 5.48(s, 1H), 5.17(br, 1H), 3.75(d, J=6.4Hz, 2H ), 2.39(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ): δppm 143.5, 137.1, 134.3, 131.7, 130.2, 129.8, 129.7, 127.2, 126.7, 124.5, 123.6, 122.1, 89.4, 88.1, 47.7, 21.5. HRMS (ESI): Calcd. for _C18H16BrNO2S [M+Na] ⁺ : _411.9977 , _found : 412.0013.

Yield: 68%. ¹ H NMR (500MHz, CDCl ₃ ): δppm 8.15(d, J=8.1Hz, 1H), 7.79(d, J=8.0Hz, 2H), 7.73(s, 1H), 7.57( d, J=7.8Hz, 1H), 7.39(t, J=7.8Hz, 1H), 7.31-7.27(m, 2H), 5.50(s, 1H), 5.47(s, 1H), 4.77(br, 1H ), 3.81 (d, J=6.0Hz, 2H), 2.38 (s, 3H), 1.68 (s, 9H). ¹³ C NMR (125MHz, CDCl ₃ ): δppm 148.8, 143.3, 137.0, 130.0, 129.5, 129.0 , 127.2, 127.0, 126.9, 125.2, 123.2, 122.4, 120.0, 115.1, 102.6, 90.3, 84.4, 83.1, 47.7, 28.0, 21.3. HRMS (ESI): Calculated for C ₂₅ H ₂₆ N ₂ O ₄₈ [M+Na ] ⁺ : 473.1505, detected value: 473.1494..

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the implementation scope of the present invention. Anyone with ordinary knowledge in the technical field may make various changes and modifications without departing from the spirit and scope of the present invention, and the protection scope of the present invention shall be determined by the protection scope defined in the claims.

Claims (7)

1. the preparation method of an arylalkyne ene compound, is characterized in that, take arylalkyne compounds and propargyl alcohol or propargylamine compounds as raw material, with [Rh (COD) Cl] ₂The rhodium complex that generates with the part effect is catalyzer, and in organic solvent, reaction obtains the described arylalkyne ene compound shown in formula (I);

Described preparation method's reaction scheme is as with as shown in following formula (A):

Wherein, R ₁For hydrogen, methoxyl group, carboxaldehyde radicals, nitro, bromine, amino or-NHAc;

R ₂For-OH or-NHTs.

2. preparation method as claimed in claim 1, is characterized in that, described arylalkyne compounds: propargyl alcohol or propargylamine compounds: [Rh (COD) Cl] ₂: the mol ratio of part is 1: 1-1.5: 0.05: 0.2-0.3.

3. preparation method as claimed in claim 1, is characterized in that, described part is:

4. preparation method as claimed in claim 1, is characterized in that, described part is:

5. preparation method as claimed in claim 1, is characterized in that, described organic solvent is methylene dichloride, trichloromethane, tetrahydrofuran (THF) or 1,2-ethylene dichloride.

6. preparation method as claimed in claim 1, is characterized in that, the described reaction times is 10-12 hour.

7. preparation method as claimed in claim 1, is characterized in that, described temperature of reaction is 25 ℃ to 40 ℃.