CN101544554B - Preparation of alpha-tetralone by two-step catalysis method - Google Patents
Preparation of alpha-tetralone by two-step catalysis method Download PDFInfo
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- CN101544554B CN101544554B CN2008100308943A CN200810030894A CN101544554B CN 101544554 B CN101544554 B CN 101544554B CN 2008100308943 A CN2008100308943 A CN 2008100308943A CN 200810030894 A CN200810030894 A CN 200810030894A CN 101544554 B CN101544554 B CN 101544554B
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- Prior art keywords
- naphthane
- tetralone
- alpha
- transition metal
- metalloporphyrin
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Abstract
The invention discloses a novel method for preparing alpha-tetralone by using tetrahydronaphthalene as a raw material. The method comprises the following two steps: a first step, under the condition without solvent and assistant, 1 to 20 atm (absolute pressure) of air or oxygen or mixed gas of oxygen and inert gases is introduced, the reaction temperature is between 60 and 150 DEG C, monometallicporphyrin of general formula (I) or (II) and mu-O-bimetallic porphyrin or solid carriers thereof are used as a catalyst, the concentration of the catalyst is 1 to 80 ppm, the reaction time is 1 to 12hours, and oxidized mixed solution containing high alpha-tetrahydronaphthalene peroxide and alpha-tetralone can be selectively obtained; and a second step, the alpha-tetrahydronaphthalene peroxide inthe oxidized mixed solution obtained in the first step is high selectively and directionally decomposed into the alpha-tetralone by using transition metal salt as a catalyst. In the step of catalyticdecomposition, the molar ratio of transition metal irons to the alpha-tetrahydronaphthalene peroxide is 1:1-100, and the reaction temperature is between 0 and 100 DEG C. The method has the advantagesof short reaction time, mild reaction conditions, little using amount of the catalyst, high conversion rate and good selectivity of a target product; and the used catalyst is environment-friendly andhas no corrosion to equipment.
Description
(1) technical field
The present invention relates to the method that a kind of two-stage catalysis legal system is equipped with α-Tetralone an intermediate of Sertraline.The first step is under catalysis of metalloporphyrin, and naphthane is α-naphthane hydrogen peroxide and α-Tetralone an intermediate of Sertraline by the air or oxygen selective oxidation; α-naphthane hydrogen peroxide that second step utilized the transition metal ion catalytic decomposition the first step to produce, thus highly selective is prepared α-Tetralone an intermediate of Sertraline.
(2) background technology
α-Tetralone an intermediate of Sertraline is the important intermediate of many pharmaceutical production, and industrial main employing at present is a Primary Catalysts with the chromic salts, is the production technique of cocatalyst catalytic air oxidation naphthane with the pyridine compounds and their.The main and auxiliary catalyst consumption of this kind technology is big, cost is high; And chromic salts is poisonous, is difficult for separating polluted product and environment from product.Except that α-Tetralone an intermediate of Sertraline, also contain a large amount of α-naphthane hydrogen peroxide and α-naphthane alcohol in the oxidation products of molecular oxygen oxidation naphthane, the selectivity of α-Tetralone an intermediate of Sertraline is not high.Wherein α-naphthane alcohol has very big disadvantageous effect to the follow-up use of α-Tetralone an intermediate of Sertraline, and the boiling point of the pure and mild α-Tetralone an intermediate of Sertraline of α-naphthane is very approaching, is difficult to separate.U.S. Pat 4,175,098 has reported in the DMF solvent, with chromic salts and N, N-dialkyl amide compounds catalyzed oxidation α-naphthane prepares the method for α-Tetralone an intermediate of Sertraline; This method will be used solvent, and catalyzer is poisonous and consumption is big, cost is high.U.S. Pat 4,283,352 have reported that a kind of non-catalyst oxidation prepares the technology of α-Tetralone an intermediate of Sertraline; The oxidising process of this method is not used catalyzer, makes the reaction times very long, and the keto-alcohol of products therefrom is higher than not.
(3) summary of the invention
The object of the present invention is to provide a kind of reaction times short, catalyst levels is few, pollution-free, the novel method of preparation α-Tetralone an intermediate of Sertraline that target product selectivity is high.
Technical scheme of the present invention: reaction divided for two steps carried out.The first step, feeding under the 1-20atm air conditions, temperature of reaction is 60-150 ℃, select for use by the monometallic porphyrin of general formula (I) or general formula (II) μ-oxygen bimetallic porphyrin or above-mentioned metalloporphyrin and inorganic or immobilized thing that organic polymer constitutes separately as catalyzer, catalyst concn is 1-80ppm.Metalloporphyrin can be efficient as biological enzyme under biological concentration, highly selective catalytic air or dioxygen oxidation naphthane, the naphthane transformation efficiency is more than 30%, the selectivity of α-naphthane hydrogen peroxide is more than 90%, and the overall selectivity of α-naphthane hydrogen peroxide and α-Tetralone an intermediate of Sertraline is more than 95%.Second step, the oxidation liquid that obtains with abovementioned steps is reactant, in temperature of reaction is under the 0-100 ℃ of condition, the salt of selecting transition-containing metal ion for use is catalyzer, control wherein α-naphthane hydrogen peroxide and the mol ratio of transition metal ion be 1-100: 1 scope, then the α in the oxidation liquid-naphthane hydrogen peroxide is by directed fully decomposition, and the overall selectivity of α-Tetralone an intermediate of Sertraline reaches more than 94% in the degradation production.
General formula (I)
General formula (II)
Atoms metal M, M in the above-mentioned metal porphyrins structure
1Or M
2Can be transition metal atoms or lanthanide series metal atom; Substituent R on the phenyl ring
1, R
2Or R
3Can be hydrogen, alkyl, alkoxyl group, halogen, matrix, amino, glycosyl, replacement glycosyl or cyclodextrin.Dentate X can be compounds such as acetate, acetate acetone, halogen or pyridine.
Naphthane oxide catalyst among the present invention can be one or more of above-mentioned metalloporphyrin.Also can be above-mentioned metalloporphyrin and supported metalloporphyrin inorganic and that organic polymer constitutes by physics or chemical process; The carrier that constitutes the supported metalloporphyrin catalyzer with above-mentioned metalloporphyrin has: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, titanium dioxide, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene etc.
The catalyzer that decomposes as oxidation liquid among the present invention is the transition metal salt of Fe, Cu, Zn, Co, Mn and Ni etc., can be one or more of these transition metal salts.
(4) embodiment
Embodiment 1:
The metalloporphyrin that will have general formula (I) structure dissolves in the 50ml naphthane, and the concentration of metalloporphyrin is 14.75ppm, R
1=Cl, R
2=R
3=H, M=Fe, X=Cl. is with the gas speed bubbling air of 300ml/min.Reacted 8 hours down at 90 ℃, the transformation efficiency of naphthane is 15.32%, and α-naphthane hydrogen peroxide selectivity is 89.88%, and the overall selectivity of α-naphthane hydrogen peroxide and α-Tetralone an intermediate of Sertraline is 95.37%.Get oxidation liquid 24.40g, splash into 30ml FeSO
47H
2The aqueous solution of O (is dissolved with the FeSO of 0.86g
47H
2O), temperature in the ice-water bath control reaction process is about 0 ℃, stir down and dropwise drip, 30min dropwises, continue to stir 60min, after the decompress filter separating treatment, the α in the oxidation liquid-naphthane hydrogen peroxide almost completely is decomposed into α-Tetralone an intermediate of Sertraline, the overall selectivity 95.31% of α-Tetralone an intermediate of Sertraline.
Embodiment 2:
The metalloporphyrin that will have general formula (I) structure dissolves in the 50ml naphthane, and the concentration of metalloporphyrin is 14.75ppm, R
1=Cl, R
2=R
3=H, M=Co, X=Cl.With 300ml/min gas speed bubbling air, reacted 8 hours down at 90 ℃, the transformation efficiency of naphthane is 34.22%, and α-naphthane hydrogen peroxide selectivity is 83.36%, and the overall selectivity of α-naphthane hydrogen peroxide and α-Tetralone an intermediate of Sertraline is 95.40%.Get oxidation liquid 28.94g, splash into the aqueous solution (being dissolved with the CuCl of 0.36g) of 30ml CuCl, temperature in the ice-water bath control reaction process is about 0 ℃, stir down dropwise to go into, 30min dropwises, and continues to stir 60min, after the decompress filter separating treatment, α in the oxidation liquid-naphthane hydrogen peroxide almost completely is decomposed into α-Tetralone an intermediate of Sertraline, the overall selectivity 94.66% of α-Tetralone an intermediate of Sertraline.
Embodiment 3:
The metalloporphyrin that will have general formula (I) structure dissolves in the 50ml naphthane, and the concentration of metalloporphyrin is 29.50ppm, R
1=Cl, R
2=R
3=H, M=Co, X=Cl.With 300ml/min gas speed bubbling air, reacted 4 hours down at 90 ℃, the transformation efficiency of naphthane is 25.02%, and α-naphthane hydrogen peroxide selectivity is 83.09%, and the overall selectivity of α-naphthane hydrogen peroxide and α-Tetralone an intermediate of Sertraline is 94.27%.Get oxidation liquid 25.00g, splash into the FeSO of 30ml
47H
2The O aqueous solution (is dissolved with the FeSO of 0.9g
47H
2O), temperature in the ice-water bath control reaction process is about 0 ℃, stir down dropwise to go into, 30min dropwises, continue to stir 60min, after the decompress filter separating treatment, the α in the oxidation liquid-naphthane hydrogen peroxide almost completely is decomposed into α-Tetralone an intermediate of Sertraline, the overall selectivity 94.26% of α-Tetralone an intermediate of Sertraline.
Embodiment 4:
The metalloporphyrin that will have general formula (I) structure dissolves in the 50ml naphthane, and the concentration of metalloporphyrin is 14.75ppm, R
1=Cl, R
2=R
3=H, M=Co, X=Cl.With 300ml/min gas speed bubbling air, reacted 4 hours down at 100 ℃, the transformation efficiency of naphthane is 30.27%, and α-naphthane hydrogen peroxide selectivity is 78.51%, and the overall selectivity of α-naphthane hydrogen peroxide and α-Tetralone an intermediate of Sertraline is 94.56%.Get oxidation liquid 25.00g, splash into the aqueous solution aqueous solution (being dissolved with the CuCl of 0.51g) of the CuCl of 30ml, temperature in the ice-water bath control reaction process is about 0 ℃, stir down dropwise to go into, 30min dropwises, and continues to stir 60min, after the decompress filter separating treatment, α in the oxidation liquid-naphthane hydrogen peroxide almost completely is decomposed into α-Tetralone an intermediate of Sertraline, the overall selectivity 94.43% of α-Tetralone an intermediate of Sertraline.
Embodiment 5:
The metalloporphyrin that will have general formula (II) structure dissolves in the 50ml naphthane, and the concentration of metalloporphyrin is 14.50ppm, R
1=Cl, R
2=R
3=H, M=Mn.With 300ml/min gas speed bubbling air, reacted 3 hours down at 100 ℃, the transformation efficiency of naphthane is 28.20%, and α-naphthane hydrogen peroxide selectivity is 81.42%, and the overall selectivity of α-naphthane hydrogen peroxide and α-Tetralone an intermediate of Sertraline is 95.37%.Get oxidation liquid 25.00g, splash into the FeSO of 30ml
47H
2The O aqueous solution (is dissolved with the FeSO of 0.92g
47H
2O), temperature in the ice-water bath control reaction process is about 0 ℃, stir down dropwise to go into, 30min dropwises, continue to stir 60min, after the decompress filter separating treatment, the α in the oxidation liquid-naphthane hydrogen peroxide almost completely is decomposed into α-Tetralone an intermediate of Sertraline, the overall selectivity 94.79% of α-Tetralone an intermediate of Sertraline.
Embodiment 6:
With the metalloporphyrin that supported on silica-gel 0.5mg has general formula (I) structure, R
1=Cl, R
2=R
3=H, M=Mn, X=Cl, add in the 50ml naphthane, with 300ml/min gas speed bubbling air, reacted 8 hours down at 90 ℃, the transformation efficiency of naphthane is 25.20%, α-naphthane hydrogen peroxide selectivity is 87.53%, and the overall selectivity of α-naphthane hydrogen peroxide and α-Tetralone an intermediate of Sertraline is 96.67%.Get oxidation liquid 29.05g, splash into the FeSO of 30ml
47H
2The mixture aqueous solution of O and CuCl (is dissolved with the FeSO of 0.45g
47H
2The CuCl of O and 0.35g), temperature in the ice-water bath control reaction process is about 0 ℃, stir down dropwise to go into, 30min dropwises, continue to stir 60min, after the decompress filter separating treatment, the α in the oxidation liquid-naphthane hydrogen peroxide almost completely is decomposed into α-Tetralone an intermediate of Sertraline, the overall selectivity 96.29% of α-Tetralone an intermediate of Sertraline.
Claims (4)
1. catalytic air or dioxygen oxidation naphthane prepare the method for α-Tetralone an intermediate of Sertraline, it is characterized in that: the first step, with the naphthane is raw material, under the condition of solvent-free no auxiliary agent, feed the air or oxygen of absolute pressure 0.1-2MPa, temperature of reaction is 60-150 ℃, selects for use by the monometallic porphyrin of general formula (I) or general formula (II) μ-oxygen bimetallic porphyrin or their immobilized thing as catalyzer, catalyst consumption is 1-80ppm, M, M in metalloporphyrin (I), (II) structure
1Or M
2Be transition metal atoms, substituent R on the phenyl ring
1, R
2Or R
3Be hydrogen, halogen, dentate X is a halogen; Second step, oxidation liquid with above-mentioned the first step gained is raw material, under 0-100 ℃ of condition, adds transition metal ion again and makees catalyzer, decompose α-naphthane hydrogen peroxide wherein, the mol ratio of transition metal ion and contained α-naphthane hydrogen peroxide is 1: 1-100
2. method according to claim 1 is characterized in that: the reaction pressure of metalloporphyrin or its immobilized thing catalytic oxidation of tetralin is absolute pressure 0.1-1MPa, and temperature of reaction is 70-130 ℃.
3. method according to claim 1 is characterized in that: the temperature of transition metal ion catalytic decomposition oxidation liquid is 0-60 ℃, and the mol ratio of transition metal ion and contained α-naphthane hydrogen peroxide is 1: 1-50.
4. according to the described method of claim 1, it is characterized in that: metalloporphyrin can constitute supported metalloporphyrin with following carrier: silica gel, aluminum oxide, titanium dioxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, poly-peroxide ethene or polystyrene.
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| CN2008100308943A CN101544554B (en) | 2008-03-25 | 2008-03-25 | Preparation of alpha-tetralone by two-step catalysis method |
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|---|---|---|---|
| CN2008100308943A CN101544554B (en) | 2008-03-25 | 2008-03-25 | Preparation of alpha-tetralone by two-step catalysis method |
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| CN101544554B true CN101544554B (en) | 2011-12-28 |
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| CN106748689B (en) * | 2016-12-07 | 2019-06-25 | 中国科学院大连化学物理研究所 | A method of preparing α-tetralone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283352A (en) * | 1975-07-14 | 1981-08-11 | Kureha Kagaku Kogyo Kabushiki Kaisha | Method for the production of α-tetralone |
-
2008
- 2008-03-25 CN CN2008100308943A patent/CN101544554B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283352A (en) * | 1975-07-14 | 1981-08-11 | Kureha Kagaku Kogyo Kabushiki Kaisha | Method for the production of α-tetralone |
Non-Patent Citations (1)
| Title |
|---|
| YANG Wei-jun, et al..Preparation of p-menthane hydroperoxide from p-menthane in presence of metalloporphyrins.《J. Cent. South Univ. Technol.》.2007,第14卷(第5期),660-665. * |
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