CN112645784B - Simple and efficient biaromatic alkyne synthesis method - Google Patents
Simple and efficient biaromatic alkyne synthesis method Download PDFInfo
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- CN112645784B CN112645784B CN202011541561.4A CN202011541561A CN112645784B CN 112645784 B CN112645784 B CN 112645784B CN 202011541561 A CN202011541561 A CN 202011541561A CN 112645784 B CN112645784 B CN 112645784B
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Abstract
The embodiment of the invention discloses a simple and efficient synthesis method of biaromatic alkyne, which comprises the following steps: takes arylmethyl benzotriazol and aromatic aldehyde as raw materials, and is prepared in bis (trimethylsilyl) amino salt MN (SiMe) 3 ) 2 Under the action of the catalyst, the biaromatic alkyne is synthesized by an addition reaction and a double beta-elimination reaction through a one-pot method. The method has the advantages of easily obtained raw materials and chemical reagents, mild reaction conditions, simple operation, good substrate universality and high product yield, and is a simple and efficient synthesis method of the biaromatic alkyne.
Description
Technical Field
The invention belongs to the field of organic synthesis, and relates to a simple and efficient synthesis method for preparing biaromatic alkyne from aromatic aldehyde.
Background
The biaromatic alkyne is an important pharmaceutical and chemical intermediate, and is widely applied to the fields of modern organic synthesis, pharmaceutical chemistry, material science and the like. Therefore, the efficient synthesis of biaromatic alkynes has received considerable attention from researchers. Among them, coupling reactions of halogenated aromatic hydrocarbons with alkyne compounds, such as Sonogashira coupling reactions, are the main method for synthesizing biaromatic alkynes. On the basis, researchers have further realized that aromatic hydrocarbon C (sp 3 ) Coupling of H with alkyne compounds extends the substrate range from halogenated aromatic hydrocarbons to normal aromatic hydrocarbons. However, these coupling reactions are all very limited by the use of existing aromatic alkynes to prepare biaromatic alkynesThe diversity of target products is produced. Furthermore, the self-coupling between alkynes, i.e., the Glaser-eaginton coupling, as a competitive side reaction, would result in wasteful consumption of alkyne reagents. In addition, when a coupling reaction is used to prepare a pharmaceutically active molecule containing a biaromatic alkyne backbone, the cost of purifying the target product will be greatly increased due to the use of a transition metal catalyst. Therefore, it is necessary to develop a highly efficient, non-transition catalytic, and readily available starting materials synthesis process for biaromatic alkynes.
In the existing non-transition metal catalyzed biaromatic alkyne synthesis method, double beta-elimination reaction (double beta-elimination) gradually becomes a reaction type with competitive power and application prospect. Wherein, the aryl methyl sulfone and the aromatic aldehyde can be prepared in the form of bis (trimethylsilyl) lithium amide LiN (SiMe) 3 ) 2 And diethyl chlorophosphate ClP (O) (OEt) 2 Under the action of the catalyst, the biaromatic alkyne is generated through addition and double beta-elimination reactions. Although the method uses easily available aryl methyl sulfone and aromatic aldehyde as raw materials, diethyl chlorophosphate ClP (O) (OEt) is used in the reaction 2 As an additive, the addition product is converted into phosphate, and then the phosphate can be used for preparing the lithium bis (trimethylsilyl) amide LiN (SiMe 3 ) 2 The beta-elimination reaction is continued to generate the biaromatic alkyne.
In addition, the arylmethyl benzotriazol is proved to be capable of generating a biaromatic alkyne through Mannich addition and double beta-elimination reaction with aromatic imine under the action of t-BuOK of potassium tert-butoxide, and the aromatic imine used is not stable enough and needs to be prepared in advance although no additional additive is needed in the reaction, so that the practical application of the method is limited.
Since aromatic imines are usually prepared from the corresponding aromatic aldehydes, if aromatic aldehydes can be directly used for reacting with arylmethyl benzotriazoles, and no additional additives are needed, the one-step synthesis of the biaromatic alkyne is an ideal biaromatic alkyne synthesis method, and more choices are provided for the synthesis of the biaromatic alkyne.
Disclosure of Invention
The invention aims to solve the technical problems of the existing biaromatic alkyne synthesis method, such as preparation of biaromatic alkyne by using existing aromatic alkyne, need of additives, unstable raw materials, need of preparation in advance, and the like, and provides a simple and efficient biaromatic alkyne synthesis method.
In order to solve the technical problems, the invention provides a simple and efficient synthesis method of biaromatic alkyne, which comprises the following steps: takes arylmethyl benzotriazol and aromatic aldehyde as raw materials, and is prepared in bis (trimethylsilyl) amino salt MN (SiMe) 3 ) 2 Under the action of the catalyst, the biaromatic alkyne is synthesized by an addition reaction and a double beta-elimination reaction by a one-pot method, and the chemical reaction formula is as follows:
wherein, the arylmethyl benzotriazole is one of benzyl benzotriazole containing different substituents Me, F, cl, br, I and 1- (2-naphthylmethyl) benzotriazole;
aromatic aldehyde is a polymer containing electron-donating group OMe, me, SMe and electron-withdrawing group F, cl, br, I, CF 3 1-or 2-naphthaldehyde, terephthalaldehyde, aromatic heteroaldehyde;
MN(SiMe 3 ) 2 is bis (trimethylsilyl) lithium amide LiN (SiMe) 3 ) 2 Sodium bis (trimethylsilyl) amide NaN (SiMe) 3 ) 2 And potassium bis (trimethylsilyl) amide KN (SiMe) 3 ) 2 One of them.
Further, the simple and efficient reaction conditions of the biaromatic alkyne synthesis method are as follows: MN (SiMe 3 ) 2 Adding the solution into tetrahydrofuran solution of arylmethyl benzotriazol and aromatic aldehyde, stirring the reaction in an oil bath under the protection of nitrogen, cooling to room temperature, quenching the reaction with water, filtering the reaction solution through a short silica gel column, flushing with ethyl acetate, distilling under reduced pressure to remove the solvent in the filtrate, and separating residues through silica gel column chromatography to obtain the product of the biaromatic alkyne.
Further, the diaryl alkyne is diphenyl acetylene, and the reaction conditions are as follows: 1.6mmol of 1.0mol/LMN (SiMe) 3 ) 2 Tetrahydrofuran solution, adding into 3.0mL tetrahydrofuran solution of 0.44mmol of benzyl benzotriazole and 0.4mmol of benzaldehyde, stirring the reaction for 18h in an oil bath at 60 ℃ under the protection of nitrogen, quenching the reaction with 7 drops of water after cooling to room temperature, filtering the reaction solution through a short silica gel column, flushing with ethyl acetate for 4 times, removing the solvent in the filtrate by reduced pressure distillation, separating the residue through silica gel column chromatography, and taking n-hexane as an eluent to obtain the target product diphenyl acetylene with the yield of 90 percent, wherein the chemical reaction formula is as follows:
the embodiment of the invention has the following beneficial effects: the simple and efficient synthesis method of the biaromatic alkyne can directly use the reaction of aromatic aldehyde and arylmethyl benzotriazol, does not need to add additional additives, and is simple and efficient.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a simple and efficient biaromatic alkyne synthesis method, which comprises the following steps: takes arylmethyl benzotriazol and aromatic aldehyde as raw materials, and is prepared in bis (trimethylsilyl) amino salt MN (SiMe) 3 ) 2 Under the action of the catalyst, the biaromatic alkyne is synthesized by an addition reaction and a double beta-elimination reaction by a one-pot method, and the chemical reaction formula is as follows:
wherein, the arylmethyl benzotriazole is one of benzyl benzotriazole containing different substituents Me, F, cl, br, I and 1- (2-naphthylmethyl) benzotriazole;
aromatic aldehyde is a polymer containing electron-donating group OMe, me, SMe and electron-withdrawing group F, cl, br, I, CF 3 1-or 2-naphthaldehyde, terephthalaldehyde, aromatic heteroaldehyde;
MN(SiMe 3 ) 2 is bis (trimethylsilyl) lithium amide LiN (SiMe) 3 ) 2 Sodium bis (trimethylsilyl) amide NaN (SiMe) 3 ) 2 And potassium bis (trimethylsilyl) amide KN (SiMe) 3 ) 2 One of them.
Further, the simple and efficient reaction conditions of the biaromatic alkyne synthesis method are as follows: MN (SiMe 3 ) 2 Adding the solution into tetrahydrofuran solution of arylmethyl benzotriazol and aromatic aldehyde, stirring the reaction in an oil bath under the protection of nitrogen, cooling to room temperature, quenching the reaction with water, filtering the reaction solution through a short silica gel column, flushing with ethyl acetate, distilling under reduced pressure to remove the solvent in the filtrate, and separating residues through silica gel column chromatography to obtain the product of the biaromatic alkyne.
When the target product of the diaryl alkyne is diphenyl acetylene, the reaction conditions are as follows: 1.6mmol of 1.0mol/LMN (SiMe) 3 ) 2 Tetrahydrofuran solution, added to 0.44mmol of benzyl benzeneAnd 3.0mL of tetrahydrofuran solution of triazole and 0.4mmol of benzaldehyde are stirred for 18h in an oil bath at 60 ℃ under the protection of nitrogen, after the reaction is cooled to room temperature, 7 drops of water are used for quenching the reaction, the reaction solution is filtered by a short silica gel column, the reaction solution is washed for 4 times by ethyl acetate, the solvent in the filtrate is removed by reduced pressure distillation, the residue is separated by silica gel column chromatography, and n-hexane is used as an eluent to obtain the target product diphenylacetylene, the yield is 90 percent, and the chemical reaction formula is:
under the optimal reaction conditions, the substrate range of aromatic aldehyde is examined by taking arylmethyl benzotriazole as a reference and adopting 1-benzyl benzotriazole as a reference. Various electron-donating groups (e.g. OMe, me, SMe), electron-withdrawing groups (F, cl, br, I, CF) 3 ) The benzaldehyde of (2) can be efficiently converted into corresponding biaromatic alkyne; 1-or 2-naphthaldehyde, terephthalaldehyde, aromatic heteroaldehydes (such as 2-thiophenecarboxaldehyde and 2-furancarbaldehyde) can also be efficiently converted to biaromatic alkynes. The chemical reaction formula is as follows:
in other embodiments, when the product is
The yields are respectively as follows:
it should be noted in particular that the reaction can be scaled up to gram levels. For example: 1-Benzylbenzotriazole (1.38 g,6.6 mmol) was reacted with 4-bromobenzaldehyde (1.11 g,6.0 mmol) to give the above product 20: r=4-Br (1.37 g,5.32mmol,89% yield).
Under the optimal condition, 4-chlorobenzaldehyde is selected as a reference, and the substrate range of the 1-arylmethyl benzotriazole is examined. Benzyl benzotriazole containing different substituents (such as Me, F, cl, br and I) and 1- (2-naphthylmethyl) benzotriazole can react with 4-chlorobenzaldehyde to synthesize the corresponding biaromatic alkyne derivative. The chemical reaction formula is as follows:
according to the difference of reactants, the following products are respectively prepared, and the yields are respectively as follows:
when the aromatic aldehyde was 2-furaldehyde, the substrate range of 1-arylmethylbenzotriazole was examined. The benzyl benzotriazole containing different substituents (such as Me, F, cl and Br) can react with the benzyl benzotriazole to generate a series of furan ring-containing biaromatic alkyne derivatives. The chemical reaction formula is as follows:
according to the difference of reactants, the following products are respectively prepared, and the yields are respectively as follows:
in order to study the reaction history of the present synthetic method, the synthesis was performed by reacting MN (SiMe 3 ) 2 The amount of (C) was reduced from 1.6mmol to 0.8mmol and the reaction temperature was lowered to room temperature to give enamine 45 (yield: 74%) which was found in MN (SiMe) 3 ) 2 Can be further reacted to form diphenylalkyne 3 (yield: 96%), wherein the numbers are structural formula numbers in the following reaction formulae. From this, it was confirmed that enamine was a reaction intermediate in the synthesis of biaromatic alkyne.
According to the research results, the reaction mechanism of the synthesis method of the biaromatic alkyne is as follows: aldehyde is first reacted with MN (SiMe) 3 ) 2 The reaction generates imine 47 in situ. At the same time, 1-arylmethyl benzotriazoles are useful in the treatment of MN (SiMe 3 ) 2 Under action, benzyl carbanion 48 is formed, followed by nucleophilic attack on the imine to form addition product 50. In MN (SiMe) 3 ) 2 Under the action of this, the first β -elimination of the addition product takes place to give enamine intermediate 51, which is then carried out in MN (SiMe 3 ) 2 A second beta-elimination reaction occurs under the action to produce the target product diaryl alkyne 54.
The embodiment of the invention has the following beneficial effects: the method for synthesizing the biaromatic alkyne is easy to obtain the used raw materials and chemical reagents, mild in reaction conditions, simple to operate, good in substrate universality and high in product yield, and is a simple and efficient method for synthesizing the biaromatic alkyne.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (2)
1. The simple and efficient biaromatic alkyne synthesis method is characterized by comprising the following steps of: takes arylmethyl benzotriazol and aromatic aldehyde as raw materials, and is prepared in bis (trimethylsilyl) amino salt MN (SiMe) 3 ) 2 Under the action of the catalyst, the biaromatic alkyne is synthesized by an addition reaction and a double beta-elimination reaction by a one-pot method, and the chemical reaction formula is as follows:
wherein: the arylmethyl benzotriazole is one of benzyl benzotriazole containing different substituents Me, F, cl, br, I and 1- (2-naphthylmethyl) benzotriazole;
aromatic aldehyde is a polymer containing electron-donating group OMe, me, SMe and electron-withdrawing group F, cl, br, I, CF 3 1-or 2-naphthaldehyde, terephthalaldehyde, aromatic heteroaldehyde;
MN(SiMe 3 ) 2 is bis (trimethylsilyl) lithium amide LiN (SiMe) 3 ) 2 Sodium bis (trimethylsilyl) amide NaN (SiMe) 3 ) 2 And potassium bis (trimethylsilyl) amide KN (SiMe) 3 ) 2 One of the following;
the simple and efficient reaction conditions of the biaromatic alkyne synthesis method are as follows: MN (SiMe 3 ) 2 Adding the solution into tetrahydrofuran solution of arylmethyl benzotriazol and aromatic aldehyde, stirring the reaction in an oil bath under the protection of nitrogen, cooling to room temperature, quenching the reaction with water, filtering the reaction solution through a short silica gel column, flushing with ethyl acetate, distilling under reduced pressure to remove the solvent in the filtrate, and separating residues through silica gel column chromatography to obtain the product of the biaromatic alkyne.
2. The method for synthesizing the simple and efficient biaromatic alkyne according to claim 1, wherein the biaromatic alkyne is diphenylacetylene, and the reaction conditions are as follows: 1.6mmol of 1.0mol/L MN (SiMe) 3 ) 2 Tetrahydrofuran solution, adding into 3.0mL tetrahydrofuran solution of 0.44mmol of benzyl benzotriazole and 0.4mmol of benzaldehyde, stirring the reaction for 18h in an oil bath at 60 ℃ under the protection of nitrogen, quenching the reaction with 7 drops of water after cooling to room temperature, filtering the reaction solution through a short silica gel column, flushing with ethyl acetate for 4 times, removing the solvent in the filtrate by reduced pressure distillation, separating the residue through the silica gel column chromatography, and taking n-hexane as an eluent to obtain the target product diphenylacetylene with the yield of 90 percent, wherein the target product is prepared by the steps ofThe chemical reaction formula is:
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| Haixing Guan et al.One-Pot Aminoalkylation of Aldehydes: Diastereoselective Synthesis of Vicinal Diamines with Azaarylmethylamines.《Org. Lett.》.2019,第21卷(第21期),第8679–8683页. * |
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