JP4297307B2 - 1-Indanone production method - Google Patents

Description

【００３３】

【００３４】

【００３５】

【００３６】
【発明の効果】
本発明の方法によれば、原料であるインダン類の溶液のインダン類濃度、触媒使用量を規定し、マイルドな条件でインダン類を酸化することにより、高転化率、かつ高選択率にて１−インダノン類を得ることができるので、安価にかつ工業的規模での１−インダノン類の製造が可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for industrially advantageously producing 1-indanones useful as intermediate raw materials for pharmaceuticals and agricultural chemicals from indanes. In the present invention, “indanes” means indane and substituted derivatives thereof, and “1-indanone” means 1-indanone and substituted derivatives thereof.
[0002]
[Prior art]
As a conventional method for producing 1-indanone,
(1) A method of cyclizing 3-phenylpropionic acid in the presence of a catalyst such as aluminum chloride,
(2) A method of oxidizing 1-chloroindane through hydrogen chloride gas to indene and then oxidizing with chromic acid, and (3) a method of oxidizing indane obtained by hydrogenating indene,
Etc. are known.
[0003]
[Problems to be solved by the invention]
The method (1) has a problem that it is difficult to obtain 3-phenylpropionic acid at low cost. Further, the method (2) has a problem of using chromic acid having a large environmental load. Therefore, a method for synthesizing 1-indanone by oxidizing indane obtained by hydrogenating indene as in the above method (3) has been studied. For example, a method for producing 1-indanone in the presence of an N, N-dialkyl fatty acid amide using a soluble chromium salt and / or cobalt salt as a catalyst is known (Japanese Patent Laid-Open No. 56-32439). This method has a problem that when the indane conversion rate is high, the 1-indanone selectivity is low, whereas when the selectivity is high, the conversion rate must be lowered.
[0004]
Further, the method for producing 1-indanone in the presence of an N-alkyl fatty acid amide using a soluble chromium salt and / or cobalt salt as a catalyst (Japanese Patent Laid-Open No. 9-136659) is said to have good conversion and selectivity. Although there are advantages, this reaction requires a severe reaction condition of a pressure of 30 kg / cm ² and a temperature of around 100 ° C., which is not preferable from the viewpoint of work safety. Further, in the method in which oxygen is allowed to act in the presence of a transition metal catalyst such as chromium and manganese and aldehydes (JP-A-5-246914), both the conversion rate of indane and the selectivity to 1-indanone are low. It is hard to say that it is a practical method.
Accordingly, an object of the present invention is to provide a method for producing 1-indanones which eliminates the problems in the prior art.
[0005]
[Means for Solving the Problems]
As a result of repeated studies to solve the above-described problems of the prior art, the present inventor has reached the present invention.
That is, the present invention relates to indane in an organic solvent solution , or 1, 2, 3 position of the alicyclic ring of indane and 4, 5, 6, 7 position of benzene ring, methoxy group, chloro group, nitro group, methyl group and A compound having at least one substituent selected from phenyl groups (hereinafter referred to as “indanes”) is oxidized with oxygen or an oxygen-containing gas in the presence of a transition metal-bromine catalyst to give 1-indanone , or 1- A compound having at least one substituent selected from a methoxy group, a chloro group, a nitro group, a methyl group and a phenyl group at positions 1, 2, 3 of the alicyclic ring of indanone and positions 4, 5, 6, 7 of the benzene ring ( hereinafter in producing the as "1-indanones'), the indanes concentration of indanes solution was 20 wt% 5 wt% or more, the atomic ratio of Co / Mn of the transition metal catalyst And 4 above, to provide a production method of 1-indanones, which comprises adjusting the reaction temperature to 15 ℃ above 30 ° C. or less.
[0006]
According to the method of the present invention, the conversion rate of indans as raw materials can be improved, while the by-products of 1-indanols can be reduced, and 1-indanones can be produced in high yield.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail with reference to preferred embodiments.
The indan used as a raw material in the present invention is indane or a substituted derivative thereof. A substituted derivative of indane is a compound having a substituent in at least one of 1, 2, 3 position of indane alicyclic ring and 4, 5, 6, 7 position of benzene ring, specifically 1-methoxyindane. , 1,2-indane, 3,4-dimethoxy indane, 4- chloroindan, 4-nitroindan, 1-methyl indane, and 2-methyl-indan and 2-phenyl inductor emissions.
[0008]
In the present invention, indans are oxidized in an organic solvent. As the organic solvent to be used, a known lower fatty acid having 1 to 6 carbon atoms is preferably used. For example, the fatty acid having 1 to 6 carbon atoms, specifically, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, etc. caprylic acid, and can be mixtures thereof, Substantially acetic acid is preferably used.
[0009]
The indane concentration of the raw material indans solution is 5% by weight to 20% by weight, more preferably 5% by weight to 10% by weight as the lower fatty acid solution. When the concentration of indans exceeds 20% by weight, not only the conversion rate of indans decreases, but also the byproduct of 1-indanols becomes prominent. On the other hand, if it is less than 5% by weight, the production efficiency of 1-indanones decreases, which is not preferable.
[0010]
The transition metal-bromine catalyst used in the present invention may be a known one used industrially. Specifically, it is soluble in indane solutions such as acetates, nitrates, etc. of transition metals such as cobalt, manganese, cerium, etc. Cobalt compounds and manganese compounds are essential, and one or more other combinations are used. It is preferable to use one.
[0011]
The use ratio of the cobalt compound and the manganese compound is preferably 4 or more as Co / Mn (atomic ratio). When Co / Mn is less than 4, the oxidation reaction further proceeds, the bond of the alicyclic portion of the indane skeleton is cleaved, and the production of carboxylic acid derivatives increases, which is not preferable. The amount of the transition metal salt used is 0.1 mol or less, preferably 0.03 mol or more and 0.07 mol or less as the total number of moles of the transition metal salt per 1 mol of indane as a raw material.
[0012]
The bromine compound constituting the catalyst system can be exemplified by sodium bromide, ammonium bromide and the like as those capable of supplying bromine ions, but the amount used is from 0.5 as bromine / transition metal (atomic ratio). It should be 2.0. If the amount of bromine is too small, the reaction rate decreases.
[0013]
The reaction temperature is maintained at 15 ° C to 30 ° C, particularly preferably 20 ° C to 25 ° C. When the reaction temperature exceeds 30 ° C., the alicyclic portion of the indanes is cleaved to generate a carboxylic acid derivative, or the indanes that are the raw materials are promoted to be heavy, and the reaction selectivity is lowered. When the liquid temperature rises due to the oxidation reaction, it is desirable to maintain the reaction liquid at a predetermined temperature by cooling. The reaction time varies depending on the reaction temperature, but is about 1 to 50 hours in the above reaction temperature range.
[0014]
As the molecular oxygen-containing gas used as the oxidizing agent, pure oxygen, air, and other oxygen-containing exhaust gases can be used, but there is no problem with ordinary air. The reaction mode of the present invention can be either batch or continuous. Separation and purification of the target 1-indanones from the reaction product can be easily carried out by applying known methods such as distillation and recrystallization.
[0015]
【Example】
EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited at all by this.
Example 1
To a 100 ml flask equipped with a stirrer, thermometer, gas blowing tube and reflux condenser, 12.0 g of indane (purity 98.0%, 0.1 mol), 1.35 g of cobalt acetate (II) tetrahydrate ( 5.4 mmol), 0.15 g (0.6 mmol) of manganese (II) acetate tetrahydrate, 0.91 g (8.8 mmol) of sodium bromide and 90.4 g of acetic acid, and 100 ml of air per minute. The mixture was allowed to react at a reaction temperature of 20 ° C. for 12 hours. After completion of the reaction, this reaction solution was analyzed by gas chromatography. The indan conversion was 98.2% and 1-indanone selectivity was 85.7%. 1-indanone / 1-indanol (molar ratio) was 11.3.
[0016]
Example 2
The same procedure as in Example 1 was performed except that 1.23 g (12 mmol) of sodium bromide was used. The results are shown in Table 1.
[0017]
Example 3
As catalysts, cobalt (II) acetate tetrahydrate 0.90 g (3.6 mmol), manganese (II) acetate tetrahydrate 0.10 g (0.4 mmol) and sodium bromide 0.82 g (8 mmol). ) Was used in the same manner as in Example 1 except that. The results are shown in Table 1.
[0018]
Example 4
As catalysts, 1.44 g (5.8 mmol) of cobalt (II) acetate tetrahydrate, 0.05 g (0.2 mmol) of manganese (II) acetate tetrahydrate and 1.23 g (12 mmol) of sodium bromide. ) The procedure was the same as in Example 1 except that it was used. The results are shown in Table 1.
[0019]
Example 5
As catalysts, 1.39 g (5.6 mmol) of cobalt (II) acetate tetrahydrate, 0.10 g (0.42 mmol) of manganese (II) acetate tetrahydrate and 1.23 g (12 mmol) of sodium bromide. ) The procedure was the same as in Example 1 except that it was used. The results are shown in Table 1.
[0020]
Example 6
As catalysts, 1.27 g (5.1 mmol) of cobalt (II) acetate tetrahydrate, 0.22 g (0.9 mmol) of manganese (II) acetate tetrahydrate and 1.23 g (12 mmol) of sodium bromide. ) The procedure was the same as in Example 1 except that it was used. The results are shown in Table 1.
[0021]
Example 7
As catalysts, 1.20 g (4.8 mmol) of cobalt (II) acetate tetrahydrate, 0.29 g (1.2 mmol) of manganese (II) acetate tetrahydrate and 1.23 g (12 mmol) of sodium bromide. ) The procedure was the same as in Example 1 except that it was used. The results are shown in Table 1.
[0022]
Example 8
The reaction was performed in the same manner as in Example 7 except that the reaction temperature was 15 ° C. The results are shown in Table 1.
[0023]
Example 9
7.5 g of indane (purity 98.0%, 0.062 mol), 0.82 g (3.3 mmol) of cobalt (II) acetate tetrahydrate, 0.09 g (0) of manganese (II) acetate tetrahydrate .37 mmol) and 0.76 g (7.4 mmol) of sodium bromide were used. The results are shown in Table 1.
[0024]
Example 10
Indane 15.3 g (purity 98.0%, 0.127 mol), cobalt (II) acetate tetrahydrate 1.69 g (6.8 mmol), manganese (II) acetate tetrahydrate 0.19 g (0 .76 mmol) and 1.56 g (15.2 mmol) of sodium bromide were used. The results are shown in Table 1.
[0025]
Example 11
The reaction was performed in the same manner as in Example 2 except that the reaction temperature was 30 ° C. The results are shown in Table 1.
Example 12
The reaction was performed in the same manner as in Example 2 except that the reaction time was 8 hours. The results are shown in Table 1.
[0026]
Example 13
The reaction was performed in the same manner as in Example 2 except that the reaction time was 24 hours. The results are shown in Table 1.
Example 14
The same procedure as in Example 2 was performed, except that 13.6 g of 2-methylindane (purity 97%, 0.1 mol) was used as the indanes. The results are shown in Table 1.
[0027]
Example 15
The same procedure as in Example 2 was carried out except that 20.2 g of 2-phenylindane (purity 96%, 0.1 mol) was used as the indan and 148 g of acetic acid was used. The results are shown in Table 1.
Example 16
The same procedure as in Example 2 was performed, except that 15.3 g of 1-methoxyindane (purity 97%, 0.1 mol) was used as the indan and 112 g of acetic acid was used. The results are shown in Table 1.
[0028]
Example 17
The same procedure as in Example 2 was performed, except that 18.6 g (purity 96%, 0.1 mol) of 5,6-dimethoxyindane was used as indanes, and 130 g of acetic acid was used. The results are shown in Table 1.
Example 18
The same procedure as in Example 2 was carried out except that 1.18 g (5.4 mmol) of cobalt (II) bromide was used as the cobalt-bromine compound. The results are shown in Table 1.
[0029]
Example 19
The same procedure as in Example 2 was performed, except that 1.58 g (5.4 mmol) of cobalt (II) acetylacetonate dihydrate was used as the cobalt compound. The results are shown in Table 1.
Example 20
As the cobalt compound, 1.58 g (5.4 mmol) of cobalt (II) acetylacetonate dihydrate and 0.17 g (0.6 mmol) of manganese (II) acetylacetonate dihydrate as the manganese compound were used. Except for this, the procedure was the same as in Example 2. The results are shown in Table 1.
[0030]
Comparative Example 1
Indan 25.0 g (purity 98.0%, 0.212 mol), cobalt acetate (II) tetrahydrate 2.84 g (11.4 mmol), manganese acetate (II) tetrahydrate 0.31 g (1 .3 mmol) and 2.62 g (25.4 mmol) of sodium bromide were used. The results are shown in Table 1.
Comparative Example 2
The reaction was performed in the same manner as in Example 2 except that the reaction temperature was 60 ° C. The results are shown in Table 1.
[0031]
Comparative Example 3
Performed in the same manner as in Example 2 except that 0.75 g (3 mmol) of cobalt (II) acetate tetrahydrate and 0.74 g (3 mmol) of manganese (II) acetate tetrahydrate were used as catalysts. It was. The results are shown in Table 1.
[0032]

[0033]

[0034]

[0035]

[0036]
【The invention's effect】
According to the method of the present invention, the concentration of indanes and the amount of catalyst used in a solution of indans as a raw material are defined, and the indanes are oxidized under mild conditions. -Since indanones can be obtained, 1-indanones can be produced inexpensively and on an industrial scale.

Claims (2)

At least one selected from methoxy, chloro, nitro, methyl, and phenyl groups at the 1,2,3 positions of the indane in the organic solvent solution, and the 4, 5, 6, 7 positions of the benzene ring A compound having one substituent (hereinafter referred to as “indanes”) is oxidized with oxygen or an oxygen-containing gas in the presence of a transition metal-bromine catalyst and 1-indanone or 1-indanone alicyclic ring 1 Compounds having at least one substituent selected from a methoxy group, a chloro group, a nitro group, a methyl group and a phenyl group at the 2, 3, 3 position and the 4, 5, 6, 7 position of the benzene ring (hereinafter referred to as “1-indanones”) in producing a "hereinafter), the indanes concentration of indanes solution and 5 to 20% by weight, and the atomic ratio of Co / Mn of the transition metal catalyst 4 or more, the reaction temperature Method for producing a 1-indanones, characterized in that to adjust to 15 ℃ above 30 ° C. or less. The method for producing 1-indanes according to claim 1, wherein a lower fatty acid having 1 to 6 carbon atoms is used as the organic solvent.