CN101205225B - Method for preparing lactones by biomimetic catalytic oxidation of ketone compounds - Google Patents

Method for preparing lactones by biomimetic catalytic oxidation of ketone compounds Download PDF

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CN101205225B
CN101205225B CN2007100313260A CN200710031326A CN101205225B CN 101205225 B CN101205225 B CN 101205225B CN 2007100313260 A CN2007100313260 A CN 2007100313260A CN 200710031326 A CN200710031326 A CN 200710031326A CN 101205225 B CN101205225 B CN 101205225B
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ketone compounds
oxygen
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纪红兵
袁秋兰
周贤太
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South China University of Technology SCUT
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Abstract

The invention discloses a method for putting the oxydone compounds into the biomimetic catalysis to prepare the lactone. With the ketone compounds as the raw materials, the invention selects the mononuclear metalloporphyrins with structure in the general formulas (I) and (II) or Mu-oxygen-binuclear metalloporphyrins with structure in the general formula (III) as the catalysts; the concentration of the catalysts ranges from 2 multiplied by 10<-5>mol/L to 2 multiplied by 10<-2>mol/L and the concentration of the ketone compounds ranges from 0.02mol/L to 0.8mol/L; with the benzene, the toluene, the xylene, the benzotrifluoride or the cyclohexane as the solvents, the benzaldehyde, isobutyraldehyde or butyraldehyde with a molar ratio to the ketone compounds ranging from 0.5 to 1 to 20 to 1 is added in the mixtures; the oxygen with a pressure ranging from 0.1MPa to 1.6MPa is pumped in the mixtures; the reaction temperature is controlled to a range from 40 DEG C to 150 DEG C and the reaction time is controlled to a range from 1 to 10 hours. The invention has the advantages of gentile reaction conditions, a small dosage of catalysts, good catalytic effects, and high product selectivity, etc.

Description

A kind of method of preparing lactones by biomimetic catalytic oxidation of ketone compounds
Technical field
The present invention relates to a kind of preparation method of lactone compound, specifically, relating to a kind of is the method for the preparing lactones by biomimetic catalytic oxidation of ketone compounds of oxygenant with oxygen.
Background technology
Lactone is a kind of important organic synthesis intermediate, 1899, Baeyer and Villiger reported first utilize persulfuric acid to make oxygenant piperitone is changed into corresponding lactone, Baeyer-Villiger reaction after this is widely used in the organic synthesis.Preparing by the Baeyer-Villiger oxidizing reaction in the method for lactone at present, the oxygenant of employing all is organic peracid such as m-CPBA (metachloroperbenzoic acid), trifluoroperacetic acid, Peracetic Acid etc. usually.Use not only expense height but also can produce a large amount of objectionable impuritiess of these oxygenants, environment is polluted.
Therefore, preparing by the Baeyer-Villiger oxidizing reaction in the method research of lactone, the oxygen that adopts cleaning, safety is as oxygenant people's attention extremely.Tomonori etc. have reported that in 2005 a kind of is that oxygenant is in conjunction with the oxidation of auxiliary agent phenyl aldehyde to ketone with oxygen, it is catalyzer that reaction system is selected the doped meso-porous silicon-dioxide of iron for use, the highest yield of product can reach 77% in this method, but the reaction times need reach 15 hours, and catalyst preparation process complexity (Kawabata T, et al.J.Mol.Catal.A 2005,236,99-106).Their study group in 2006 has reported that again with the load iron hydrotalcite be catalyzer, the ketone oxidation system of combination with oxygen phenyl aldehyde.Though the good catalytic effect of this reactant cording, Preparation of Catalyst are comparatively complicated, and have used nitric acid (the Kawabata T that equipment is had severe corrosive in preparation process, et al.J.Mol.Catal.A 2006,253,279-289), there is the problem that environment is polluted.
Summary of the invention
The object of the invention is to provide that a kind of technology is simple, cost is low and environment amenable efficient catalytic dioxygen oxidation ketone compounds prepares the method for lactone.
For realizing purpose of the present invention, the technical scheme that is adopted is: be raw material with the ketone compounds, described ketone compounds is cyclic ketones class or derivatives thereof or many cyclic ketones class or straight chain ketone, select for use the monokaryon metalloporphyrin of general formula (I), (II) structure or the μ-oxygen-dinuclear metalloporphyrin of general formula (III) structure to make catalyzer, catalyst concn is 2 * 10 -5Mol/L～2 * 10 -2Mol/L, the concentration of raw ketone compounds is 0.02mol/L～0.8mol/L, with benzene or toluene or dimethylbenzene or phenylfluoroform or cyclohexane give solvent, adding and reactant molar ratio are 0.5: 1～20: 1 phenyl aldehyde or isobutyric aldehyde or butyraldehyde-n, feed the oxygen of 0.1～1.6MPa, control reaction temperature is 40～150 ℃, 1～10 hour reaction times.Among general formula (I), (II), (III), M 1, M 2, M 3Be transition metal atoms, M 1=Fe, Mn, Co, Cu, Zn, M 2=Fe, Mn, Co, Ru, M 3=Fe, Mn, R 1, R 2Can be hydrogen, halogen, nitro, hydroxyl, alkoxyl group, dentate X are chlorine,
Catalysis of metalloporphyrin agent described in the inventive method preferably has the monokaryon metalloporphyrin of general formula (II) structure or the μ-oxygen-dinuclear metalloporphyrin of general formula (III) structure.
Figure GSB00000553633300021
General formula (I) general formula (II)
Figure GSB00000553633300022
General formula (III)
The ketone compounds that is applicable to the inventive method is cyclic ketones class or many cyclic ketones class.
Catalyzer of the present invention is preferably the have general formula monokaryon metalloporphyrin of (II), wherein M 2=Ru, Fe or Mn, R 1=NO 2Or Cl, R 2=H, X=Cl.
Or catalyzer of the present invention is preferably the have general formula μ-oxygen-dinuclear metalloporphyrin of (III), wherein M 3=Fe or Mn, R 1=NO 2Or Cl, R 2=H.
The preferred oxygen pressure scope of the inventive method is 0.1～1.0MPa, and preferred temperature range is 40～100 ℃, preferred catalyst concn 2 * 10 -4Mol/L～2 * 10 -3Mol/L, the mol ratio of preferred phenyl aldehyde or isobutyric aldehyde or butyraldehyde-n and reactant is 3: 1～15: 1.
Ketone compounds oxidation provided by the present invention prepares the method for lactone, owing to used the metal porphyrins of biological enzyme similar to make catalyzer, thereby have the following advantages:
1. owing to simulated the biological activity of enzyme, make this reaction conditions gentleness, required temperature of reaction and pressure are all lower.
2. the high efficiency of analogue enztme and specificity make that the reaction times short, the selectivity of product height.
3. use oxygen as oxygenant, by product is a water, makes whole process cleaning, pollution-free and cost is low.
4. metal porphyrins is few as catalyst levels, and chemical property and reactant and resultant differ greatly, and makes that operation is simple, easily goes that post catalyst reaction separates with reaction system easily.
Embodiment
The invention will be further described below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
Contain 2 * 10 at 5mL -5Four of mol/L-(o-nitrophenyl) manganoporphyrin (is R in the general formula (I) 1=NO 2, R 2=H, M 1In=Mn) the toluene solution, add pimelinketone and the 0.05mmol phenyl aldehyde of 0.02mol/L, feed the oxygen of 0.1MPa, 40 ℃ of following reaction stirred 6 hours, the transformation efficiency of pimelinketone was 96%, and the yield of hexamethylene lactone is 96%.
Figure GSB00000553633300031
Embodiment 2
Contain 2 * 10 at 5mL -4Four of mol/L-(neighbour-chloro-phenyl-) iron porphyrin (is R in the general formula (I) 1=Cl, R 2=H, M 1In=Fe) the toluene solution, add 4-methylcyclohexanone and the 0.5mmol phenyl aldehyde of 0.1mol/L, feed the oxygen of 0.5MPa, 60 ℃ of following reaction stirred 6 hours, the transformation efficiency of 4-methylcyclohexanone was 90%, and the yield of 4-methyl cyclohexane lactone is 90%.
Figure GSB00000553633300041
Embodiment 3
Contain 2 * 10 at 5mL -3Four of mol/L-(neighbour-p-methoxy-phenyl) cobalt porphyrin (is R in the general formula (I) 1=OCH 3, R 2=H, M 1In=Co) the toluene solution, add 2-methylcyclohexanone and the 5mmol phenyl aldehyde of 0.5mol/L, feed the oxygen of 0.8MPa, 80 ℃ of following reaction stirred 2 hours, the transformation efficiency of 2-methylcyclohexanone was 85%, and the yield of 2-methyl cyclohexane lactone is 85%.
Figure GSB00000553633300042
Embodiment 4
Contain 2 * 10 at 5mL -3Four of mol/L-(right-aminomethyl phenyl) zinc protoporphyrin (is R in the general formula (I) 1=H, R 2=CH 3, M 1In=Zn) the xylene solution, add pimelinketone and the 40mmol phenyl aldehyde of 0.8mol/L, feed the oxygen of 1.2MPa, 80 ℃ of following reaction stirred 8 hours, the transformation efficiency of pimelinketone was 86%, and the yield of hexamethylene lactone is 86%.
Embodiment 5
Contain 2 * 10 at 5mL -2Four of mol/L-(right-nitrophenyl) iron porphyrin (is R in the general formula (I) 1=H, R 2=NO 2, M 1In=Fe) the xylene solution, add cyclopentanone and the 15mmol phenyl aldehyde of 0.2mol/L, feed the oxygen of 1.6MPa, 120 ℃ of following reaction stirred 6 hours, the transformation efficiency of cyclopentanone was 82%, and the yield of ring valerolactone is 82%.
Figure GSB00000553633300051
Embodiment 6
Contain 2 * 10 at 5mL -3The tetraphenylarsonium chloride base iron porphyrin of mol/L (is R in the general formula (II) 1=H, R 2=H, M 2=Fe in phenylfluoroform solution X=Cl), adds 3-tertiary butyl pimelinketone and the 20mmol phenyl aldehyde of 0.2mol/L, feed the oxygen of 1.0MPa, 150 ℃ of following reaction stirred 6 hours, the transformation efficiency of 3-tertiary butyl pimelinketone was 93%, and the yield of 3-tertiary butyl hexamethylene lactone is 93%.
Figure GSB00000553633300052
Embodiment 7
Contain 2 * 10 at 5mL -3The tetraphenylarsonium chloride base ruthenium porphyrin of mol/L (is R in the general formula (II) 1=H, R 2=H, M 2=Ru in toluene solution X=Cl), adds methyln-hexyl ketone and the 10mmol phenyl aldehyde of 0.2mol/L, feeds the oxygen of 1.2MPa, and 80 ℃ of following reaction stirred 10 hours, the transformation efficiency of methyln-hexyl ketone was 79%, and the yield of hexyl acetate is 79%.
Figure GSB00000553633300053
Embodiment 8
Contain 2 * 10 at 5mL -3The tetraphenylarsonium chloride base ruthenium porphyrin of mol/L (is R in the general formula (II) 1=H, R 2=H, M 2=Ru in cyclohexane solution X=Cl), adds pimelinketone and the 15mmol phenyl aldehyde of 0.2mol/L, feeds the oxygen of 0.8MPa, and 80 ℃ of following reaction stirred 8 hours, the transformation efficiency of pimelinketone was 84%, and the yield of hexamethylene lactone is 84%.
Figure GSB00000553633300061
Embodiment 9
Contain 2 * 10 at 5mL -3The chlorination four of mol/L-(o-nitrophenyl) iron porphyrin (is R in the general formula (II) 1=NO 2, R 2=H, M 2=Fe in benzole soln X=Cl), adds 2-methylcyclohexanone and the 15mmol phenyl aldehyde of 0.2mol/L, feeds the oxygen of 0.2MPa, and 80 ℃ of following reaction stirred 5 hours, the transformation efficiency of 2-methylcyclohexanone was 98%, and the yield of 2-methyl cyclohexane lactone is 98%.
Figure GSB00000553633300062
Embodiment 10
Contain 2 * 10 at 5mL -2The chlorination four of mol/L-(o-nitrophenyl) manganoporphyrin (is R in the general formula (II) 1=NO 2, R 2=H, M 2=Mn in phenylfluoroform solution X=Cl), adds cyclopentanone and the 15mmol isobutyric aldehyde of 0.2mol/L, feeds the oxygen of 0.5MPa, and 60 ℃ of following reaction stirred 6 hours, the transformation efficiency of cyclopentanone was 80%, and the yield of ring valerolactone is 80%.
Embodiment 11
Contain 2 * 10 at 5mL -2The chlorination four of mol/L-(o-nitrophenyl) manganoporphyrin (is R in the general formula (II) 1=NO 2, R 2=H, M 2=Mn in phenylfluoroform solution X=Cl), adds 3-tertiary butyl pimelinketone and the 15mmol phenyl aldehyde of 0.4mol/L, feed the oxygen of 0.4MPa, 80 ℃ of following reaction stirred 4 hours, the transformation efficiency of 3-tertiary butyl pimelinketone was 98%, and the yield of 3-tertiary butyl hexamethylene lactone is 98%.
Figure GSB00000553633300071
Embodiment 12
Contain 2 * 10 at 5mL -3The chlorination four of mol/L-(neighbour-aminomethyl phenyl) ruthenium porphyrin (is R in the general formula (II) 1=CH 3, R 2=H, M 2=Ru in phenylfluoroform solution X=Cl), adds 2-Buddha's warrior attendant ketone and the 15mmol phenyl aldehyde of 0.2mol/L, feeds the oxygen of 0.2MPa, and 80 ℃ of following reaction stirred 8 hours, the transformation efficiency of 2-Buddha's warrior attendant ketone was 95%, and the yield of 2-Buddha's warrior attendant lactone is 95%.
Figure GSB00000553633300072
Embodiment 13
Contain 2 * 10 at 5mL -3The chlorination four of mol/L-(right-p-methoxy-phenyl) manganoporphyrin (is R in the general formula (II) 1=H, R 2=OCH 3, M 2=Mn in phenylfluoroform solution X=Cl), adds 3-hexanone and the 12mmol phenyl aldehyde of 0.2mol/L, feeds the oxygen of 1.5MPa, and 80 ℃ of following reaction stirred 10 hours, the transformation efficiency of pimelinketone was 75%, and the yield of propyl propionate is 75%.
Figure GSB00000553633300073
Embodiment 14
Contain 2 * 10 at 5mL -3The chlorination four of mol/L-(neighbour-p-methoxy-phenyl) cobalt porphyrin (is R in the general formula (II) 1=OCH 3, R 2=H, M 2=Co in toluene solution X=Cl), adds benzophenone and the 15mmol phenyl aldehyde of 0.2mol/L, feeds the oxygen of 0.4MPa, and 70 ℃ of following reaction stirred 6 hours, the transformation efficiency of benzophenone was 78%, and the yield of phenol benzoate is 78%.
Figure GSB00000553633300081
Embodiment 15
Contain 2 * 10 at 5mL -3The tetraphenylarsonium chloride base iron porphyrin of mol/L (is R in the general formula (II) 1=H, R 2=H, M 2=Fe in phenylfluoroform solution X=Cl), adds 3-methylcyclohexanone and the 15mmol butyraldehyde-n of 0.2mol/L, feed the oxygen of 0.5MPa, 60 ℃ of following reaction stirred 8 hours, the transformation efficiency of 3-methylcyclohexanone was 96%, and the yield of 3-methylcyclohexanone lactone is 96%.
Figure GSB00000553633300082
Embodiment 16
Contain 2 * 10 at 5mL -4μ-oxygen of mol/L-double-core four-(neighbour-chloro-phenyl-) manganoporphyrin (is R in the general formula (III) 1=Cl, R 2=H, M 3In=Mn) the toluene solution, add pimelinketone and the 15mmol butyraldehyde-n of 0.2mol/L, feed the oxygen of 0.1MPa, 70 ℃ of following reaction stirred 6 hours, the transformation efficiency of pimelinketone was 94%, and the yield of hexamethylene lactone is 94%.
Figure GSB00000553633300083
Embodiment 17
Contain 2 * 10 at 5mL -3μ-oxygen of mol/L-double-core four-(o-nitrophenyl) iron porphyrin (is R in the general formula (III) 1=NO 2, R 2=H, M 3In=Fe) the phenylfluoroform solution, add 2-methylcyclohexanone and the 10mmol phenyl aldehyde of 0.1mol/L, feed the oxygen of 0.8MPa, 60 ℃ of following reaction stirred 8 hours, the transformation efficiency of 2-methylcyclohexanone was 97%, and the yield of hexamethylene lactone is 97%.
Figure GSB00000553633300091
Embodiment 18
Contain 2 * 10 at 5mL -4μ-oxygen of mol/L-double-core tetraphenyl iron porphyrin (is R in the general formula (III) 1=H, R 2=H, M 3In=Fe) the phenylfluoroform solution, add methyln-hexyl ketone and the 10mmol phenyl aldehyde of 0.1mol/L, feed the oxygen of 1.0MPa, 100 ℃ of following reaction stirred 8 hours, the transformation efficiency of pimelinketone was 83%, and the yield of hexyl acetate is 83%.
Figure GSB00000553633300092
Embodiment 19
Contain 2 * 10 at 5mL -3μ-oxygen of mol/L-double-core tetraphenyl manganoporphyrin (is R in the general formula (III) 1=H, R 2=H, M 3In=Mn) the toluene solution, add benzophenone and the 15mmol phenyl aldehyde of 0.2mol/L, feed the oxygen of 0.4MPa, 70 ℃ of following reaction stirred 6 hours, the transformation efficiency of pimelinketone was 84%, and the yield of phenol benzoate is 84%.
Figure GSB00000553633300093
Embodiment 20
Contain 2 * 10 at 5mL -3μ-oxygen of mol/L-double-core four-(neighbour-chloro-phenyl-) iron porphyrin (is R in the general formula (III) 1=Cl, R 2=H, M 3In=Fe) the xylene solution, add 2-Buddha's warrior attendant ketone and the 18mmol phenyl aldehyde of 0.2mol/L, feed the oxygen of 0.1MPa, 60 ℃ of following reaction stirred 8 hours, the transformation efficiency of 2-Buddha's warrior attendant ketone was 94%, and the yield of 2-Buddha's warrior attendant lactone is 94%.
Figure GSB00000553633300101
Embodiment 21
Contain 2 * 10 at 5mL -3μ-oxygen of mol/L-double-core four-(o-nitrophenyl) manganoporphyrin (is R in the general formula (III) 1=NO 2, R 2=H, M 3In=Mn) the phenylfluoroform solution, add 3-hexanone and the 15mmol phenyl aldehyde of 0.2mol/L, feed the oxygen of 1.5MPa, 80 ℃ of following reaction stirred 10 hours, the transformation efficiency of 3-hexanone was 82%, and the yield of propyl propionate is 82%.
Figure GSB00000553633300102
Embodiment 22
Contain 2 * 10 at 5mL -3μ-oxygen of mol/L-double-core four-(neighbour-chloro-phenyl-) iron porphyrin (is R in the general formula (III) 1=Cl, R 2=H, M 3In=Fe) the toluene solution, add pimelinketone and the 12mmol phenyl aldehyde of 0.2mol/L, feed the oxygen of 0.5MPa, 60 ℃ of following reaction stirred 6 hours, the transformation efficiency of pimelinketone was 95%, and the yield of hexamethylene lactone is 95%.

Claims (7)

1. the method for a preparing lactones by biomimetic catalytic oxidation of ketone compounds, it is characterized in that with the ketone compounds being raw material, select for use the monokaryon metalloporphyrin of general formula (I), (II) structure or the μ-oxygen-dinuclear metalloporphyrin of general formula (III) structure to make catalyzer, catalyst concn is 2 * 10 -5Mol/L～2 * 10 -2Mol/L, described ketone compounds is cyclic ketones class or many cyclic ketones class, its concentration is 0.02～0.8mol/L, with benzene,toluene,xylene, phenylfluoroform or cyclohexane give solvent, adding and ketone compounds mol ratio are 0.5: 1～20: 1 phenyl aldehyde, isobutyric aldehyde or butyraldehyde-n, feed the oxygen of 0.1～1.6MPa, control reaction temperature is 40～150 ℃, 1～10 hour reaction times;
Figure FA20189524200710031326001C00011
Among general formula (I), (II), (III), M 1, M 2, M 3Be transition metal atoms, wherein, M 1=Fe, Mn, Co, Cu, Zn; M 2=Fe, Mn, Co, Ru; M 3=Fe, Mn, R 1, R 2Be hydrogen, halogen, nitro, hydroxyl or alkoxyl group; Dentate X is a chlorine.
2. the method for preparing lactones by biomimetic catalytic oxidation of ketone compounds according to claim 1 is characterized in that described catalyzer is for having the monokaryon metalloporphyrin of general formula (II), wherein M 2=Ru, Fe or Mn, R 1=NO 2Or Cl, R 2=H, X=Cl.
3. the method for preparing lactones by biomimetic catalytic oxidation of ketone compounds according to claim 1 is characterized in that described catalyzer is for having μ-oxygen-dinuclear metalloporphyrin of general formula (III), wherein M 3=Fe or Mn, R 1=NO 2Or Cl, R 2=H.
4. the method for preparing lactones by biomimetic catalytic oxidation of ketone compounds according to claim 1 is characterized in that described oxygen pressure is 0.1～1.0MPa.
5. the method for preparing lactones by biomimetic catalytic oxidation of ketone compounds according to claim 1 is characterized in that described temperature is 40～100 ℃.
6. the method for preparing lactones by biomimetic catalytic oxidation of ketone compounds according to claim 1 is characterized in that described catalyst concn is 2 * 10 -4Mol/L～2 * 10 -3Mol/L.
7. the method for preparing lactones by biomimetic catalytic oxidation of ketone compounds according to claim 1, the mol ratio that it is characterized in that described phenyl aldehyde or isobutyric aldehyde or butyraldehyde-n and ketone compounds is 3: 1～15: 1.
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CN102391238B (en) * 2011-09-28 2013-07-03 江苏飞翔化工股份有限公司 Method for preparing epsilon-caprolactone by catalyzing oxidation of cyclohexanone
CN103450144A (en) * 2013-09-12 2013-12-18 中山大学 Method for preparing epsilon-caprolactone through biomimetic catalysis of cyclohexanone oxidation
CN103724314A (en) * 2013-12-16 2014-04-16 中山大学 Method for preparing inner ester through composite catalysis of ketone compounds

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Lorenza Cammarota et al..One-pot synthesis of ketones and lactones by oxidation of the parent hydrocarbons with KHSO5 catalyzed by manganese(III) porphyrins in a biphasic, solid-liquid, system.《Journal of Molecular Catalysis A: Chemical》.1999,第137卷155-160. *
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