CN118772026A - A method for synthesizing (E)-1-phenyl-3-(p-tolylthio)but-2-en-1-one - Google Patents

Abstract

The present invention belongs to the field of compound synthesis, and specifically relates to a method for synthesizing (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one. The synthesis method is: 1-phenylbutane-2,3-diene-1-one, p-methylthiophenol, and acetonitrile are added to a reaction tube, and the reaction is carried out at room temperature under an air atmosphere. After the reaction is completed, (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one is obtained by post-treatment. The present invention directly constructs a C-S bond by an addition reaction of the C=C bond of the allene, without the need to add a transition metal, high temperature, or additional additives, and the reaction conditions are mild, and the method has good application prospects, and provides a highly selective, efficient, and green synthesis method for the synthesis of (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one and vinyl sulfide.

Description

A method for synthesizing (E)-1-phenyl-3-(p-tolylthio)but-2-en-1-one

Technical Field

The invention belongs to the field of compound synthesis, and specifically relates to a method for synthesizing (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one.

Background Art

Due to the unique properties of organosulfur compounds, they are widely used in organic synthesis, medicinal chemistry and materials science. The development of simple and direct methods for sulfur-containing compounds and the synthesis of new organosulfur compounds have become a research hotspot today (Chem. Soc. Rev. 2020, 49, 4307−4359; Org. Chem. Front. 2020, 7, 1395−1417). Among all types of organosulfur compounds, vinyl sulfides are particularly important because they are multifunctional intermediates in organic chemistry and coordination chemistry, and are also key structural units for many natural products and bioactive compounds (J. Org. Chem. 2022, 87, 11796−11804). Therefore, it is of great research significance to develop green and efficient methods to synthesize new vinyl sulfides.

The present invention develops a method for synthesizing (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one by reaction using 1-phenylbutane-2,3-diene-1-one and p-methylthiophenol as substrates. The method directly constructs a C-S bond by addition reaction of the C=C bond of the allene, does not require the addition of transition metals, high temperatures, or additional additives, and has mild reaction conditions. It has good application prospects and provides a highly selective, efficient, and green synthesis method for the synthesis of (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one and vinyl sulfide.

Summary of the invention

The purpose of the present invention is to provide a method for synthesizing (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one in view of the shortcomings and deficiencies of the prior art. The present invention develops a method for synthesizing (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one by using 1-phenylbutane-2,3-diene-1-one and p-methylthiophenol as raw materials and acetonitrile as solvent. The method avoids constructing a C-S bond through a carbon-halogen bond, but directly constructs a C-S bond through a C=C bond addition reaction of an allene, does not require transition metals, does not require high temperatures, and does not require additional additives. The reaction conditions are mild and the method has good application prospects. The method provides a highly selective, efficient, and green synthesis method for the synthesis of (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one and vinyl sulfide.

The purpose of the present invention is achieved through the following technical solutions.

A method for synthesizing (E)-1-phenyl-3-(p-tolylthio)but-2-en-1-one comprises the following steps:

1-phenylbutane-2,3-dien-1-one, p-methylthiophenol and acetonitrile were added to a reaction tube, and the reaction was carried out at room temperature under an air atmosphere. After the reaction was completed, (E)-1-phenyl-3-(p-tolylthio)but-2-en-1-one was obtained through separation and purification.

Further, the chemical reaction equation of the synthesis process is as follows:

Furthermore, the solvent is acetonitrile.

Furthermore, the atmosphere is air.

Furthermore, the temperature is room temperature.

Furthermore, the separation and purification operation is as follows: adding the reaction solution to ethyl acetate, washing and extracting twice with a saturated NaCl solution, taking the upper organic phase solution, drying it with anhydrous sodium sulfate, filtering it, concentrating it under reduced pressure, and then separating and purifying it by column chromatography to obtain the (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one.

Furthermore, the molar ratio of the compound described in structural formula I to the compound described in structural formula II is 1:1.

Furthermore, the stirring reaction time is 3.5 hours.

The invention uses 1-phenylbutane-2,3-diene-1-one and p-methylthiophenol as reaction raw materials, realizes the regioselective and stereoselective hydrogen sulfidation reaction of the allene by the nucleophilic addition reaction of the sulfur anion in the p-methylthiophenol and the allene group of 1-phenylbutane-2,3-diene-1-one, and synthesizes the target product, thus providing a highly selective, efficient and green synthesis method for the synthesis of (E)-1-phenyl-3-(p-tolylthio)but-2-ene-1-one and vinyl sulfide.

Compared with the existing technology, the present invention has the following advantages and beneficial effects:

The invention utilizes the C=C bond addition reaction of p-methylthiophenol to allene to construct a C-S bond, thereby avoiding the use of a halogen-containing substrate as a reaction precursor and having the advantage of high atom economy.

The present invention does not require transition metals, high temperatures, or additional additives, has simple reaction conditions, readily available raw materials, and good functional group compatibility, and is therefore expected to be applied to actual industrial production for better application.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a ¹ H NMR spectrum of (E)-1-phenyl-3-(p-tolylthio)but-2-en-1-one.

FIG2 is a ¹³ C NMR spectrum of (E)-1-phenyl-3-(p-tolylthio)but-2-en-1-one.

FIG3 is a crystal molecular structure diagram of (E)-1-phenyl-3-(p-tolylthio)but-2-en-1-one.

Specific implementation methods

The technical solution of the present invention is further described in detail below in conjunction with specific embodiments and drawings, but the protection scope and implementation methods of the present invention are not limited thereto.

Example

1-Phenylbutane-2,3-diene-1-one (0.2 mmol), p-methylthiophenol (0.2 mmol), acetonitrile (2.0 mL) and a magnetic stirrer were added to the reaction tube in sequence, and the mixture was reacted for 3.5 hours at room temperature under air atmosphere. The reaction solution was added to ethyl acetate, and washed and extracted twice with saturated NaCl solution. The upper organic phase solution was taken, dried with anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography to obtain the target product with a yield of 55.6%. The hydrogen spectrum and carbon spectrum of the obtained target product are shown in Figures 1 and 2, respectively, and the nuclear magnetic resonance data are shown as follows:

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.66 (d, J = 7.5 Hz, 2H), 7.45 (d, J = 7.0Hz, 3H), 7.36 (t, J = 7.5 Hz, 2H), 7.28 (d , J = 8.0 Hz, 2H), 6.37 (s, 1H), 2.51 (s, 3H), 2.41 (s, 3H); ¹³ C NMR (126 MHz, CDCl ₃ ) δ 188.11, 162.54, 140.35,139.56, 135.44 , 131.99, 130.58, 128.36, 127.92, 126.37, 115.37, 21.37, 21.02.

In order to determine the absolute configuration of the product, petroleum ether was used as a solvent to dissolve the product, and the solvent was controlled to evaporate and crystallize at 20-35 °C to obtain colorless transparent crystals. The crystal structure of the obtained target product is shown in Figure 3. The measured crystal data are as follows:

The crystal belongs to the monoclinic system, space group P 2 ₁ / n , a = 5.4605(12) Å, b = 19.767(4) Å, c =13.357(4) Å, β = 92.834(3)°, V = 1439.9(6) Å ³ , Z = 4, D c=1.238Mg·m ^-3 , μ (MoKa)=0.214mm ^-1 , F (000)= 568, 1.842°＜ θ ＜25.008°, R _gt ( F ) = 0.0398, wR _ref ( F ² ) = 0.1144, T= 296 (2) K, crystal size: 0.31 x 0.26 x 0.23mm.

The structure of the target product is inferred from the above data as follows:

.

Claims (6)

1. A process for the synthesis of (E) -1-phenyl-3- (p-toluenesulfonyl) but-2-en-1-one, characterized by the steps of:

；

adding 1-phenylbutane-2, 3-diene-1-ketone shown in a formula I, p-toluenesulfonic acid shown in a formula II and a solvent into a reaction tube, reacting at room temperature in an air atmosphere, and separating and purifying after the reaction is finished to obtain (E) -1-phenyl-3- (p-toluenesulfonyl) but-2-en-1-ketone shown in a formula III;

The solvent is acetonitrile;

The temperature is room temperature;

the reaction atmosphere is air.

2. The synthetic method of claim 1 wherein the separation and purification is performed by: the reaction solution is added into ethyl acetate, the saturated NaCl solution is used for washing and extracting twice, the upper organic phase solution is taken, dried by anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and separated and purified by column chromatography to obtain the (E) -1-phenyl-3- (p-toluenesulfonyl) but-2-en-1-one.

3. The synthetic method of claim 1 wherein the molar ratio of the compound of formula I to the compound of formula II is 1:1.

4. The method of claim, wherein the reaction time period is 3.5 hours.

5. (E) -1-phenyl-3- (p-toluenesulfonyl) but-2-en-1-one according to claim 1, its nuclear magnetic spectrum data ：¹H NMR (500 MHz, CDCl₃) δ 7.66 (d, J = 7.5 Hz, 2H), 7.45 (d, J = 7.0 Hz, 3H), 7.36 (t, J = 7.5 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 6.37 (s, 1H), 2.51 (s, 3H), 2.41 (s, 3H);

¹³C NMR (126 MHz, CDCl₃) δ 188.11, 162.54, 140.35, 139.56, 135.44, 131.99, 130.58, 128.36, 127.92, 126.37, 115.37, 21.37, 21.02.

6. (E) -1-phenyl-3- (p-tolylthio) but-2-en-1-one according to claim 1, wherein (E) -1-phenyl-3- (p-tolylthio) but-2-en-1-one has a crystal structure with the following crystallographic data: monoclinic system, space group P2₁/n,a = 5.4605(12) Å, b = 19.767(4) Å, c = 13.357(4) Å, β = 92.834(3)°, V = 1439.9(6) ų, Z = 4, R_gt(F) = 0.0398, wR_ref(F²) = 0.1144, T = 296 (2) K.