CN103724314A - Method for preparing inner ester through composite catalysis of ketone compounds - Google Patents
Method for preparing inner ester through composite catalysis of ketone compounds Download PDFInfo
- Publication number
- CN103724314A CN103724314A CN201310693309.9A CN201310693309A CN103724314A CN 103724314 A CN103724314 A CN 103724314A CN 201310693309 A CN201310693309 A CN 201310693309A CN 103724314 A CN103724314 A CN 103724314A
- Authority
- CN
- China
- Prior art keywords
- ketone
- tubes
- walled carbon
- carbon nano
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- -1 ketone compounds Chemical class 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 7
- 150000002148 esters Chemical class 0.000 title abstract 3
- 150000002576 ketones Chemical class 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 150000002596 lactones Chemical class 0.000 claims description 15
- 239000002048 multi walled nanotube Substances 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 150000004032 porphyrins Chemical class 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 230000033444 hydroxylation Effects 0.000 claims description 5
- 238000005805 hydroxylation reaction Methods 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Chemical group 0.000 claims description 4
- 239000001257 hydrogen Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 5
- LFSAPCRASZRSKS-UHFFFAOYSA-N 2-methylcyclohexan-1-one Chemical compound CC1CCCCC1=O LFSAPCRASZRSKS-UHFFFAOYSA-N 0.000 description 4
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 0 *c(c(*)c1[Al])c(*)c(*)c1I Chemical compound *c(c(*)c1[Al])c(*)c(*)c1I 0.000 description 1
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing inner ester through the composite catalysis of ketone compounds. The method comprises the following steps: using ketone as a raw material, oxygen as an oxidant, and a metalloporphyrin compound and a carbon material as compound catalysts, and carrying out a catalytic reaction at the reaction temperature of 25-70 DEG C and under the normal pressure to selectively obtain the inner ester. The method has the advantages of simple process, high yield, low catalyst consumption, mild condition, safety and the like.
Description
Technical field
The present invention relates to a kind of preparation method of lactone, specifically, relate to a kind of method that composite catalyzing ketone dioxygen oxidation is prepared lactone.
Background technology
Lactone is the important organic synthesis intermediate of a class, the method of industrial production lactone mainly realizes by Baeyer-Villiger oxidizing reaction at present, the oxygenant adopting is all that organic peracid is as Peracetic Acid conventionally, in use procedure, there is the problems such as poor stability, energy consumption be large, the application of this technique is restricted.Therefore, use clean oxygen/air to substitute traditional oxidant stoichiometry as oxygenant, selecting suitable catalyzer and effective response path, adopt the solvent few or nontoxic to environmental hazard, is to realize safety, environmental friendliness to prepare one of gordian technique of lactone.
Carbon material is as the catalyzer of liquid phase oxidation reaction in recent years, is applied to synthetic, the organic synthesis, acid-base catalysis of preparation, the fine chemicals of high added value chemical intermediate etc.Peng Feng etc. successfully adopt carbon nanometer pipe catalytic oxidizing ethyle alkyl, ethylbenzene and phenylcarbinol, and the catalytic activity that has proposed reaction depends on the transfer transport characteristic of carbon pipe.Kang etc. reported carbon pipe can catalysis benzene, the hydroxylating of toluene, chlorobenzene and oil of mirbane, the discovery gacs such as Fortuny can be used as the catalyzer of phenolic wastewater, have realized under mild conditions the phenol in can catalyzed oxidation water.
Therefore, develop and a kind ofly take ketone as raw material, oxygen is oxygenant, and clean energy-saving, technique is simple, Financial cost is low, mild condition, lactone preparation technology that selectivity is high will have very important application prospect.
Summary of the invention
The object of the invention is to provide a kind of clean energy-saving, mild condition, the simple catalyzing ketone oxidation of technique to prepare the method for lactone.
For realizing object of the present invention, the technical scheme adopting is: take ketone as raw material, take oxygen as oxygenant, agitator is being housed, in the reactor of temperature regulator and condenser, add auxiliary agent phenyl aldehyde, be dissolved in organic solvent, and add metal porphyrins, carbon material composite catalyst, be controlled at normal pressure, under the condition of 20～70 ℃, carry out catalyzed reaction and obtain lactone, wherein: metalloporphyrin is for having the compound of general formula (I) structure, carbon material is gac, graphite, graphite oxide, Graphene, graphene oxide, multi-walled carbon nano-tubes, a kind of in carboxylated multi-walled carbon nano-tubes or hydroxylation multi-walled carbon nano-tubes, the consumption of metal porphyrins is 1-100ppm, carbon material and raw material ketone mass ratio are 1/10000～1/1000, the mol ratio of auxiliary agent phenyl aldehyde and raw material ketone is 0.5～2.5:1,
M in general formula (I) is atoms metal Mn, Fe, Co, Ni, Cu or Sn, and X is halogen or hydrogen, R
1, R
2, R
3, R
4and R
5all be selected from hydrogen, halogen, nitro, alkyl, alkoxyl group, hydroxyl, carboxyl, sulfydryl or sulfonic group, dentate X
1fluorine or chlorine or imidazoles or pyridine.
At above-mentioned composite catalyzing, prepare in the method for 6-caprolactone, described metal porphyrins preferable alloy atom is Fe, Co, Cu or Sn, and X is fluorine, R
1, R
2, R
3, R
4and R
5be halogen or nitro or hydroxyl, X
1for fluorine or chlorine.
At above-mentioned composite catalyzing, prepare in the method for lactone the preferred gac of described carbon material, graphite, graphite oxide, multi-walled carbon nano-tubes, carboxylated multi-walled carbon nano-tubes or hydroxylation multi-walled carbon nano-tubes.
At above-mentioned composite catalyzing, prepare in the method for lactone, described organic solvent is for being selected from ethyl acetate, 1, at least one in 2-ethylene dichloride, Isosorbide-5-Nitrae-dioxane, acetonitrile.
The preferred metalloporphyrin consumption of the present invention is 1-50ppm, and preferred carbon material and raw material ketone mass ratio are 1/8000～1/2000, and the mol ratio of preferred auxiliary agent phenyl aldehyde and raw material ketone is 0.6～1:1, and preferred temperature of reaction is 30～50 ℃.
Metal porphyrins of the present invention and carbon material are composite catalyst, and under the condition existing at oxygen, catalysis oxidation of ketones generates lactone.Metalloporphyrin can activate oxygen, form high price actives, and the large pi-conjugated system of carbon material can be by the free radical producing in π-π interaction fixation reaction process, improved the utilising efficiency of auxiliary agent, extended the life-span of free radical, accelerate the complexing of metalloporphyrin high price actives and ketone, be conducive to the generation of lactone.
Compared with prior art, the present invention has following beneficial effect:
1, the present invention uses catalyst levels low and easily reclaim and reuse.
2, the present invention uses oxygen for oxygenant, has avoided the safety issue of using peracid to bring.
3, easily separation of simple, the product of operating procedure of the present invention, clean energy-saving, Financial cost are low, have good prospects for commercial application.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but protection scope of the present invention is not limited to the scope that embodiment represents.
In embodiment, reagent used is commercially available analytical reagent.
In embodiment, the bionic catalysts such as metalloporphyrin used are by prior art (Alder AD, et al.J.Org.Chem.1967,32,476; Wang LZ et al.Org.Process Res.Dev.2006,10,757) described method is prepared.
Embodiment 1
At 10mL, contain metalloporphyrin (M=Fe, X=F, the R that 30ppm has general formula (I)
1, R
2, R
3,r
4, R
5=H, X
1=F) in ethyl acetate solution, add the pimelinketone of 2mmol and the phenyl aldehyde of 4mmol, add the carboxylated multi-walled carbon nano-tubes of 5mg, passing into oxygen, is stirring reaction 4 hours at 30 ℃ in temperature, analyzes after testing, the transformation efficiency of pimelinketone is 94%, and the selectivity of 6-caprolactone is greater than 99%.
Embodiment 2
At 10mL, contain metalloporphyrin (M=Sn, X=H, the R that 1ppm has general formula (I)
1=NO
2, R
2, R
3, R
4, R
5=H, X
1=Cl) 1, in 2-dichloroethane solution, add the 4-tertiary butyl pimelinketone of 2mmol and the phenyl aldehyde of 2mmol, the gac that adds 10mg, in temperature, it is stirring reaction 5 hours at 60 ℃, analyze after testing, the transformation efficiency of 4-tertiary butyl pimelinketone is that the selectivity of 92%, 4-tertiary butyl hexamethylene lactone is greater than 99%.
Embodiment 3
At 10mL, contain metalloporphyrin (M=Cu, X=F, the R that 10ppm has general formula (I)
1=CH
3, R
3=Cl, R
2, R
4, R
5=H, X
1=Cl) in acetonitrile solution, add the 4-methylcyclohexanone of 2mmol and the phenyl aldehyde of 2mmol, add the graphite of 2mg, in temperature, it is stirring reaction 8 hours at 50 ℃, analyze after testing, the transformation efficiency of 4-methylcyclohexanone is that the selectivity of 96%, 4-methyl cyclohexane lactone is greater than 99%.
Embodiment 4
At 10mL, contain metalloporphyrin (M=Cu, X=F, the R that 50ppm has general formula (I)
3=OH, R
1, R
2, R
4, R
5=H, X
1=F) 1, in 2-dichloroethane solution, add the cyclopentanone of 2mmol and the phenyl aldehyde of 4mmol, the graphite oxide that adds 5mg, is stirring reaction 7 hours at 60 ℃ in temperature, analyzes after testing, the transformation efficiency of cyclopentanone is 89%, and the selectivity of ring valerolactone is greater than 99%.
Embodiment 5
At 10mL, contain metalloporphyrin (M=Fe, X=F, the R that 50ppm has general formula (I)
3=OH, R
1, R
2, R
4, R
5=H, X
1=F) in ethyl acetate solution, add the 2-methylcyclohexanone of 2mmol and the phenyl aldehyde of 5mmol, add the multi-walled carbon nano-tubes of 2mg, in temperature, it is stirring reaction 6 hours at 30 ℃, analyze after testing, the transformation efficiency of 2-methylcyclohexanone is that the selectivity of 90%, 2-methyl cyclohexane lactone is greater than 99%.
Embodiment 6
At 10mL, contain metalloporphyrin (M=Co, the R that 8ppm has general formula (I)
1, R
2, R
3, R
4, R
5=H, X
1=Cl), in Isosorbide-5-Nitrae-dioxane solution, add the methyln-hexyl ketone of 2mmol and the phenyl aldehyde of 5mmol, the carboxylated Single Walled Carbon Nanotube that adds 10mg, is stirring reaction 12 hours at 50 ℃ in temperature, analyzes after testing, the transformation efficiency of methyln-hexyl ketone is 87%, and the selectivity of hexyl acetate is greater than 99%.
Embodiment 7
At 10mL, contain metalloporphyrin (M=Sn, the R that 10ppm has general formula (I)
1, R
2, R
3, R
4, R
5=OH, X
1=F) in acetonitrile solution, add the pimelinketone of 2mmol and the phenyl aldehyde of 4mmol, add the hydroxylation Single Walled Carbon Nanotube of 10mg, in temperature, it is stirring reaction 8 hours at 30 ℃, analyze after testing, the transformation efficiency of pimelinketone is 97%, and the selectivity of 6-caprolactone is greater than 99%.
Embodiment 8
At 10mL, contain metalloporphyrin (M=Co, the R that 20ppm has general formula (I)
1, R
2, R
3, R
4, R
5=Cl, X
1=Cl) in ethyl acetate solution, add the 2-methylcyclohexanone of 2mmol and the phenyl aldehyde of 4mmol, add the Single Walled Carbon Nanotube of 5mg, in temperature, it is stirring reaction 6 hours at 40 ℃, analyze after testing, the transformation efficiency of 2-methylcyclohexanone is that the selectivity of 96%, 2-methyl cyclohexane lactone is greater than 99%.
Claims (8)
1. a composite catalyzing ketone compounds is prepared the method for lactone, it is characterized in that take that ketone is as raw material, take oxygen as oxygenant, agitator is being housed, in the reactor of temperature regulator and condenser, add auxiliary agent phenyl aldehyde, be dissolved in organic solvent, and add by metal porphyrins, the composite catalyst that carbon material forms, be controlled at normal pressure, under the condition of 20～70 ℃, carry out catalyzed reaction and obtain lactone, wherein: metal porphyrins is for having the compound of general formula (I) structure, carbon material is gac, graphite, graphite oxide, Graphene, graphene oxide, multi-walled carbon nano-tubes, a kind of in carboxylated multi-walled carbon nano-tubes or hydroxylation multi-walled carbon nano-tubes, the consumption of metal porphyrins is 1-100ppm, carbon material and raw material ketone mass ratio are 1/10000～1/1000, the mol ratio of auxiliary agent phenyl aldehyde and raw material ketone is 0.5～2.5:1,
M in general formula (I) is atoms metal Mn, Fe, Co, Ni, Cu or Sn, and X is halogen or hydrogen, R
1, R
2, R
3, R
4and R
5all be selected from hydrogen, halogen, nitro, alkyl, alkoxyl group, hydroxyl, carboxyl, sulfydryl or sulfonic group, dentate X
1fluorine or chlorine or imidazoles or pyridine.
2. method according to claim 1, the atoms metal that it is characterized in that described metal porphyrins is Fe, Co, Cu or Sn, X is fluorine, R
1, R
2, R
3, R
4and R
5be halogen or nitro or hydroxyl, X
1for fluorine or chlorine.
3. method according to claim 1, is characterized in that carbon material is gac, graphite, graphite oxide, multi-walled carbon nano-tubes, carboxylated multi-walled carbon nano-tubes or hydroxylation multi-walled carbon nano-tubes.
4. method according to claim 1, the consumption that it is characterized in that metal porphyrins is 1-50ppm.
5. method according to claim 1, is characterized in that carbon material and raw material ketone mass ratio are 1/8000～1/2000.
6. method according to claim 1, the mol ratio that it is characterized in that auxiliary agent phenyl aldehyde and raw material ketone is 0.6～1:1.
7. method according to claim 1, is characterized in that temperature of reaction is 30-50 ℃.
8. method according to claim 1, is characterized in that described organic solvent is ethyl acetate, 1, at least one in 2-ethylene dichloride, Isosorbide-5-Nitrae-dioxane, acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310693309.9A CN103724314A (en) | 2013-12-16 | 2013-12-16 | Method for preparing inner ester through composite catalysis of ketone compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310693309.9A CN103724314A (en) | 2013-12-16 | 2013-12-16 | Method for preparing inner ester through composite catalysis of ketone compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103724314A true CN103724314A (en) | 2014-04-16 |
Family
ID=50448647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310693309.9A Pending CN103724314A (en) | 2013-12-16 | 2013-12-16 | Method for preparing inner ester through composite catalysis of ketone compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103724314A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980078A (en) * | 2014-05-08 | 2014-08-13 | 中山大学 | Method for preparing lactone through catalyzing oxidation of ketone compound, and its special catalyst |
| CN105688998A (en) * | 2016-03-10 | 2016-06-22 | 中山大学惠州研究院 | Catalyst for catalyzing alkene epoxidation |
| CN105749975A (en) * | 2016-03-04 | 2016-07-13 | 江苏大学 | Immobilized metal porphyrin enzyme catalyst and preparation method thereof |
| CN111018823A (en) * | 2019-12-12 | 2020-04-17 | 河南能源化工集团研究总院有限公司 | Process for preparing epsilon-caprolactone and co-producing methacrylic acid by cyclohexanone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205225A (en) * | 2007-11-09 | 2008-06-25 | 华南理工大学 | Method for preparing lactones by biomimetic catalytic oxidation of ketone compounds |
| CN102603446A (en) * | 2012-02-13 | 2012-07-25 | 湖南大学 | Method for preparing organic lactone by catalyzing and oxidizing organic ketone with carbon materials |
-
2013
- 2013-12-16 CN CN201310693309.9A patent/CN103724314A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205225A (en) * | 2007-11-09 | 2008-06-25 | 华南理工大学 | Method for preparing lactones by biomimetic catalytic oxidation of ketone compounds |
| CN102603446A (en) * | 2012-02-13 | 2012-07-25 | 湖南大学 | Method for preparing organic lactone by catalyzing and oxidizing organic ketone with carbon materials |
Non-Patent Citations (1)
| Title |
|---|
| 马红等: "卟啉在催化剂方面的应用研究进展", 《河北工业科技》, vol. 26, no. 3, 31 May 2009 (2009-05-31), pages 205 - 209 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980078A (en) * | 2014-05-08 | 2014-08-13 | 中山大学 | Method for preparing lactone through catalyzing oxidation of ketone compound, and its special catalyst |
| CN105749975A (en) * | 2016-03-04 | 2016-07-13 | 江苏大学 | Immobilized metal porphyrin enzyme catalyst and preparation method thereof |
| CN105688998A (en) * | 2016-03-10 | 2016-06-22 | 中山大学惠州研究院 | Catalyst for catalyzing alkene epoxidation |
| CN111018823A (en) * | 2019-12-12 | 2020-04-17 | 河南能源化工集团研究总院有限公司 | Process for preparing epsilon-caprolactone and co-producing methacrylic acid by cyclohexanone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ji et al. | Highly efficient oxidation of alcohols to carbonyl compounds in the presence of molecular oxygen using a novel heterogeneous ruthenium catalyst | |
| CN102675072B (en) | Method for producing acetophenone through catalytic oxidation of ethylbenzene | |
| Saedi et al. | MIL-101 metal–organic framework: A highly efficient heterogeneous catalyst for oxidative cleavage of alkenes with H2O2 | |
| Nabae et al. | Catalysis by carbon materials for the aerobic baeyer–villiger oxidation in the presence of aldehydes | |
| CN102260157B (en) | Method for preparing corresponding diacid by cyclone oxide | |
| CN103724314A (en) | Method for preparing inner ester through composite catalysis of ketone compounds | |
| Yasukawa et al. | Rate‐Acceleration in Gold‐Nanocluster‐Catalyzed Aerobic Oxidative Esterification Using 1, 2‐and 1, 3‐Diols and Their Derivatives | |
| Torbina et al. | Propylene glycol oxidation with tert-butyl hydroperoxide over Cr-containing metal-organic frameworks MIL-101 and MIL-100 | |
| CN105585541B (en) | A kind of preparation method of 7-oxa-bicyclo[4.1.0 | |
| CN105585469B (en) | A kind of method that phenol gas phase hydrogenation prepares cyclohexanone | |
| Chattopadhyay et al. | Copper (II)-coordinated organic nanotube: A novel heterogeneous catalyst for various oxidation reactions | |
| CN103980078A (en) | Method for preparing lactone through catalyzing oxidation of ketone compound, and its special catalyst | |
| North et al. | Catalytic, asymmetric cyanohydrin synthesis in propylene carbonate | |
| CN103467434B (en) | Method for preparing eta-caprolactone by composite catalysis | |
| CN108821952B (en) | Method for cracking lignin by heterogeneous cobalt catalytic oxidation | |
| CN104628548A (en) | Method for preparing acetophenone by bionic catalytic oxidation of ethylbenzene | |
| Kaewmati et al. | Aerobic oxygenation of phenylboronic acid promoted by thiol derivatives under gold-free conditions: A warning against gold nanoparticle catalysis | |
| CN101899022B (en) | Method for preparing epoxypropane by bionically catalyzing epoxidation of propylene | |
| JP2016517846A (en) | Method for synthesizing acetophenone | |
| CN109180608A (en) | A kind of method of epoxidation of styrene Styryl oxide | |
| Peng et al. | Graphene oxide and its derivatives: Their synthesis and use in organic synthesis | |
| CN103450144A (en) | Method for preparing epsilon-caprolactone through biomimetic catalysis of cyclohexanone oxidation | |
| Xie et al. | Hydration of Alkynes to Ketones with an Efficient and Practical Polyoxomolybdate‐based Cobalt Catalyst | |
| CN103274883A (en) | Method for preparing lactone through catalyzing oxidation of ketone compound | |
| CN107129426B (en) | Preparation method of 2, 5-dichlorophenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140416 |