Method for synthesizing beta-hydroxyl / keto aryl propionitrile through electric pulse wave
The synthesis of β-hydroxy/ketone aromatic propionitrile by electrical pulse wave solves the problems of using strong bases and highly toxic substances in existing technologies, realizing a green and simple synthesis method, and improving atom utilization and reaction safety.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-12
- Publication Date
- 2026-03-31
AI Technical Summary
Existing methods for synthesizing β-keto aromatic propionitrs typically use strong bases or highly toxic cyanides, which do not meet the requirements of green chemistry and involve metal catalysts and oxidants.
Aromatic aldehydes are reacted with acetonitrile using an electric pulse wave under inert gas protection. The reaction is carried out electrochemically between electrodes via an electrolyte, avoiding the use of metal catalysts and oxidants, to prepare β-hydroxy/ketone aromatic propionitrile.
It achieves green synthesis without metal catalysts, oxidants, and strong bases, with simple steps, high atom utilization, and mild reaction conditions, which is in line with the principles of green chemistry.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of chemical organic synthesis technology, specifically relating to an electric pulse wave synthesis method. β Method for -hydroxy / ketone aromatic propionitrile. Background Technology
[0002] β -Hydroxy / ketone aromatic propionitrile is an important intermediate in the synthesis of fine chemicals and pharmaceuticals. The nitrile group is a precursor in the synthesis of amino and carbonyl compounds. β -Hydroxyaromatic propionitrile can be converted into other structural units, such as β α-hydroxycarboxylic acid derivatives, c -Amino alcohols, aminopyrazoles, imidazoles, furans, thiophenes, and pyridones ( Org.Lett. (2014, 16, 350-353.). Furthermore, these compounds are also used as synthetic biologically and pharmacologically active compounds, such as anti-HCV drugs and inhibitors of NHE-1. J. Org. Chem. , 2020, 85, 6143-6150.). β Benzoyl acetonitrile in ketone aromatic propionitrile has unique aromatic odor and structural characteristics, and can be used as a fragrance and acne treatment agent. Furthermore, it can be used in various reactions to synthesize a variety of heterocyclic structures with biological and pharmacological activities. Bioorg. Med. Chem. Lett., 2007, 17, 3266-3270.
[0003] Currently, regarding this type of... β - Ketone aromatic propionitrile products are often prepared in the presence of a strong base by condensation of alkyl nitriles and esters or by substitution with cyanides of α-bromoketones, as shown below:
[0004] Such reactions typically use strong bases or highly toxic cyanides, which does not meet the requirements of green chemistry.
[0005] In recent years, targeting β Extensive research has been conducted on green and economical synthetic methods for α-ketone aromatic propionitrs. In 2014, R. Liu's research group synthesized the corresponding α-ketone aromatic propionitrs by coupling alkyl nitriles with aldehydes / primary alcohols under oxygen conditions via copper chloride catalysis. β -Ketonitrile ( Org. Lett., (2014, 16, 350−353.); In 2019, F. Liu's research group also achieved [the desired effect] under the same conditions by synthesizing a copper-supported heterogeneous catalyst. β Synthesis of ketone nitrile ( Chem. Select., 2019, 4, 10653-10659). And regarding... βSynthesis of hydroxynitriles: In 2008, Goto A et al. synthesized hydroxynitriles by rhodium-catalyzed coupling of alkyl nitriles with aromatic aldehydes. β -hydroxynitrogen ( Chem. Commun., (2008, 19, 2212-2214). However, these methods also involve the use of metal catalysts, oxidants, and strong bases. Summary of the Invention
[0006] The purpose of this invention is to provide a solution that does not require metal catalysts, oxidants, or strong bases. β A method for preparing -hydroxy / ketone aryl propionitrile, specifically, provides a method for preparing it by reacting aromatic (or heteroaryl) aldehyde compounds with acetonitrile under the action of an electric pulse wave. β A green synthesis method for -hydroxy / ketonitriles.
[0007] The technical solution adopted in this invention is as follows: An electrical pulse wave synthesis β A method for -hydroxy / ketone aromatic propionitrile includes the following steps: dissolving the compound of formula (I) in an organic solvent under an inert gas atmosphere, adding an electrolyte, inserting two electrodes into the reaction solution and reacting under ambient temperature and electrical pulse wave conditions, and after post-processing, obtaining the compound of formula (II) or formula (III). β -Hydroxy / ketone aromatic propionitrile, with acetonitrile or a mixture of acetonitrile and propionitrile as the organic solvent, the reaction formula is as follows:
[0008] When R1 is phenyl, alkyl-substituted phenyl, or halogen-substituted phenyl, and R2 is hydrogen, the compound shown in formula (II) is obtained. When R1 is biphenyl, naphthalene, pyridine, or thiophene, and R2 is alkyl or hydrogen, the compound shown in formula (III) is obtained. When R1 is biphenyl, naphthalene, pyridine, or thiophene, and R2 is alkyl or hydrogen, the product is difficult to be further oxidized to II by the anode, so the product remains at the β-hydroxyaromatic propionitrile stage.
[0009] Furthermore, the mixed organic solvents for acetonitrile include methanol, dichloromethane, ethyl acetate, dichloroethane, acetone, and... N, N - A mixed solvent of dimethylformamide or dimethyl sulfoxide and acetonitrile, wherein the concentration of the compound represented by formula (I) in an organic solvent is 0.05 mmol / mL to 2 mmol / mL.
[0010] Furthermore, the electrolyte is tetrabutylammonium hexafluorophosphonate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium perchlorate, or tetrabutylammonium bromide, and its amount is 0.5-3 equivalents of the molar amount of the compound shown in formula (I).
[0011] Furthermore, the electrical pulse wave is set to a sine wave waveform, amplitude 4-16V, bias 2-8V, frequency 0.1-100Hz, and duty cycle 20-80%.
[0012] Furthermore, the two electrodes are one of Pt(+)|Pt(-), C(+)|Pt(-), and C(+)|C(-).
[0013] Furthermore, when R1 is a phenyl, alkyl-substituted phenyl, or halogen-substituted phenyl, stirring is required during the reaction.
[0014] Furthermore, when R1 is biphenyl, naphthalene, pyridine, or thiophene, no stirring is required during the reaction.
[0015] Further, the post-reaction processing steps were as follows: After the reaction was completed, pure water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the crude product. The crude product was purified by chromatography to obtain the target compound. β -Hydroxy / ketone aromatic propionitrile.
[0016] By employing the above-described technology, compared with the prior art, the present invention has the following significant advantages: (1) β The synthesis of -hydroxy / ketone aromatic propionitrile does not require metal catalysts, strong bases, or oxidants, which aligns with the principles of green chemistry.
[0017] (2) This method has simple steps, high atom utilization, mild reaction conditions, and simple post-processing operations. Detailed Implementation
[0018] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.
[0019] Example 1 Benzoylacetonitrile
[0020] Benzaldehyde (1.06 g, 10 mmol), acetonitrile (100 mL), and tetrabutylammonium tetrafluoroborate (TBABF4, 6.59 g, 20 mmol) were added to a pre-dried 250 mL three-necked flask (equipped with a magnetic stirrer, platinum anode, and platinum cathode). The reaction vessel was sealed with a rubber septum and sealing film, purged with argon for 5 minutes, and then subjected to a sinusoidal electrical pulse with an amplitude of 10 V, a bias of 5 V, a frequency of 1 Hz, and a duty cycle of 50% at room temperature. The reaction was stirred for 8 hours. After the reaction was complete, the mixture was extracted with ethyl acetate and water. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the crude product. The crude product was purified by column chromatography on silica gel using a 5:1 (v / v) hexane / ethyl acetate mixture to obtain benzoylacetonitrile (1.06 g, 80% yield).
[0021] The final product NMR data are as follows: 1 H NMR (600 MHz, CDCl3) δ7.97-7.86 (m, 2H), 7.67 (td, J = 7.2, 1.2 Hz, 1H), 7.53 (t, J = 8.4 Hz, 2H), 4.09 (s, 2H). 13 C NMR (151 MHz, CDCl3) δ187.1, 134.7, 134.3, 129.1, 128.4, 113.8,29.4. Example 2: p-Toluene-acetonitrile
[0022] To a pre-dried 250 mL three-necked flask (equipped with a magnetic stirrer, platinum anode, and platinum cathode), p-tolualdehyde (1.20 g, 10 mmol), acetonitrile (100 mL), and tetrabutylammonium tetrafluoroborate (TBABF4, 6.59 g, 10 mmol) were added. The reaction vessel was sealed with a rubber septum and sealing film, purged with argon for 5 minutes, and then subjected to a sinusoidal electrical pulse wave with an amplitude of 8 V, a bias of 4 V, a frequency of 5 Hz, and a duty cycle of 50% at room temperature. The reaction was stirred for 12 hours. After the reaction was complete, the mixture was extracted with ethyl acetate and water. The combined organic phases were dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the crude product. The crude product was purified on a silica gel column using a 5:1 (v / v) hexane / ethyl acetate mixture to obtain p-toluamide acetonitrile (0.96 g, 60% yield).
[0023] The final product NMR data are as follows: 1 H NMR (600 MHz, CDCl3) δ 7.82 (d,J = 8.4 Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H), 4.04 (s, 2H), 2.44 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ186.6, 146.0, 131.9, 129.8, 128.6, 113.9,29.2, 21.8. Example 3 4-tert-Butylbenzoylacetonitrile
[0024] 4-tert-butylbenzaldehyde (1.62 g, 10 mmol), acetonitrile (100 mL), and tetrabutylammonium tetrafluoroborate (TBABF4, 6.59 g, 20 mmol) were added to a pre-dried 250 mL three-necked flask (equipped with a magnetic stirrer, platinum anode, and platinum cathode). The reaction vessel was sealed with a rubber septum and sealing film, purged with argon for 5 minutes, and then subjected to a sinusoidal electrical pulse with an amplitude of 10 V, a bias of 5 V, a frequency of 1 Hz, and a duty cycle of 50% at room temperature. The reaction was stirred for 8 hours. After the reaction was complete, the mixture was extracted with ethyl acetate and water. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the crude product. The crude product was purified by column chromatography using a 5:1 (v / v) hexane / ethyl acetate mixture to obtain 4-tert-butylbenzoylacetonitrile (1.50 g, 75% yield).
[0025] The final product NMR data are as follows: 1 H NMR (600 MHz, CDCl3) δ 7.86 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H), 4.05 (s, 2H), 1.35 (s, 9H). 13 C NMR (151 MHz, CDCl3) δ186.6, 158.9, 131.7, 128.5, 126.1, 113.9,35.3, 31.0, 29.2. Example 4 4-Fluorobenzoylacetonitrile
[0026] 4-fluorobenzaldehyde (1.24 g, 10 mmol), acetonitrile (100 mL), and tetrabutylammonium tetrafluoroborate (TBABF4, 6.59 g, 20 mmol) were added to a pre-dried 250 mL three-necked flask (equipped with a magnetic stirrer, platinum anode, and platinum cathode). The reaction vessel was sealed with a rubber septum and sealing film, purged with argon for 5 minutes, and then subjected to a sinusoidal electrical pulse with an amplitude of 12 V, a bias of 6 V, a frequency of 1 Hz, and a duty cycle of 50% at room temperature. The reaction was stirred for 8 hours. After the reaction was complete, the mixture was extracted with ethyl acetate and water. The combined organic phases were dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the crude product. The crude product was purified by column chromatography on a silica gel column using a 5:1 (v / v) hexane / ethyl acetate mixture to obtain 4-fluorobenzoylacetonitrile (1.19 g, 73% yield).
[0027] The final product NMR data are as follows: 1 H NMR (600 MHz, CDCl3) δ 8.24-7.81 (m, 2H), 7.21 (t, J = 8.4 Hz, 2H), 4.06 (s, 2H). 13 C NMR (151 MHz, CDCl3) δ185.5, 167.4, 165.7, 131.3, 131.2, 130.7,130.7, 116.5, 116.3, 113.5, 29.3. Example 5 4-Chlorobenzoylacetonitrile
[0028] 4-fluorobenzaldehyde (1.40 g, 10 mmol), acetonitrile (100 mL), and tetrabutylammonium tetrafluoroborate (TBABF4, 6.59 g, 20 mmol) were added to a pre-dried 250 mL three-necked flask (equipped with a magnetic stirrer, platinum anode, and platinum cathode). The reaction vessel was sealed with a rubber septum and sealing film, purged with argon for 5 minutes, and then subjected to a sinusoidal electrical pulse wave with an amplitude of 10 V, a bias of 5 V, a frequency of 1 Hz, and a duty cycle of 50% at room temperature. The reaction was stirred for 8 hours. After the reaction was complete, the mixture was extracted with ethyl acetate and water. The combined organic phases were dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the crude product. The crude product was purified on a silica gel column using a 5:1 (v / v) hexane / ethyl acetate mixture to obtain 4-chlorobenzoylacetonitrile (0.86 g, 48% yield).
[0029] The final product NMR data are as follows: 1H NMR (600 MHz, CDCl3) δ7.87 (d, J = 8.4 Hz, 2H), 7.51 (d, J = 8.4 Hz, 2H), 4.07 (s, 2H). 13 C NMR (151 MHz, CDCl3) δ 186.0, 141.5, 134.7, 132.5, 129.8, 129.5,113.5. Example 6 3-([1,1'-biphenyl]-4-yl)-3-hydroxypropionitrile
[0030] To a pre-dried 250 mL three-necked flask (equipped with a magnetic stirrer, platinum anode, and platinum cathode), p-phenylbenzaldehyde (1.82 mg, 10 mmol), acetonitrile (100 mL), and tetrabutylammonium tetrafluoroborate (TBABF4, 6.59 g, 20 mmol) were added. The reaction vessel was sealed with a rubber septum and sealing film, purged with argon for 5 minutes, and then subjected to a sinusoidal electrical pulse wave with an amplitude of 8 V, a bias of 4 V, a frequency of 1 Hz, and a duty cycle of 50% at room temperature for 8 hours without stirring. After the reaction was complete, the mixture was extracted with ethyl acetate and water, the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified on a silica gel column using a 5:1 (v / v) hexane / ethyl acetate mixture to obtain 3-([1,1'-biphenyl]-4-yl)-3-hydroxypropionitrile (1.12 g, 50% yield).
[0031] The final product NMR data are as follows: 1 H NMR (600 MHz, CDCl3) 7.61 (d, J = 7.8 Hz, 2H), 7.57 (d, J = 7.8 Hz, 2H), 7.45 (dd, J = 16.2, 7.8 Hz, 4H), 7.36 (t, J = 7.5 Hz, 1H), 5.09 (t, J = 6.3Hz, 1H), 2.82–2.79 (m, 2H), 2.51 (s, 1H). 13C NMR (151 MHz, CDCl3) δ141.81, 140.33, 139.89, 128.84, 127.62,127.59, 127.08, 125.98, 117.22, 69.92, 27.90. Example 7 3-Hydroxy-3-(naphth-2-yl)propionitrile
[0032] 2-Naphthaldehyde (1.56 g, 10 mmol), acetonitrile (100 mL), and tetrabutylammonium tetrafluoroborate (TBABF4, 6.59 g, 20 mmol) were added to a pre-dried 250 mL three-necked flask (equipped with a magnetic stirrer, platinum anode, and platinum cathode). The reaction vessel was sealed with a rubber septum and sealing film, purged with argon for 5 minutes, and then subjected to a sinusoidal electrical pulse wave with an amplitude of 10 V, a bias of 5 V, a frequency of 1 Hz, and a duty cycle of 50% at room temperature for 8 hours without stirring. After the reaction was complete, the mixture was extracted with ethyl acetate and water, the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the crude product. The crude product was purified on a silica gel column using a 3:1 (v / v) hexane / ethyl acetate mixture to give 3-hydroxy-3-(naphth-2-yl)propionitrile (1.02 g, 52% yield).
[0033] The final product NMR data are as follows: 1 H NMR (600 MHz, CDCl3) δ 8.18–7.67 (m, 4H), 7.60–7.32 (m, 3H), 5.21(t, J = 6.2 Hz, 1H), 2.93–2.80 (m, 2H), 2.52 (s, 1H). 13 C NMR (151 MHz, CDCl3) δ138.3, 133.4, 133.1, 128.9, 128.1, 127.8,126.6, 126.5, 124.8, 122.9, 70.2, 27.9. Example 8 3-Hydroxy-3-(pyridin-2-yl)propionitrile
[0034] 2-Pyridinecarboxaldehyde (1.07 g, 10 mmol), acetonitrile (100 mL), and tetrabutylammonium tetrafluoroborate (TBABF4, 6.59 g, 20 mmol) were added to a pre-dried 250 mL three-necked flask (equipped with a magnetic stirrer, platinum anode, and platinum cathode). The reaction vessel was sealed with a rubber septum and sealing film, purged with argon for 5 minutes, and then subjected to a sinusoidal electrical pulse with an amplitude of 12 V, a bias of 6 V, a frequency of 1 Hz, and a duty cycle of 50% at room temperature for 12 hours without stirring. After the reaction was complete, the mixture was extracted with ethyl acetate and water, the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the crude product. The crude product was purified on a silica gel column using a 2:1 (v / v) hexane / ethyl acetate mixture to give 3-hydroxy-3-(pyridin-2-yl)propionitrile (1.04 g, 70% yield).
[0035] The final product NMR data are as follows: 1 H NMR (600 MHz, CDCl3) δ 8.58 (d, J = 4.2 Hz, 1H), 7.78 (m, 1H), 7.43(d, J = 7.9 Hz, 1H), 7.33–7.29 (m, 1H), 5.05 (t, J = 5.8 Hz, 1H), 4.34 (s, 1H), 3.05–2.73 (m, 2H). 13 C NMR (151 MHz, CDCl3) δ158.1, 148.7, 137.4, 123.6, 120.6, 117.2,68.8, 27.1. Example 9 3-Hydroxy-3-(thiophen-2-yl)propionitrile
[0036] 2-Thiophenecarboxaldehyde (1.12 g, 10 mmol), acetonitrile (100 mL), and tetrabutylammonium tetrafluoroborate (TBABF4, 6.59 g, 20 mmol) were added to a pre-dried 250 mL three-necked flask (equipped with a magnetic stirrer, platinum anode, and platinum cathode). The reaction vessel was sealed with a rubber septum and sealing film, purged with argon for 5 minutes, and then subjected to a sinusoidal electrical pulse wave with an amplitude of 12 V, a bias of 6 V, a frequency of 1 Hz, and a duty cycle of 50% at room temperature for 12 hours without stirring. After the reaction was complete, the mixture was extracted with ethyl acetate and water, the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the crude product. The crude product was purified on a silica gel column using a 2:1 (v / v) hexane / ethyl acetate mixture to give 3-hydroxy-3-(thiophene-2-yl)propionitrile (0.90 g, 60% yield).
[0037] The final product NMR data are as follows: 1 H NMR (600 MHz, CDCl3) δ 7.32 (d, J = 5.1 Hz, 1H), 7.08 (d, J = 3.6 Hz,1H), 7.02–6.99 (m, 1H), 5.28 (t, J = 6.3 Hz, 1H), 2.91–2.82 (m, 2H), 2.80 (s,1H). 13 C NMR (151 MHz, CDCl3) δ144.4, 127.1, 125.8, 124.7, 116.8, 66.3,28.2. Example 10 3-(1,1'-biphenyl-4-yl)-3-hydroxybutyronitrile
[0038] Biphenyl ethyl ketone (1.96 g, 10 mmol), acetonitrile (100 mL), and tetrabutylammonium tetrafluoroborate (TBABF4, 6.59 g, 20 mmol) were added to a pre-dried 250 mL three-necked flask (equipped with a magnetic stirrer, platinum anode, and platinum cathode). The reaction vessel was sealed with a rubber septum and sealing film, purged with argon for 5 minutes, and then subjected to a sinusoidal electrical pulse wave with an amplitude of 8 V, a bias of 4 V, a frequency of 1 Hz, and a duty cycle of 50% at room temperature for 12 hours without stirring. After the reaction was complete, the mixture was extracted with ethyl acetate and water, the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the crude product. The crude product was purified on a silica gel column using a 2:1 (v / v) hexane / ethyl acetate mixture to obtain 3-(1,1'-biphenyl-4-yl)-3-hydroxybutyronitrile (0.71 g, 30% yield).
[0039] The final product NMR data are as follows: 1 H NMR (600 MHz, CDCl3) δ7.70 – 7.62 (m, 4H), 7.60 (d, J = 8.4 Hz, 2H), 7.46 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 7.4 Hz, 1H), 5.82 (s, 1H), 3.09 – 2.89 (m,2H), 1.57 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ146.3, 140.3, 139.3, 129.4, 127.9, 127.1,126.8, 126.0, 119.2, 71.6, 33.1, 29.9. Example 11 Experimental data under other reaction conditions Experiment 1: The operation was the same as in Example 1, except that the type and ratio of solvent were changed. The experimental results are listed in Table 1 below.
[0040] Table 1. Screening of solvent types and ratios
[0041] As can be seen from Table 1, the yield is highest when acetonitrile is used as both a solvent and a reactant. Adding other solvents dilutes its concentration, which slows down the reaction rate and reduces the yield.
[0042] Experiment 2: The operation was the same as in Example 1, except that the equivalent amount of electrolyte was changed. The experimental results are listed in Table 2 below.
[0043] Table 2 Screening of Electrolyte Equivalents and Types
[0044] Table 2 shows that the optimal electrolyte concentration is 2 equivalents. There is no significant difference between TBAPF6 and TBAPF4, so TBAPF4 is the better choice from an economic perspective.
[0045] Experiment 3: The operation is the same as in Example 1, except that the waveform of the electrical pulse wave is changed. The experimental results are listed in Table 3 below.
[0046] Table 3 Screening of Electrical Pulse Waveforms
[0047] Table 3 shows that a sine wave is optimal because using a rectangular wave with high voltage output will reduce the product yield.
[0048] Experiment 4: The operation was the same as in Example 1, except that the amplitude and bias of the electrical pulse wave were changed. The experimental results are listed in Table 4 below.
[0049] Table 4 Screening of Electrical Pulse Wave Amplitude and Bias
[0050] Table 4 shows that an amplitude of 10 V and an offset of 5 V result in the best yield. Higher amplitudes and offsets may cause product decomposition, while lower amplitudes and offsets will reduce the reaction rate and thus the yield.
[0051] Experiment 5: The operation is the same as in Example 1, except that the frequency of the electrical pulse wave is changed. The experimental results are listed in Table 5 below.
[0052] Table 5. Screening of Electrical Pulse Wave Frequencies
[0053] Table 5 shows that 1 Hz is the optimal frequency. The lower the frequency, the closer the reaction is to direct current. The higher the frequency, the lower the reaction rate.
[0054] Experiment 6: The operation is the same as in Example 1, except that the duty cycle of the electrical pulse wave is changed. The experimental results are listed in Table 6 below.
[0055] Table 6 Screening of Electrical Pulse Duty Cycle
[0056] Table 6 shows that a duty cycle of 50% is optimal, but the other duty cycles do not show significant changes.
[0057] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.
Claims
1. A method for synthesizing electrical pulse waves β The method for -hydroxy / ketone aromatic propionitrile, characterized in that... Includes the following steps: Under inert gas protection, the compound represented by formula (I) is dissolved in an organic solvent, an electrolyte is added, two electrodes are inserted into the reaction solution, and the reaction is carried out under ambient temperature and electrical pulse wave conditions. After the reaction is completed, post-processing is performed to obtain the compound represented by formula (II) or formula (III). β -Hydroxy / ketone aromatic propionitrile, with acetonitrile or a mixture of acetonitrile and propionitrile as the organic solvent, the reaction formula is as follows: ， When R1 is phenyl, alkyl-substituted phenyl, or halogen-substituted phenyl, and R2 is hydrogen, the compound shown in formula (II) is obtained. When R1 is biphenyl, naphthalene, pyridine, or thiophene, and R2 is alkyl or hydrogen, the compound shown in formula (III) is obtained.
2. An electrical pulse wave synthesis according to claim 1 β The method for -hydroxy / ketone aromatic propionitrile, characterized in that... The mixed organic solvents for acetonitrile are methanol, dichloromethane, ethyl acetate, dichloroethane, and acetone. N,N - A mixed solvent of dimethylformamide or dimethyl sulfoxide and acetonitrile, wherein the concentration of the compound represented by formula (I) in an organic solvent is 0.05 mmol / mL to 2 mmol / mL.
3. An electrical pulse wave synthesis according to claim 1 β The method for -hydroxy / ketone aromatic propionitrile, characterized in that... The electrolyte is tetrabutylammonium hexafluorophosphonate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium perchlorate or tetrabutylammonium bromide, and its amount is 0.5-3 equivalents of the molar amount of the compound shown in formula (I).
4. An electrical pulse wave synthesis according to claim 1 β The method for -hydroxy / ketone aromatic propionitrile, characterized in that... The electrical pulse wave is set to a sine wave waveform, amplitude 4-16V, bias 2-8V, frequency 0.1-100 Hz, and duty cycle 20-80%.
5. An electrical pulse wave synthesis according to claim 1 β The method for -hydroxy / ketone aromatic propionitrile, characterized in that... The two electrodes are one of: Pt(+)|Pt(-), C(+)|Pt(-), or C(+)|C(-).
6. An electrical pulse wave synthesis according to claim 1 β The method for -hydroxy / ketone aromatic propionitrile, characterized in that... When R1 is a phenyl, alkyl-substituted phenyl, or halogen-substituted phenyl, stirring is required during the reaction.
7. An electrical pulse wave synthesis according to claim 1 β The method for -hydroxy / ketone aromatic propionitrile, characterized in that... When R1 is biphenyl, naphthalene, pyridine or thiophene, no stirring is required during the reaction.
8. An electrical pulse wave synthesis according to claim 1 β The method for -hydroxy / ketone aromatic propionitrile, characterized in that... The post-reaction processing steps were as follows: After the reaction, pure water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the crude product. The crude product was purified by chromatography to obtain the target compound. β -Hydroxy / ketone aromatic propionitrile.