CN107867988B - Synthesis method of 1, 3-diphenyl-1-acetone - Google Patents
Synthesis method of 1, 3-diphenyl-1-acetone Download PDFInfo
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- CN107867988B CN107867988B CN201711270163.1A CN201711270163A CN107867988B CN 107867988 B CN107867988 B CN 107867988B CN 201711270163 A CN201711270163 A CN 201711270163A CN 107867988 B CN107867988 B CN 107867988B
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
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Abstract
The invention discloses a method for synthesizing 1, 3-diphenyl-1-acetone, which comprises the following steps: adding acetophenone, benzyl alcohol, a catalyst, alkali and a solvent into a reactor in sequence; and (3) carrying out magnetic stirring reaction in an argon atmosphere, and fully reacting in an oil bath kettle. The process of the present invention avoids the problem of large amounts of by-products caused by the use of reagents in traditional synthetic processes because they are inexpensive, easy to store and environmentally friendly, and are renewable alternatives to petroleum-based compounds. The method adopts the NNN type pincerlike metal ruthenium (II) compound as the catalyst for catalytic reaction, the reaction is completed in one step, the operation is simple and convenient, the reaction efficiency is high, and the method meets the requirement of green chemical sustainable development.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of 1, 3-diphenyl-1-acetone.
Background
The ability to handle and extend the carbon function through carbon-carbon bond forming reactions is crucial for the synthesis of organic chemistry, such as pharmaceutical chemistry, pesticides, and the synthesis of natural products. In this case, aldehydes and ketones play a critical role because their carbonyl functionality can participate in the reaction array leading to carbon-carbon bond formation, such as attack by various carbonyl nucleophiles such as organometallic reagents (organolithiums, grignard reagents, etc.), cyanides, enolates derived from active methylene compounds, and the like, as well as being prepared from Wittig-type reagents. Furthermore, these compounds can also act as C nucleophiles via the corresponding enols, for example in aldol reactions. In recent years, the use of alcohols as starting materials for C — C bond formation processes has received increasing attention because they are inexpensive, easy to handle and store, environmentally friendly, and renewable alternatives to petroleum-based compounds. By using a wide variety of oxidizing reagents, primary and secondary alcohols can be converted to the corresponding aldehydes and ketones, respectively. However, these transformations suffer from waste problems due to the large amount of by-products formed by the reagents, thereby reducing atomic efficiency. Therefore, finding an efficient, selective, atom-economical and environmentally friendly process remains a key challenge for chemists.
Metal-catalyzed alcohol dehydrogenation is a direct route to carbonyl compounds such as aldehydes and ketones by extracting hydrogen directly from the substrate, and does not require an oxidizing agent. Compared with the traditional method, the transition metal catalyzes the formation reaction of carbon-carbon bonds, so that the generation problem of waste can be effectively avoided, and the atom economic efficiency is improved. Various transition metal complexes (Ir, Rh, Ru, Pd, Cu, Os, etc.) have been developed for homo-and heterogeneous BH catalysis, but there still remains a problem in reaction efficiency.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing 1, 3-diphenyl-1-acetone, which takes alcohol as a starting material for forming a C-C bond and synthesizes the 1, 3-diphenyl-1-acetone under the catalysis of a pincer-shaped metal ruthenium (II) compound, thereby greatly shortening the reaction time and improving the reaction efficiency.
In order to solve the technical problems, the invention adopts the following technical scheme:
1. a method for synthesizing 1, 3-diphenyl-1-acetone comprises the following steps: adding acetophenone, benzyl alcohol, a catalyst, alkali and a solvent into a reactor in sequence; reacting under magnetic stirring in argon atmosphere at 120 ℃ for 4h in an oil bath kettle, wherein the structural formula of the 1, 3-diphenyl-1-acetone is as follows:
the reactor is a dry and clean Schlenk tube, the Schlenk tube adopts standard technology, and the whole reaction is carried out under the protection of inert gas argon.
The mass ratio of the acetophenone to the benzyl alcohol is 1: 1.0-1: 1.2.
The catalyst is a pincer-shaped metal ruthenium (II) compound, the amount of the pincer-shaped metal ruthenium (II) compound is 0.5mol% of the amount of acetophenone substances, and the structural general formula is as follows:
the alkali is selected from one of potassium tert-butoxide, potassium hydroxide, sodium amide, sodium phenolate, sodium methoxide, potassium phosphate trihydrate, sodium ethoxide, cesium carbonate and ammonium hexafluorophosphate.
The ratio of the amount of the base substance to the amount of the acetophenone substance is 0.15-0.5: 1.
The solvent is one or a mixture of more of dichloromethane, toluene, tertiary amyl alcohol, dioxane and water.
A typical synthesis procedure is as follows: under the argon atmosphere, a certain amount of acetophenone is added, then corresponding amounts of benzyl alcohol, a pincerlike ruthenium compound, a base and a solvent are added, and the mixture is stirred for 4 hours in an oil bath kettle at 120 ℃. And (3) determining that the raw material acetophenone has completely reacted by TLC, performing vacuum rotary evaporation, separating and purifying by thin-layer chromatography, and calculating the yield of the 1, 3-diphenyl-1-acetone.
Compared with the traditional process, the method of the invention has the remarkable advantages that: (1) the new process employs alcohol as starting material for the formation of C-C bond (cheap, easy to handle and environment friendly); (2) the method avoids the problem of a large amount of byproducts caused by using various oxidants in the traditional method; (3) the method uses transition metal pincerlike catalyst ruthenium (II) compound, greatly shortens the reaction time and improves the reaction efficiency.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The synthesis method of 1, 3-diphenyl-1-propanone of this example includes the following steps:
to a 15 ml Schlenk tube, 48.1 mg (0.4 mmol) of acetophenone, 47.6 mg (0.44 mmol) of benzyl alcohol, 1.55 mg (0.5 mol%) of the pincer-like metal ruthenium (II) compound, 15.98 mg (0.15 equiv) of potassium phosphate trihydrate, 1.5ml of methylene chloride, magnetic stirring under argon atmosphere, and reaction at 120 ℃ for 4 hours were added. The starting acetophenone was reacted to completion by TLC analysis. Vacuum rotary evaporation, thin layer chromatography separation and purification, the product 1, 3-diphenyl-1-acetone mass is 16.84 mg, yield is 20%. The product is processed by1H NMR、13C NMR confirmed.1H NMR (400MHz, CDCl3)δ7.96-7.94(m, 2H),7.57-7.53 (m, 1H), 7.311 (t,J= 7.6 Hz, 2H), 7.32-7.18 (m, 5H), 3.565 (m,J= 3.29 Hz, 2H), 3.07 (t,J= 7.6 Hz, 2H).13C NMR (100 MHz, CDCl3)δ199.2,141.3, 136.9, 133.1, 128.6, 128.5, 128.4, 128.1, 126.2, 40.5, 30.1.
Example 2
The synthesis method of 1, 3-diphenyl-1-propanone of this example includes the following steps:
to a 15 ml Schlenk tube, 48.1 mg (0.4 mmol) of acetophenone, 47.6 mg (0.44 mmol) of benzyl alcohol, 1.55 mg (0.5 mol%) of a pincer-like metal ruthenium (II) compound, 10.8 mg (0.5 equiv) of sodium methoxide, 1.5ml of a mixed solvent of dioxane and water were added, and the mixture was magnetically stirred under an argon atmosphere and reacted at 120 ℃ for 4 hours. The starting acetophenone was reacted to completion by TLC analysis. Vacuum rotary evaporation and thin layer chromatography separation and purification are carried out, the mass of the product 1, 3-diphenyl-1-acetone is 45.46 mg, and the yield is 33%.
Example 3
The synthesis method of 1, 3-diphenyl-1-propanone of this example includes the following steps:
to a 15 ml Schlenk tube were added 48.1 mg (0.4 mmol) of acetophenone, 47.6 mg (0.4 mmol) of benzyl alcohol, 1.55 mg (0.5 mol%) of the pincer-like metal ruthenium (II) compound, 22.44 mg (0.5 equiv) of potassium tert-butoxide, 1.5ml of toluene, and magnetically stirred under an argon atmosphere, and reacted at 120 ℃ for 4 hours. The starting acetophenone was reacted to completion by TLC analysis. Vacuum rotary evaporation, thin layer chromatography separation and purification, product 1, 3-diphenyl-1-acetone mass is 50.46 mg, yield 54%.
Example 4
The synthesis method of 1, 3-diphenyl-1-propanone of this example includes the following steps:
to a 15 ml Schlenk tube, 48.1 mg (0.4 mmol) of acetophenone, 43.3 mg (0.4 mmol) of benzyl alcohol, 1.55 mg (0.5 mol%) of the pincer-like metal ruthenium (II) compound, 15.98 mg (0.15 equiv) of potassium phosphate trihydrate, 0.5 ml of methylene chloride, magnetic stirring under argon atmosphere, and reaction at 120 ℃ for 4 hours were added. The starting acetophenone was reacted to completion by TLC analysis. Vacuum rotary evaporation, thin layer chromatography separation and purification, the product 1, 3-diphenyl-1-acetone mass is 75.70mg, the yield is 90%.
Example 5
In a 15 ml Schlenk tube, 48.1 mg (0.4 mmol) of acetophenone, 47.6 mg (0.4 mmol) of benzyl alcohol, 1.55 mg (0.5 mol%) of the pincer-like metal ruthenium (II) compound, 15.98 mg (0.15 equiv) of potassium phosphate trihydrate, 0.5 ml of t-amyl alcohol under argon atmosphere were magnetically stirred and reacted at 120 ℃ for 4 hours. The starting acetophenone was reacted to completion by TLC analysis. Vacuum rotary evaporation and thin layer chromatography separation and purification are carried out, the mass of the product 1, 3-diphenyl-1-acetone is 81.65 mg, and the yield is 97%.
Example 6
The synthesis method of 1, 3-diphenyl-1-propanone of this example includes the following steps:
in a 15 ml Schlenk tube, 48.1 mg (0.4 mmol) of acetophenone, 51.9 mg (0.48 mmol) of benzyl alcohol, 1.55 mg (0.5 mol%) of the pincer-like metal ruthenium (II) compound, 15.98 mg (0.15 equiv) of potassium phosphate trihydrate, 0.5 ml of t-amyl alcohol, magnetic stirring under argon atmosphere, and reaction at 120 ℃ for 4 hours. The starting acetophenone was reacted to completion by TLC analysis. Vacuum rotary evaporation, thin layer chromatography separation and purification, product 1, 3-diphenyl-1-acetone mass is 79.90mg, yield is 95%.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A method for synthesizing 1, 3-diphenyl-1-acetone is characterized by comprising the following steps: adding acetophenone, benzyl alcohol, a catalyst, alkali and a solvent into a reactor in sequence; reacting under magnetic stirring in argon atmosphere at 120 ℃ for 4h in an oil bath kettle, wherein the structural formula of the 1, 3-diphenyl-1-acetone is as follows:
the catalyst is a pincer-shaped metal ruthenium (II) compound, the amount of the pincer-shaped metal ruthenium (II) compound is 0.5mol% of the amount of acetophenone substances, and the structural general formula is as follows:
2. the method for synthesizing 1, 3-diphenyl-1-propanone according to claim 1 wherein the reactor is a dry clean Schlenk tube using standard techniques and the entire reaction is carried out under the protection of inert gas argon.
3. The method for synthesizing 1, 3-diphenyl-1-propanone according to claim 1, wherein the mass ratio of acetophenone to benzyl alcohol is 1: 1.0-1: 1.2.
4. The method for synthesizing 1, 3-diphenyl-1-propanone according to claim 1, characterized in that said base is selected from one of potassium tert-butoxide, potassium hydroxide, sodium amide, sodium phenoxide, sodium methoxide, potassium phosphate trihydrate, sodium ethoxide, cesium carbonate, ammonium hexafluorophosphate.
5. The method for synthesizing 1, 3-diphenyl-1-propanone according to claim 1, characterized in that the ratio of the amount of the substance of the base to the amount of the substance of acetophenone is 0.15-0.5: 1.
6. The method for synthesizing 1, 3-diphenyl-1-propanone according to claim 1, characterized in that the solvent is one or a mixture of several of dichloromethane, toluene and tert-amyl alcohol.
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Non-Patent Citations (3)
| Title |
|---|
| "New Type of 2,6-Bis(imidazo[1,2 a]pyridin-2-yl)pyridine-Based Ruthenium Complexes: Active Catalysts for Transfer Hydrogenation of Ketones";Ke Li et al;《Organometallics》;20150317;第34卷;第1170-1176页 * |
| "Recyclable Palladium Catalyst for Highly Selective αAlkylation of Ketones with Alcohols";Min Serk Kwon et al;《Angew.Chem.Int.Ed》;20051005;第44卷;第6914页Table-3，第6915页左栏最后一段 * |
| NCN钳形铑(Ⅲ)以及CNN钳形钯(Ⅱ)和钌(Ⅱ)化合物物合成与催化性能研究;王涛;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20141231;第133-135页 * |
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