CN105646220A - Synthesizing method of propiophenone compound - Google Patents

Abstract

The invention provides a synthesizing method of a propiophenone compound, and belongs to the technical field of organic synthesizing. The synthesizing method has the advantages that the reaction steps for synthesizing the propiophenone compound can be simplified, and the reaction cost is reduced. The synthesizing method of the propiophenone compound comprises the following steps of adding propylbenzene, organic acid, iodine and tert-butyl hydroperoxide into a reaction kettle, and reacting for 8-24h at the temperature of 80-120 DEG C; after the reaction is finished, extracting a reaction solution by an organic solvent, and drying, so as to obtain the propiophenone compound. The synthesizing method can be used for the synthesizing and preparation of the propiophenone compound.

Description

A kind of synthetic method of propiophenone compound

technical field

The invention relates to the technical field of organic synthesis, in particular to a synthesis method of propiophenone compounds.

Background technique

Propiophenone compounds are important intermediates in organic synthesis, widely exist in natural products and pharmaceutical active molecules, and are widely used in chemical production such as medicine and pesticide.

In the synthesis of existing propiophenone compounds, it is often synthesized by using propiophenone as a raw material, for example, it is recorded in Angew. Ammonium iodide, ethyl acetate, and a temperature of 75°C react with organic acids and tert-butyl hydroperoxide to generate propiophenone compounds. In the reaction process, in order to obtain the target product, halides such as tetrabutylammonium iodide are added in the reaction. Of course, halogens can also be added directly, but in this case, it is necessary to add phase transfer catalyst.

But no matter which of the above synthetic routes, organic solvents other than tert-butyl hydroperoxide will be used in the reaction, and some even use phase transfer catalysts, which will not only increase the additional reaction substances, but also complicate the reaction steps. . In order to overcome the above technical problems, the inventor provides a new method for synthesizing propiophenones.

Contents of the invention

The object of the present invention is to provide a kind of synthetic method of propiophenone compound, can simplify the reaction step of synthesizing propiophenone compound, and reduce reaction cost.

The invention provides a kind of synthetic method of propiophenone compound, comprising:

Add propylbenzene, organic acid, iodine, and tert-butyl hydroperoxide into the reaction kettle, and react at 80°C-120°C for 8-24 hours;

After the reaction is finished, the reaction solution is extracted with an organic solvent, and dried to obtain the propiophenone compound:

Specifically, the R group in the structure of formula (I) is selected from one of methyl, isopropyl, ethyl, propyl or benzyl.

The added propylbenzene, organic acid, iodine, and tert-butyl hydroperoxide have a millimolar ratio of 1:1-2:0.2-0.3:6-8.

Preferably, the added propylbenzene, organic acid, iodine, and tert-butyl hydroperoxide have a millimolar ratio of 1:1:0.2:6.

The organic acid is selected from one of acetic acid, isobutyric acid, propionic acid, butyric acid or phenylacetic acid.

Preferably, add propylbenzene, organic acid, iodine, and tert-butyl hydroperoxide into the reaction kettle, and react at 100° C. for 24 hours.

The organic solvent is selected from ethyl acetate, ether, chloroform, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, toluene, 1,2-xylene or 1,2-dichloroethane at least one of the

The present invention provides a kind of synthetic method of propiophenone compound, compared with prior art, the synthetic method provided by the present invention is to utilize propyl benzene compound to synthesize propiophenone compound as raw material, in this synthetic method Among them, propylbenzene and organic acid can directly react to generate the target product under tert-butyl hydroperoxide, iodine and mild reaction conditions, and, in this synthetic method, except using tert-butyl hydroperoxide, this reaction Solvent, no need to use other solvents. The synthesis method is simple to operate, not only simplifies the synthesis route, but also reduces the reaction cost because no other solvent is used, therefore, a new method for synthesizing propiophenone compounds is provided for those skilled in the art.

detailed description

The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

The embodiment of the present invention provides a synthetic method of propiophenone compounds, comprising:

S1: Add propylbenzene, organic acid, iodine, and tert-butyl hydroperoxide into the reaction kettle, and react at 80°C-120°C for 8-24 hours.

In this step, the "one-pot method" can be used to synthesize propiophenone compounds. Specifically, propylbenzene, organic acid, tert-butyl hydroperoxide and iodine are added to the reaction kettle together, and heated at 80°C- React at 120°C for 8-24 hours to produce the target product. The specific reaction process is as follows:

S2: After the reaction is completed, the reaction solution is extracted with an organic solvent, and dried to obtain a propiophenone compound:

The embodiment of the present invention provides a kind of synthetic method of propiophenone compound, compared with prior art, the synthetic method provided by the present invention is to utilize propyl benzene compound as raw material to synthesize propiophenone compound, in this In the synthetic method, propylbenzene and organic acid can directly react to generate the target product under tert-butyl hydroperoxide, iodine and mild reaction conditions, and, in this synthetic method, except using tert-butyl hydroperoxide, this Except for the reaction solvent, there is no need to use other solvents. The synthesis method is simple to operate, not only simplifies the synthesis route, but also reduces the reaction cost because no other solvent is used, therefore, a new method for synthesizing propiophenone compounds is provided for those skilled in the art.

In an embodiment of the present invention, the R group in the structure of formula (I) is selected from one of methyl, isopropyl, ethyl, propyl or benzyl. It can be understood that the R groups listed in this embodiment are not limited to the groups listed above, and can also be other groups that are considered suitable for participating in the reaction process by those skilled in the art after analysis.

In an embodiment of the present invention, the added propylbenzene, organic acid, iodine, and tert-butyl hydroperoxide have a millimolar ratio of 1:1-2:0.2-0.3:6-8. In this embodiment, when adding the above-mentioned reactant substances into the reaction kettle to carry out the reaction using the "one-pot method", it is necessary to precisely control the amount of the above-mentioned reactant substances added, for example, each reactant substance within the above-mentioned ratio range can be added. It can be understood that, when operating the above reaction, those skilled in the art can select the appropriate addition amount of each reaction substance within the range given above.

In a preferred embodiment of the present invention, the added propylbenzene, organic acid, iodine, and tert-butyl hydroperoxide have a millimolar ratio of 1:1:0.2:6. In this example, propylbenzene, organic acid, iodine and tert-butyl hydroperoxide can be added in a millimolar ratio of 1:1:0.2:6 to obtain the target product more accurately.

In an embodiment of the present invention, the organic acid is selected from one of acetic acid, isobutyric acid, propionic acid, butyric acid or phenylacetic acid. In order to obtain the expected target product, in this embodiment, a matching organic acid can be selected and added accordingly. However, it should be understood that, since the reaction route for the synthesis of propiophenone compounds given in the examples of the application is widely used, in view of the selected R groups are not limited to those listed in the application, therefore, the used Compatible organic acids are not limited to those listed in this application.

In one embodiment of the present invention, after adding propylbenzene, organic acid, iodine, and tert-butyl hydroperoxide into the reaction kettle, the reaction was carried out at 100° C. for 24 hours. In this embodiment, in order to ensure that the reaction substances can fully and completely react, it is preferable to react at 100° C. for 24 hours. But it can be understood that, with the different organic acids participating in the reaction, the properties of the synthesized target product are also slightly different, so those skilled in the art can make slight adjustments in the above temperature and time ranges according to the preferred temperature and time conditions. Adjustment. For example, the temperature can be 85°C, 90°C, 95°C, 100°C, 110°C, 105°C, and the reaction time is 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours.

In one embodiment of the present invention, the organic solvent is selected from ethyl acetate, diethyl ether, chloroform, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, toluene, 1,2-xylene or at least one of 1,2-dichloroethane. It can be understood that the organic solvents listed in this embodiment are not limited to those listed above, and can also be other organic solvents familiar to those skilled in the art.

In order to describe the synthesis method of the propiophenone compounds provided by the examples of the present invention in more detail, the following description will be made in conjunction with the organic acids being acetic acid and isobutyric acid as specific examples.

Example 1

Add propylbenzene, acetic acid, iodine, and tert-butyl hydroperoxide with a mmol ratio of 1:1:0.2:6 into the reaction kettle, and react at 80°C for 8 hours; after the reaction is completed, use ethyl acetate The reaction solution was extracted and dried to obtain a colorless oily liquid that is Propiophenone Compound A:

The above-mentioned colorless oily liquid is subjected to nuclear magnetic spectrum analysis, and the data are as follows:

¹ HNMR (CDCl ₃ , 400MHz) δ1.56(d, J=6.8Hz, 3H), 2.17(s, 3H), 5.99(q, J=6.8Hz, 1H), 7.49–7.54(m, 2H), 7.60–7.63(m,1H), 7.95–7.97(m,2H);

¹³ CNMR (CDCl ₃ , 100MHz) δ17.2, 20.5, 71.1, 128.2, 128.6, 133.7, 134.5, 170.4, 196.9;

After identification, the spectral data corresponded to the structural formula, proving that the synthesized compound was propiophenone compound A with a yield of 60%.

Example 2

Add propylbenzene, isobutyric acid, iodine, and tert-butyl hydroperoxide with a mmol ratio of 1:2:0.3:8 into the reaction kettle, and react at 120°C for 24 hours; after the reaction is completed, use acetic acid The reaction solution was extracted with ethyl ester and dried to obtain a colorless oily liquid, i.e. propiophenone compound B:

Carry out nuclear magnetic spectrum analysis to above-mentioned colorless oily liquid, the data are as follows:

¹ HNMR (CDCl ₃ , 300MHz) δ1.19-1.20(m, 6H), 1.55(q, J=6.9Hz, 3H), 2.65(hept, J=6.9Hz, 1H), 5.97(q, J=6.9 Hz,1H), 7.44-7.53(m,2H), 7.58-7.63(m,1H), 7.93-7.98(m,2H);

¹³ CNMR (CDCl ₃ , 75MHz) δ17.1, 18.7, 18.9, 33.9, 71.1, 128.4, 128.7, 133.6, 134.5, 176.8, 197.3;

After identification, the spectral data corresponded to the structural formula, proving that the synthesized compound was propiophenone compound B with a yield of 69%.

As can be seen from the foregoing examples, the synthesis method of the propiophenone compound provided by the application is simple to operate compared to the prior art, simplifies the synthesis route and reduces the reaction cost, and the yield of the target product obtained by synthesis is The yield is relatively higher than that in the prior art.

Apparently, the above-mentioned embodiments are only examples for clear description, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. However, the obvious changes or changes derived therefrom still fall within the scope of protection of the present invention.

Claims (7)

1. a synthetic method of propiophenone compound, is characterized in that, comprises: Add propylbenzene, organic acid, iodine, and tert-butyl hydroperoxide into the reaction kettle, and react at 80°C-120°C for 8-24 hours; After the reaction is finished, the reaction solution is extracted with an organic solvent, and dried to obtain the propiophenone compound: 2. the synthetic method of Propiophenones according to claim 1, is characterized in that, in described formula (I) structure, R group is selected from methyl, isopropyl, ethyl, propyl or benzyl kind of. 3. the synthetic method of propiophenone compound according to claim 1 is characterized in that, the millimol ratio of added propylbenzene, organic acid, iodine, tert-butyl hydroperoxide is 1: 1-2: 0.2-0.3:6-8. 4. the synthetic method of propiophenone compound according to claim 3 is characterized in that, the millimol ratio of added propylbenzene, organic acid, iodine, tert-butyl hydroperoxide is 1: 1: 0.2: 6. 5. the synthetic method of Propiophenones according to claim 1, is characterized in that, described organic acid is selected from the one in acetic acid, isobutyric acid, propionic acid, butyric acid or phenylacetic acid. 6. the synthetic method of propiophenone compound according to claim 1 is characterized in that, propylbenzene, organic acid, iodine, tert-butyl hydroperoxide are added in the reactor, reacted 24 hours at 100 ℃ . 7. the synthetic method of propiophenone compound according to claim 1, is characterized in that, described organic solvent is selected from ethyl acetate, ether, chloroform, dimethylsulfoxide, N,N-dimethyl formaldehyde At least one of amides, tetrahydrofuran, toluene, 1,2-xylene or 1,2-dichloroethane.