CN117567332A - Method for simultaneously synthesizing thioether compounds and nitrile compounds - Google Patents

Method for simultaneously synthesizing thioether compounds and nitrile compounds Download PDF

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CN117567332A
CN117567332A CN202311554375.8A CN202311554375A CN117567332A CN 117567332 A CN117567332 A CN 117567332A CN 202311554375 A CN202311554375 A CN 202311554375A CN 117567332 A CN117567332 A CN 117567332A
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compound
thioether
nitrile
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stirring
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蔡志华
刘翠翠
罗玉萍
杜广芬
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Shihezi University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/42—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

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Abstract

The invention provides a method for simultaneously synthesizing thioether compounds and nitrile compounds, belonging to the technical field of organic synthesis; according to the invention, thioamide compounds, fluoride and acetonitrile are mixed, and then a benzyne precursor is added into the mixture, so that the simultaneous synthesis of thioether compounds and nitrile compounds under the condition of room temperature is realized; the method is simple, convenient and quick, does not need transition metal catalysis, has wide substrate range, and can not cause environmental pollution due to the low-cost and easily-obtained fluorine source; the method has the advantages of simple process, mild reaction conditions, good universality and the like, and the yield of the synthesized thioether compounds and nitrile compounds is very high, and the maximum of the thioether compounds and nitrile compounds can reach 98 percent, so that the method has very high industrial popularization value.

Description

Method for simultaneously synthesizing thioether compounds and nitrile compounds
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for simultaneously synthesizing thioether compounds and nitrile compounds.
Background
Organic thioether compounds have been widely used in the fields of medicine, biology, agriculture, optical materials and the like. To date, various methods of preparing various catalysts and promoters have been reported. The reaction processes reported to date involving organic halides (e.g. olefins, aromatic hydrocarbons, heteroaromatic compounds) or organic borides with sulfur sources (thiols, thiophenols, thioamides, potassium xanthate, potassium thiocyanate, elemental sulfur, sodium thiomethoxide, sodium sulfide, carbon disulfide, disulfides and sulfonyl hydrazides) often employ conditions such as metal catalysts, heating, etc. However, the above methods have disadvantages of poor atom economy, large odor of raw materials, and the like, so that novel, green and efficient methods for synthesizing sulfur-containing compounds have been hot spots for organic chemistry research.
Nitriles are naturally found in various bacteria, fungi, plants and animals, and are widely used as raw materials for the production of various medicines, agrochemicals, polymers, materials, etc. Examples of the nitrile group-containing drugs include the antidiabetic drug vildagliptin and the drug anastrazole for the treatment of breast cancer. In addition, nitrile functions have been used as versatile intermediates in organic synthesis and can be readily converted into a variety of other important functional groups, i.e., aldehydes, carboxylic acids, esters, primary amines, imines, oximes, amides, and the like. Various methods for synthesizing nitriles have been developed including multiple bond addition reactions, amine oxidation reactions, nitroalkane reduction reactions, alcohol reactions, oxime and amidoxime dehydration or rearrangement reactions, amide dehydration, thioamide dehydrosulfidation reactions, and the like. However, these drawbacks are common to existing methods for synthesizing nitriles: very high temperatures, use of metal catalysts, limitations of poor functional group tolerance due to harsh reaction conditions, use of stoichiometric reagents and the generation of metal waste, etc. The synthesis of such extremely valuable nitrile functions has therefore been one of the promising areas of research in organic chemistry.
The organic thioether compound and the nitrile compound are widely applied organic compounds, and if the organic thioether compound and the nitrile compound can be synthesized simultaneously, not only can byproducts in the reaction process be reduced, but also the utilization rate of atoms can be improved. In addition, the organic thioether compound and the nitrile compound have larger polarity difference and are easier to separate, so that the separation can be simply and rapidly realized, and the method has good industrial popularization value. However, there is no disclosure in the literature of one-pot processes based on the participation of benzyne for the preparation of organic thioether compounds and nitrile compounds.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for simultaneously synthesizing thioether compounds and nitrile compounds; according to the invention, thioamide compounds, fluoride and acetonitrile are mixed, and then a benzyne precursor is added into the mixture, so that the simultaneous synthesis of thioether compounds and nitrile compounds under the condition of room temperature is realized; the method is simple, convenient and quick, does not need transition metal catalysis, has wide substrate range, and can not cause environmental pollution due to the low-cost and easily-obtained fluorine source; the method has the advantages of simple process, mild reaction conditions, good universality and the like, and the yield of the synthesized thioether compounds and nitrile compounds is very high, and the maximum of the thioether compounds and nitrile compounds can reach 98 percent, so that the method has very high industrial popularization value.
In order to achieve the technical purpose, the invention adopts the following technical means:
the invention provides a method for simultaneously synthesizing thioether compounds and nitrile compounds, which specifically comprises the following steps:
adding solvent into thioamide compound and fluoride under the protection of nitrogen gas, mixing, then dropwise adding benzene alkyne precursor into the mixture under the condition of stirring, uniformly mixing to obtain a mixture, and carrying out nucleophilic protonizing desulfurization and dehydrogenation reaction on the mixture to simultaneously generate thioether compound and nitrile compound.
Preferably, the thioamide compound includes:
preferably, R in the thioamide compound 2 Including methoxy, 4-phenyl, 3, 5-dimethoxy, 3,4, 5-trimethoxy, 4-nitro, 3-nitro, 2, 5-chloro, 1-naphthyl, 2-naphthyl, 4- (1H-imidazol-1-yl), 1-methyl-1H-indole, 2- (1H-indol-3-yl), 1-naphthylethyl.
Preferably, the benzyne precursor comprises:
preferably, R in the benzyne precursor 1 Including hydrogen, 4, 5-phenyl, 4, 5-cyclopentylalkyl, 4, 5-dimethoxy, 4, 5-dimethyl, 3-methoxy or 3-fluoro.
Preferably, the fluoride comprises tetramethyl ammonium fluoride and the solvent comprises acetonitrile.
Preferably, the dosage ratio of the thioamide compound, the fluoride and the solvent is 0.2 mmol/0.4-0.9 mmoL/2.0 mL.
Preferably, the rotation speed of the stirring is 300-450 r/min;
the dripping speed of the benzene alkyne precursor is as follows: the dropwise addition was carried out at a rate of 2 s/drop in a 100. Mu.L microsyringe. The dripping speed is controlled to ensure that the added raw materials are rapidly dispersed in the reaction system, so that splashing is avoided.
Preferably, the molar ratio of the thioamide compound to the benzyne precursor is 1:2.0-3.0.
Preferably, the reaction conditions of the nucleophilic protonation desulfurization and dehydrogenation reaction are as follows: the reaction was carried out at room temperature for 2h in a closed environment. Compared with the prior art, the invention has the beneficial effects that:
the invention mixes thioamide compound, fluoride and acetonitrile, adds benzene alkyne precursor, and synthesizes at room temperature in one step to obtain ether and nitrile compounds. In the invention, thioamide compounds and fluoride are preferably mixed, acetonitrile is added into the obtained mixture, and a benzene alkyne precursor is dropwise added at the rate of 2 s/drop of a 100 mu L microsyringe under the condition of room temperature and stirring, and nucleophilic addition, hydrogen transfer, nucleophilic addition, hydrogen transfer and desulfurization reactions are carried out under the atmosphere of nitrogen protection. In the nucleophilic addition, hydrogen transfer, nucleophilic addition, hydrogen transfer and desulfurization reaction processes, sulfur nucleophilic attack benzene alkyne of thioamide compounds generates an amphoteric intermediate A, the intermediate A generates B through proton transfer, then the intermediate B generates C with one molecule benzene alkyne, and the intermediate C generates diphenyl sulfide and benzonitrile through proton transfer and C-S bond cleavage.
According to the invention, the phenylacetylene and thioamide are utilized to prepare the thioether compound and the nitrile compound simultaneously, so that the atomic utilization rate of the reaction reaches 100%, and the two products have larger polarity difference, so that the separation is easier. The preparation method is simple, convenient and quick, transition metal catalysis is not needed, the substrate range is wide, the used fluorine source is low in cost and easy to obtain, part of the used raw materials can be purchased, and part of the used raw materials can be prepared by using an amide and Lawsen reagent simple method; the method has the advantages of no environmental pollution, simple process, mild reaction conditions, high yields (up to 98 percent) of the thioether compounds and the nitrile compounds prepared at the same time, good universality and the like; the synthesis method has extremely high industrial popularization value.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention. The experimental procedures, without specific conditions noted in the examples below, were selected according to methods and conditions conventional in the art, or according to the commercial specifications. Reagents and starting materials not specifically identified in the examples below may be prepared by conventional methods or are commercially available.
The mechanism of the nucleophilic protonation, desulfuration and dehydrogenation reaction process is as follows:
one of the equations for the nucleophilic addition, hydrogen transfer, desulfurization reactions is:
after the nucleophilic addition, hydrogen transfer, nucleophilic addition, hydrogen transfer and desulfurization reaction are completed, the reaction system is preferably depressurized to remove the solvent, and the ether and nitrile compounds are simultaneously obtained by separating through column chromatography.
The above mechanism is described in detail by the following examples.
Example 1:
accurately weighing 0.2mmol of p-methoxythiobenzamide and 0.44mmol of tetramethyl ammonium fluoride (TMAF), placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of benzyne precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and p-methoxybenzonitrile.
The p-methoxybenzonitrile was a white solid, yield 23.2mg, 87%. Characterization is carried out on the prepared p-methoxybenzonitrile, and the structural formula of the p-methoxybenzonitrile is as follows:the characterization result is: 1 HNMR(400MHz,Chloroform-d)δ7.59(d,J＝9.0Hz,2H),6.95(d,J＝9.0Hz,2H),3.86(s,3H). 13 C NMR(100MHz,Chloroform-d)δ162.8,134.0,119.2,114.8,104.0,55.5.
the characterization results show that the p-methoxybenzonitrile is successfully synthesized.
The diphenyl sulfide was a colorless liquid with a yield of 23.5mg and a yield of 90%. Characterizing the prepared diphenyl sulfide, wherein the structural formula of the diphenyl sulfide is as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ7.36-7.32(m,4H),7.32-7.27(m,4H),7.26-7.21(m,2H). 13 C NMR(100MHz,Chloroform-d)δ135.8,131.0,129.2,127.0,77.3,77.0,76.7.
the characterization results show that diphenyl sulfide is successfully synthesized.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds p-methoxyl benzonitrile.
Example 2:
accurately weighing 0.2mmol of 4-phenylthiobenzamide and 0.44mmol of TMAF, placing the mixture into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of benzene precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 4-phenyl benzonitrile.
The 4-phenylbenzonitrile was a white solid, yield was 36.2mg, and the yield was 95%. The prepared 4-phenylbenzonitrile is characterized, and the structural formula of the characterized 4-phenylbenzonitrile is as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ7.70(q,J＝8.6Hz,4H),7.59(d,J＝7.0Hz,2H),7.48(t,J＝7.3Hz,2H),7.45-7.39(m,1H). 13 C NMR(100MHz,Chloroform-d)δ145.7,139.2,132.6,129.1,128.7,127.7,127.2,110.9.
the above characterization results demonstrate the successful synthesis of 4-phenylbenzonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 4-phenylbenzonitrile.
Example 3:
accurately weighing 0.2mmol of 3, 5-dimethoxy thiobenzoyl and 0.44mmol of TMAF, placing the mixture into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of benzene precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 3, 5-dimethoxy benzonitrile.
The 3, 5-dimethoxy benzonitrile is a white solid, the yield is 31.4mg, and the yield is 96%. The 3, 5-dimethoxy benzonitrile prepared is characterized, and the structural formula of the 3, 5-dimethoxy benzonitrile is characterized as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ6.76(d,J＝2.4Hz,2H),6.65(t,J＝4.6Hz,1H),3.81(s,6H). 13 C NMR(100MHz,Chloroform-d)δ161.0,118.8,113.4,109.9,105.6,55.7.
the characterization results show that the 3, 5-dimethoxy benzonitrile is successfully synthesized.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 3, 5-dimethoxy benzonitrile.
Example 4:
accurately weighing 0.2mmol of 3,4, 5-trimethoxy thiobenzoyl and 0.44mmol of TMAF, placing the mixture into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of a benzyne precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 3,4, 5-trimethoxy benzonitrile.
The 3,4, 5-trimethoxybenzonitrile was a white solid with a yield of 39.0mg and 96%. The 3,4, 5-trimethoxy benzonitrile prepared is characterized, and the structural formula of the 3,4, 5-trimethoxy benzonitrile is characterized as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ6.87(s,2H),3.89(d,J＝8.5Hz,9H). 13 C NMR(100MHz,Chloroform-d)δ153.6,142.3,119.0,109.5,106.7,61.1,56.4.
the characterization results show that the 3,4, 5-trimethoxy benzonitrile is successfully synthesized.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 3,4, 5-trimethoxy benzonitrile.
Example 5:
accurately weighing 0.2mmol of 4-nitrothiobenzamide and 0.44mmol of TMAF, placing the mixture into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of a benzene precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 4-nitrobenzonitrile.
The 4-nitrobenzonitrile was a white solid, yield 26.3mg, 89%. The prepared 4-nitrobenzonitrile is characterized, and the structural formula of the characterized 4-nitrobenzonitrile is as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ8.37(d,J＝9.0Hz,2H),7.90(d,J＝9.0Hz,2H). 13 C NMR(100MHz,Chloroform-d)δ150.0,133.5,124.3,118.3,116.8.
the above characterization results demonstrate the successful synthesis of 4-nitrobenzonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 4-nitrobenzonitrile.
Example 6:
accurately weighing 0.2mmol of 3-nitrothiobenzamide and 0.44mmol of TMAF, placing the mixture into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of a benzene precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 3-nitrobenzonitrile.
The 3-nitrobenzonitrile was a yellow solid, yield 27.1mg, 92%. The 3-nitrobenzonitrile obtained by the preparation is characterized, and the structural formula of the 3-nitrobenzonitrile is as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ8.54(s,1H),8.49(d,J＝8.4Hz,1H),8.01(d,J＝7.8Hz,1H),7.75(t,J＝8.0Hz,1H). 13 C NMR(100MHz,Chloroform-d)δ148.3,137.6,130.7,127.5,116.5,114.2.
the above characterization results demonstrate the successful synthesis of 3-nitrobenzonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 3-nitrobenzonitrile.
Example 7:
accurately weighing 0.2mmol of 2-nitrothiobenzamide and 0.44mmol of TMAF, placing the mixture into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of a benzene precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 2-nitrobenzonitrile.
The 2-nitrobenzonitrile was a yellow solid, yield 21.3mg, 59%. The prepared 2-nitrobenzonitrile is characterized, and the structural formula of the characterized 2-nitrobenzonitrile is as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ8.36(s,1H),7.95(s,1H),7.90-7.82(m,2H). 13 C NMR(100MHz,Chloroform-d)δ135.6,134.3,133.7,125.6,114.9,108.1.
the characterization results described above demonstrate the successful synthesis of 2-nitrobenzonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 2-nitrobenzonitrile.
Example 8:
accurately weighing 0.2mmol of 2, 5-dichloro-thio-benzamide and 0.44mmol of TMAF, placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of a benzyne precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 2, 5-dichlorobenzonitrile.
The 2, 5-dichlorobenzonitrile was a white solid with a yield of 24.7mg and a yield of 72%. The prepared 2, 5-dichlorobenzonitrile is characterized in that the structural formula of the 2, 5-dichlorobenzonitrile is as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ7.62(d,J＝8.4Hz,1H),7.55(d,J＝2.0Hz,1H),7.38(dd,J＝8.4,2.0Hz,1H). 13 C NMR(100MHz,Chloroform-d)δ140.1,137.8,134.6,130.3,127.9,115.2,111.9.
the above characterization results demonstrate the successful synthesis of 2, 5-dichlorobenzonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 2, 5-dichlorobenzonitrile.
Example 9:
accurately weighing 0.2mmol of 1-naphthalene thiobenzamide and 0.44mmol of TMAF, placing the mixture into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of benzene precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 1-naphthalene nitrile.
The 1-naphthalenenitrile was obtained as a yellow liquid in a yield of 28.2mg and a yield of 92%. The prepared 1-naphthalene nitrile is characterized, and the structural formula of the characterized 1-naphthalene nitrile is as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ8.23(d,J＝8.3Hz,1H),8.07(d,J＝8.3Hz,1H),7.93-7.88(m,2H),7.71-7.66(m,1H),7.64-7.59(m,1H),7.54-7.49(m,1H). 13 C NMR(100MHz,Chloroform-d)δ133.3,132.9,132.6,132.3,128.6,128.6,127.5,125.1,124.9,117.8,110.2.
the above characterization results demonstrate the successful synthesis of 1-naphthalonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 1-naphthalene nitrile.
Example 10:
accurately weighing 0.2mmoL of 2-naphthalene thiobenzamide and 0.44mmoLTMAF, placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmoL of benzene precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 2-naphthalene nitrile.
The 2-naphthonitrile was a white solid, yield was 27.2mg, and 89%. The prepared 2-naphthalene nitrile is characterized, and the structural formula of the characterized 2-naphthalene nitrile is as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ8.24(s,1H),7.91(t,J＝9.0Hz,3H),7.67-7.59(m,3H). 13 C NMR(100MHz,Chloroform-d)δ134.7,134.2,132.3,129.2,129.0,128.4,128.1,127.7,126.4,119.2,109.4.
the above characterization results demonstrate successful synthesis of 2-naphthonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 2-naphthonitrile.
Example 11:
accurately weighing 0.2mmol of 4- (1H-imidazol-1-yl) thiobenzamide and 0.44mmol of TMAF, placing the mixture into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of a benzyne precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 4- (1H-imidazol-1-yl) benzonitrile.
The 4- (1H-imidazol-1-yl) benzonitrile was a white solid, yield was 30.0mg, and yield was 89%. Characterizing the prepared 4- (1H-imidazol-1-yl) benzonitrile, wherein the structural formula of the 4- (1H-imidazol-1-yl) benzonitrile is characterized as follows:the characterization result is: 1 HNMR(400MHz,Chloroform-d)δ7.95(s,1H),7.81(d,J＝8.8Hz,2H),7.54(d,J＝8.9Hz,2H),7.35(s,1H),7.27(s,1H). 13 C NMR(100MHz,Chloroform-d)δ140.5,135.3,134.1,131.5,121.4,117.9,117.6,111.0.
the above characterization results demonstrate successful synthesis of 4- (1H-imidazol-1-yl) benzonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of this embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 4- (1H-imidazol-1-yl) benzonitrile.
Example 12:
accurately weighing 0.2mmol of 1-methyl-1H-indole-3-thiobenzamide and 0.44mmol of TMAF, placing the mixture into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of a benzyne precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 1-methyl-1H-indole-3-carbonitrile.
The 1-methyl-1H-indole-3-carbonitrile was a brown liquid with a yield of 27.0mg and 86%. The prepared 1-methyl-1H-indole-3-carbonitrile is characterized by the structural formula:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ7.75(d,J＝7.8Hz,1H),7.54(s,1H),7.41-7.27(m,3H),3.84(s,3H). 13 C NMR(100MHz,Chloroform-d)δ136.0,135.5,127.8,123.9,122.1,119.9,115.9,110.3,85.5,33.6.
the above characterization results demonstrate successful synthesis of 1-methyl-1H-indole-3-carbonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 1-methyl-1H-indole-3-carbonitrile.
Example 13:
accurately weighing 0.2mmol of 2- (1H-indol-3-yl) thio-phenylacetamide and 0.44mmol of TMAF, placing the mixture into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of a benzyne precursor 2- (trimethylsilyl) phenyl trifluoro-methanesulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction, and separating to obtain diphenyl sulfide and 2- (1H-indol-3-yl) acetonitrile.
The 2- (1H-indol-3-yl) acetonitrile is a colourless liquid, the yield is 30.0mg, the yield is 96%. Characterizing the prepared 2- (1H-indol-3-yl) acetonitrile, wherein the structural formula of the 2- (1H-indol-3-yl) acetonitrile is characterized as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ8.21(s,1H),7.58(d,J＝7.9Hz,1H),7.38(d,J＝8.2Hz,1H),7.26-7.22(m,1H),7.20-7.16(m,2H),3.82(s,2H). 13 C NMR(100MHz,Chloroform-d)δ136.3,126.0,122.9,122.8,120.3,118.2,118.1,111.5,104.8,14.4.
the above characterization results demonstrate successful synthesis of 2- (1H-indol-3-yl) acetonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 2- (1H-indol-3-yl) acetonitrile.
Example 14:
accurately weighing 0.2mmol of 1-naphthalenethioacetamide and 0.44mmoLTMAF, placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44 mmole of benzene precursor 2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain diphenyl sulfide and 1-naphthalene acetonitrile.
The 1-naphthylacetonitrile was a white solid, the yield was 35.3mg, and the yield was 98%. Characterizing the prepared 1-naphthylacetonitrile, wherein the structural formula of the characterized 1-naphthylacetonitrile is as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ7.87(dd,J＝21.4,8.0Hz,3H),7.61-7.52(m,3H),7.45(t,J＝7.5Hz,1H),4.09(s,2H). 13 C NMR(100MHz,Chloroform-d)δ130.7,129.1,129.0,127.0,126.4,126.3,125.8,125.4,122.4,117.7,21.7.
the characterization results described above demonstrate successful synthesis of 1-naphthalonitrile.
The characterization of the diphenyl sulfide was consistent with example 1, which demonstrates the successful synthesis of diphenyl sulfide.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds 1-naphthalonitrile.
Example 15:
accurately weighing 0.2mmol of 4-methoxybenzonitrile and 0.44mmol of TMAF, placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen for three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of benzoyne precursor 4, 5-dimethyl-2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing solvent under reduced pressure after the reaction is finished, and separating to obtain the bis (3, 4-dimethylphenyl) sulfide and the p-methoxybenzonitrile.
The bis (3, 4-dimethylphenyl) sulfide was a white solid, yield 47.1mg, 97%. Characterization is carried out on the prepared bis (3, 4-dimethylphenyl) thioether, and the structural formula of the bis (3, 4-dimethylphenyl) thioether is characterized as follows:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ7.11(d,J＝7.6Hz,2H),6.97(d,J＝7.6Hz,2H),6.88(s,2H),2.33(s,6H),2.22(s,6H). 13 C NMR(100MHz,Chloroform-d)δ137.5,135.5,132.8,132.2,130.3,128.6,19.7,19.4.
the above characterization results demonstrate the successful synthesis of bis (3, 4-dimethylphenyl) sulfide.
The p-methoxybenzonitrile prepared in this example is shown in example 1, which demonstrates the successful synthesis of p-methoxybenzonitrile.
In summary, the method of the embodiment can simultaneously synthesize the thioether compounds diphenyl sulfide and the nitrile compounds p-methoxyl benzonitrile.
Example 16:
accurately weighing 0.2mmol of 4-methoxybenzonitrile and 0.44mmol of TMAF, placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen for three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of benzoyne precursor 4, 5-dimethoxy-2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing solvent under reduced pressure after the reaction is finished, and separating to obtain the bis (3, 4-dimethoxy phenyl) sulfide and the p-methoxybenzonitrile.
The bis (3, 4-dimethoxyphenyl) sulfide was a white solid in 43.7mg yield of 71%. Characterizing the prepared bis (3, 4-dimethoxyphenyl) sulfide, wherein the structural formula of the bis (3, 4-dimethoxyphenyl) sulfide is characterized by:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ6.93(d,J＝2.4Hz,1H),6.91(d,J＝2.0Hz,1H),6.89(d,J＝2.0Hz,2H),6.82(s,1H),6.80(s,1H),3.87(s,6H),3.82(s,6H). 13 C NMR(100MHz,Chloroform-d)δ149.3,148.5,127.4,123.9,114.3,111.7,77.0,76.7,56.0,56.0.
the above characterization results demonstrate the successful synthesis of bis (3, 4-dimethoxyphenyl) sulfide.
The p-methoxybenzonitrile prepared in this example is shown in example 1, which demonstrates the successful synthesis of p-methoxybenzonitrile.
In summary, the method described in this example is capable of simultaneously synthesizing bis (3, 4-dimethoxyphenyl) sulfide and the nitrile compound p-methoxybenzonitrile.
Example 17:
accurately weighing 0.2mmol of 4-methoxybenzonitrile and 0.44mmol of TMAF, placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen for three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of benzoyne precursor 6- (trimethylsilyl) -2, 3-dihydro-1H-indene-5-yl triflate, stirring at room temperature for 2 hours, removing solvent under reduced pressure after the reaction is finished, and separating to obtain the bis (2, 3-dihydro-1H-indene-5-yl) thioether and the p-methoxybenzonitrile.
The bis (2, 3-dihydro-1H-inden-5-yl) sulfide was a colorless liquid, and the yield was 52.1mg, 98%. Characterization of the prepared bis (2, 3-dihydro-1H-inden-5-yl) sulfide, characterized by the bis (2, 3-dihydro-1H-inden)-5-yl) thioether has the structural formula:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ7.21(s,2H),7.13(s,4H),2.86(q,J＝7.1Hz,8H),2.10-2.02(m,4H). 13 C NMR(100MHz,Chloroform-d)δ145.4,143.3,133.5,129.1,127.1,124.9,32.7,25.4.
the above characterization results demonstrate the successful synthesis of bis (2, 3-dihydro-1H-inden-5-yl) sulfide.
The p-methoxybenzonitrile prepared in this example is shown in example 1, which demonstrates the successful synthesis of p-methoxybenzonitrile.
In summary, the method described in this example is capable of simultaneously synthesizing bis (2, 3-dihydro-1H-inden-5-yl) sulfide and the nitrile compound p-methoxybenzonitrile.
Example 18:
accurately weighing 0.2mmol of 4-methoxybenzonitrile and 0.44mmol of TMAF, placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen for three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of benzoyne precursor 6- (trimethylsilyl) benzo [ d ] [1,3] dioxol-5-yl triflate, stirring at room temperature for 2 hours, removing solvent under reduced pressure after the reaction is finished, and separating to obtain the bis (benzo [ d ] [1,3] dioxol-5-yl) thioether and the p-methoxybenzonitrile.
The bis (benzo [ d ]][1,3]Dioxol-5-yl) sulfide was a colorless liquid, yield was 52.1mg, and yield was 98%. For the bis (benzo [ d ]][1,3]Dioxol-5-yl) sulfide is characterized, the bis (benzo [ d ] is characterized][1,3]Dioxol-5-yl) sulfide has the structural formula:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ6.89(d,J＝1.8Hz,1H),6.87(d,J＝1.8Hz,1H),6.80(d,J＝1.8Hz,2H),6.75(s,1H),6.73(s,1H),5.95(s,4H). 13 C NMR(100MHz,Chloroform-d)δ148.2,147.3,128.7,125.2,111.9,108.8,101.3.
the above characterization results demonstrate the successful synthesis of bis (benzo [ d ] [1,3] dioxol-5-yl) sulfide.
The p-methoxybenzonitrile prepared in this example is shown in example 1, which demonstrates the successful synthesis of p-methoxybenzonitrile.
In summary, the method described in this example is capable of simultaneously synthesizing bis (benzo [ d ] [1,3] dioxol-5-yl) sulfide and the nitrile compound p-methoxybenzonitrile.
Example 19:
accurately weighing 0.2mmol of 4-methoxybenzonitrile and 0.44mmol of TMAF, placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen for three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of benzene precursor 3- (trimethylsilyl) naphthalene-2-yl triflate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain the di (naphthalene-2-yl) sulfide and the p-methoxybenzonitrile.
The bis (naphthalen-2-yl) sulfide was a white solid with a yield of 37.7mg and a yield of 66%. Characterizing the prepared di (naphthalene-2-yl) thioether, wherein the structural formula of the di (naphthalene-2-yl) thioether is characterized by:the characterization result is: 1 HNMR(400MHz,Chloroform-d)δ7.87(d,J＝1.4Hz,2H),7.82-7.71(m,6H),7.48-7.41(m,6H). 13 C NMR(100MHz,Chloroform-d)δ133.8,133.1,132.3,129.8,128.9,127.7,127.4,126.6,126.2.
the above characterization results demonstrate the successful synthesis of bis (naphthalen-2-yl) sulfide.
The p-methoxybenzonitrile prepared in this example is shown in example 1, which demonstrates the successful synthesis of p-methoxybenzonitrile.
In summary, the method described in this example enables the simultaneous synthesis of bis (naphthalen-2-yl) sulfide and the nitrile compound p-methoxybenzonitrile.
Example 20:
accurately weighing 0.2mmol of 4-methoxybenzonitrile and 0.44mmol of TMAF, placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of alkyne precursor 3-methoxy-2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing the solvent under reduced pressure after the reaction is finished, and separating to obtain the bis (3-methoxyphenyl) thioether and the p-methoxybenzonitrile.
The bis (3-methoxyphenyl) sulfide was colorless liquid in a yield of 42.3mg in 86%. Characterizing the prepared bis (3-methoxyphenyl) thioether, wherein the structural formula of the bis (3-methoxyphenyl) thioether is characterized in that:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ7.21(t,J＝8.0Hz,2H),6.95-6.92(m,2H),6.90-6.88(m,2H),6.78(ddd,J＝8.3,2.5,0.8Hz,2H),3.75(s,6H). 13 CNMR(100MHz,Chloroform-d)δ160.0,136.7,129.9,123.3,116.2,113.0,55.3.
the above characterization results demonstrate the successful synthesis of bis (3-methoxyphenyl) sulfide.
The p-methoxybenzonitrile prepared in this example is shown in example 1, which demonstrates the successful synthesis of p-methoxybenzonitrile.
In summary, the method described in this example is capable of simultaneously synthesizing bis (3-methoxyphenyl) sulfide and the nitrile compound p-methoxybenzonitrile.
Example 21:
accurately weighing 0.2mmol of 4-methoxybenzonitrile and 0.44mmol of TMAF, placing the materials into a 50mL reaction tube with a polytetrafluoroethylene cover, vacuumizing and replacing nitrogen three times, adding 2.0mL of acetonitrile under the protection of nitrogen, stirring at room temperature for 5 minutes, stirring at the rotating speed of 450r/min, dropwise adding 0.44mmol of alkyne precursor 3-fluoro-2- (trimethylsilyl) phenyl trifluoro methane sulfonate, stirring at room temperature for 2 hours, removing solvent under reduced pressure after the reaction is finished, and separating to obtain the bis (3-methoxyphenyl) sulfide and the p-methoxybenzonitrile.
The bis (3-fluorophenyl) sulfide was a colorless liquid, and the yield was 26.1mg, 59%. Characterizing the prepared bis (3-fluorophenyl) thioether, wherein the structural formula of the bis (3-fluorophenyl) thioether is characterized by:the characterization result is: 1 H NMR(400MHz,Chloroform-d)δ7.32-7.21(m,3H),7.17-7.00(m,03H),7.00-6.89(m,3H). 13 C NMR(100MHz,Chloroform-d)δ164.3,164.2,161.8,161.7,138.8,138.7,137.2,137.1,130.6,130.5,130.5,126.7,126.7,122.7,122.6,118.0,117.8,114.6,114.5,114.4,114.3,114.1,113.9,77.3,77.0.
the above characterization results demonstrate the successful synthesis of bis (3-fluorophenyl) sulfide.
The p-methoxybenzonitrile prepared in this example is shown in example 1, which demonstrates the successful synthesis of p-methoxybenzonitrile.
In summary, the method described in this example is capable of simultaneously synthesizing bis (3-fluorophenyl) sulfide and the nitrile compound p-methoxybenzonitrile.
In conclusion, the invention provides a method for preparing the thioether compound and the nitrile compound simultaneously by using the benzene alkyne for the first time, the preparation method is simple, convenient and quick, transition metal catalysis is not needed, the substrate range is wide, the used fluorine source is cheap and easy to obtain, and the environmental pollution is not caused; has the advantages of simple process, mild reaction conditions, high yield (up to 98 percent), good universality and the like. Has extremely high industrial popularization value.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.

Claims (9)

1. A method for simultaneously synthesizing a thioether compound and a nitrile compound, comprising the steps of:
adding solvent into thioamide compound and fluoride under the protection of nitrogen gas, mixing, then dropwise adding benzene alkyne precursor into the mixture under the condition of stirring, uniformly mixing to obtain a mixture, and carrying out nucleophilic protonizing desulfurization and dehydrogenation reaction on the mixture to simultaneously generate thioether compound and nitrile compound.
2. The method for simultaneously synthesizing a thioether compound and a nitrile compound according to claim 1, wherein the thioamide compound comprises:
3. the method for simultaneously synthesizing a thioether compound and a nitrile compound according to claim 2, wherein R in the thioamide compound 2 Including methoxy, 4-phenyl, 3, 5-dimethoxy, 3,4, 5-trimethoxy, 4-nitro, 3-nitro, 2, 5-chloro, 1-naphthyl, 2-naphthyl, 4- (1H-imidazol-1-yl), 1-methyl-1H-indole, 2- (1H-indol-3-yl), 1-naphthylethyl.
4. The method for simultaneously synthesizing a thioether compound and a nitrile compound according to claim 1, wherein the alkyne precursor comprises:
5. the method for simultaneously synthesizing a thioether compound and a nitrile compound according to claim 4, wherein R in the phenylacetylene precursor 1 Including hydrogen, 4, 5-phenyl, 4, 5-cyclopentylalkyl, 4, 5-dimethoxy, 4, 5-dimethyl, 3-methoxy or 3-fluoro.
6. The method for simultaneously synthesizing a thioether compound and a nitrile compound according to claim 1, wherein the fluoride compound comprises tetramethyl ammonium fluoride and the solvent comprises acetonitrile.
7. The method for simultaneously synthesizing a thioether compound and a nitrile compound according to claim 1, wherein the usage ratio of the thioamide compound to the fluoride to the solvent is 0.2 mmol/0.4-0.9 mmoL/2.0 mL.
8. The method for simultaneously synthesizing a thioether compound and a nitrile compound according to claim 1, wherein the molar ratio of the thioamide compound to the benzyne precursor is 1:2.0-3.0.
9. The method for simultaneously synthesizing a thioether compound and a nitrile compound according to claim 1, wherein the reaction conditions of the nucleophilic protonation desulfurization and dehydrogenation reaction are as follows: the reaction was carried out at room temperature for 2h in a closed environment.
CN202311554375.8A 2023-11-21 2023-11-21 Method for simultaneously synthesizing thioether compounds and nitrile compounds Pending CN117567332A (en)

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