CN100528825C - Method for preparing camphorquinone through catalysis of metalloporphyrin and oxidation in air - Google Patents
Method for preparing camphorquinone through catalysis of metalloporphyrin and oxidation in air Download PDFInfo
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- CN100528825C CN100528825C CNB2006101130421A CN200610113042A CN100528825C CN 100528825 C CN100528825 C CN 100528825C CN B2006101130421 A CNB2006101130421 A CN B2006101130421A CN 200610113042 A CN200610113042 A CN 200610113042A CN 100528825 C CN100528825 C CN 100528825C
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- camphorquinone
- metalloporphyrin
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- bromocamphor
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- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229930006711 bornane-2,3-dione Natural products 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 title claims description 28
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims abstract description 70
- NJQADTYRAYFBJN-FWWHASMVSA-N (1s,2s,4r)-2-bromo-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound C1C[C@@]2(C)C(=O)[C@@H](Br)[C@@H]1C2(C)C NJQADTYRAYFBJN-FWWHASMVSA-N 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 25
- 230000005587 bubbling Effects 0.000 claims description 23
- 239000012043 crude product Substances 0.000 claims description 23
- 235000009518 sodium iodide Nutrition 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 tin anhydride Chemical class 0.000 description 3
- NJQADTYRAYFBJN-UHFFFAOYSA-N 2-bromo-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound C1CC2(C)C(=O)C(Br)C1C2(C)C NJQADTYRAYFBJN-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
This invention relates to a method for preparing camphorquinone by metalloporphyrin-catalyzed air oxidation. The method comprises: (1) adding 0.01-0.1 mol% mononucleus metalloporphyrin (shown in formulae I and II) or mu-O-binuclei metalloporphyrin (shown in formula III) catalyst into 0.1-1 mol bromocamphor; (2) selecting 50-500 mL glucol, nitrobenzene, N,N-dimethyl sulfoxide or N,N-dimethyl formamide as the solvent, and NaI, mercaptan, azo or peroxide as the initiator; (3) introducing air at a flow rate of 5-15 L/h, controlling the temperature at 100-160 deg.C, and reacting for 0.5-3 h to obtain crude camphorquinone; (4) separating and purifying to obtain pure camphorquinone (m.p. 196-198 deg.C). The purity of camphorquinone is higher than 99.5% as determined by HPLC, and the yield is up to 99.8%. The method has such advantages as low cost, little pollution and high yield.
Description
Technical field
The present invention relates to a kind of method for preparing camphorquinone, specifically, relate to a kind of method of preparing camphorquinone through catalysis of metalloporphyrin and oxidation in air.
Background technology
Camphorquinone, chemical name: 1,7,7-trimethylammonium dicyclo [2.2.1]-2 is a kind of photosensitizers of high-efficiency low-toxicity, is with a wide range of applications.Medically be mainly used in manufacturing acrylic lens, tooth filler, tooth caking agent, medical cream etc.; At the industrial sealing insulator of making printed circuit board (PCB), photoelectric instrument, developing material, photopolymerisable catalyzer or the like of being mainly used in; It also is used to make the photodegradation ethene polymers of alleviating environmental pollution.In addition, camphorquinone is a kind of important chiral intermediate, also is widely used in asymmetric synthesis.
The preparation of camphorquinone has two kinds of methods: tin anhydride catalytic oxidation (the Evan W.C. of (1) camphor, Ridgion J.M., Simonsen J.L.The preparation of camphorquinone[J] .Journal ofthe Chemical Society, 1934,137.).(2) air oxidation process (the Hattori Kazuyuki of 3-bromo-camphor in the presence of the radical initiator sodium iodide, Yoshida Takashi, Rikuta Kenichi, et al.Anew oxidation of 3-bromocamphor to camphorquinone[J] .Chemical Letters, 1994,10:1885.).The weak point of above-mentioned two kinds of methods is: catalyzer tin anhydride used in the method (1) is a deadly poisonous compound, the residual of selenium class material arranged in the product, thereby has limited the application of camphorquinone aspect medical.Employing method (2) have yield and purity preferably when charging capacity is tested less than 1g, but when charging capacity was 1-100g, the reaction times reached 24h when synthesizing, and yield has only 32%.Though people such as Zhang Haobo (Zhang Haobo, Wang Mingliang, synthesizing of camphorquinone, the Jiangsu chemistry, Vol.33 No.5.Oct.2005) has reported by the method that adds the catalyst acetic acid cobalt and yield can have been brought up to 72%, makes the reaction times be reduced to 6h simultaneously, but, limited its application because of the toxicity of catalyst acetic acid cobalt is stronger; Employed radical initiator sodium iodide is excessive more in the while method (2), and its consumption is 4 times of bromocamphor consumption, thereby production cost is too high.
Summary of the invention
The purpose of this invention is to provide a kind of cost low, pollute little and the reaction times short, the method for the preparing camphorquinone through catalysis of metalloporphyrin and oxidation in air that yield is high.
The present invention realizes according to following technical scheme: add molar percentage 0.01-0.1% and have the μ-oxygen-dinuclear metalloporphyrin of the monokaryon metalloporphyrin of general formula (I), (II) structure or general formula (III) structure as catalyzer in the 0.1-1mol bromocamphor, in the formula, M
1, M
2, M
3, M
4Be transition metal atoms, M
3And M
4Can be identical, also can be different; R
1, R
2Be hydrogen, alkyl, halogen, nitro, hydroxyl or alkoxyl group, dentate X are acetate, methyl ethyl diketone or halogen are selected 50-500mL ethylene glycol for use, oil of mirbane, N, N-dimethyl sulfoxide (DMSO) (DMSO) or N, dinethylformamide (DMF) is a solvent, select sodium iodide for use, mercaptan, and azo class (as azo isobutyl cyanogen) or peroxide (as hydrogen peroxide, dialkyl peroxide, peroxidation two acyls) be radical initiator, its consumption is 0.5-4 a times of bromocamphor molar percentage, bubbling air, and flow rate control is at 5-15L/h, control reaction temperature is 100-160 ℃, reaction 0.5-3h obtains the camphorquinone crude product, adopts ordinary method to separate, behind the purifying, obtain the pure product of camphorquinone, m.p.196-198 ℃, adopt high effective liquid chromatography for measuring camphorquinone purity greater than 99.5%, its yield reaches as high as 99.8%.
General formula (I)
General formula (II)
General formula (III)
Above-mentioned catalyzer preferably has the monokaryon metalloporphyrin of general formula (I) structure.
The monokaryon metalloporphyrin that especially preferably has general formula (I) structure, wherein R
1=R
2=H, M
1=Fe is as catalyzer.
Adopt the inventive method to have following beneficial effect:
(1) use metal porphyrins as catalyzer, the catalyzer nontoxicity makes that the use range of product camphorquinone is enlarged;
(2) consumption of radical initiator reduces, and has saved production cost;
(3) with air as oxygenant, oxygenant is simple and easy to;
(4) reaction times shortens greatly, has saved the energy.
Embodiment
Embodiment 1
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 30mmol has general formula (I) structure
1=R
2=H, M
1=Fe), 500mL N, N-dimethyl sulfoxide solvent, the 2mol sodium iodide, bubbling air, flow rate control are at 10L/h, at 120 ℃ of following reaction stirred 60min, obtain the camphorquinone crude product, add reaction product and pour in the water, washing, drying, obtain pure product bromocamphor with the normal hexane recrystallization, yield is 99.3%.
Embodiment 2
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 30mmol has general formula (I) structure
1=R
2=H, M
1=Fe), 500mL N, N-dimethyl sulfoxide solvent, 4mol sodium iodide, bubbling air, flow rate control at 120 ℃ of following reaction stirred 60min, obtain the camphorquinone crude product at 10L/h, employing obtains the pure product of camphorquinone with the treatment process of embodiment 1, and its yield is 99.8%.
Embodiment 3
In the 0.1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 1mmol has general formula (I) structure
1=R
2=H, M
1=Fe), 50mL N, dinethylformamide solvent, 0.2mol sodium iodide, bubbling air, flow rate control at 130 ℃ of following reaction stirred 60min, obtain the camphorquinone crude product at 5L/h, employing obtains the pure product of camphorquinone with the treatment process of embodiment 1, and its yield is 72.3%.
Embodiment 4
In the 0.5mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 25mmol has general formula (I) structure
1=R
2=H, M
1=Fe), and 250mL oil of mirbane solvent, the 1mol sodium iodide, bubbling air, flow rate control at 160 ℃ of following reaction stirred 60min, obtains the camphorquinone crude product at 8L/h, adopts the treatment process with embodiment 1, obtains the pure product of camphorquinone, and its yield is 81.5%.
Embodiment 5
In the 0.5mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 10mmol has general formula (I) structure
1=R
2=H, M
1=Fe), and the 250mL ethylene glycol solvent, the 1mol sodium iodide, bubbling air, flow rate control at 160 ℃ of following reaction stirred 60min, obtains the camphorquinone crude product at 8L/h, adopts the treatment process with embodiment 1, obtains the pure product of camphorquinone, and its yield is 75.7%.
Embodiment 6
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 50mmol has general formula (I) structure
1=R
2=H, M
1=Fe), 500mL N, N-dimethyl sulfoxide solvent, 0.5mol decyl mercaptan, bubbling air, flow rate control at 110 ℃ of following reaction stirred 60min, obtain the camphorquinone crude product at 10L/h, employing obtains the pure product of camphorquinone with the treatment process of embodiment 1, and its yield is 66.3%.
Embodiment 7
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 30mmol has general formula (I) structure
1=R
2=H, M
1=Fe), 500mL N, N-dimethyl sulfoxide solvent, 0.5mol azo isobutyl cyanogen, bubbling air, flow rate control at 120 ℃ of following reaction stirred 60min, obtain the camphorquinone crude product at 10L/h, employing obtains the pure product of camphorquinone with the treatment process of embodiment 1, and its yield is 63.8%.
Embodiment 8
In the 0.2mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 10mmol has general formula (I) structure
1=R
2=CH
3, M
1=Mn), 100mLN, N-dimethyl sulfoxide solvent, 0.4mol sodium iodide, bubbling air, flow rate control at 130 ℃ of following reaction stirred 1.5h, obtain the camphorquinone crude product at 8L/h, employing obtains the pure product of camphorquinone with the treatment process of embodiment 1, and its yield is 76.4%.
Embodiment 9
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 35mmol has general formula (I) structure
1=R
2=NO
2, M
1=Fe), 500mL N, N-dimethyl sulfoxide solvent, 2mol sodium iodide, bubbling air, flow rate control at 120 ℃ of following reaction stirred 30min, obtain the camphorquinone crude product at 10L/h, employing obtains the pure product of camphorquinone with the treatment process of embodiment 1, and its yield is 91.6%.
Embodiment 10
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 70mmol has general formula (I) structure
1=R
2=OCH
3, M
1=Fe), 500mL N, N-dimethyl sulfoxide solvent, 2mol sodium iodide, bubbling air, flow rate control at 130 ℃ of following reaction stirred 60min, obtain the camphorquinone crude product at 10L/h, employing obtains the pure product of camphorquinone with the treatment process of embodiment 1, and its yield is 93.8%.
Embodiment 11
In the 0.3mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 20mmol has general formula (I) structure
1=R
2=H, M
1=Zn), 500mL N, N-dimethyl sulfoxide solvent, 0.6mol sodium iodide, bubbling air, flow rate control at 90 ℃ of following reaction stirred 1.5h, obtain the camphorquinone crude product at 6L/h, employing obtains the pure product of camphorquinone with the treatment process of embodiment 1, and its yield is 81.4%.
Embodiment 12
In the 0.5mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 25mmol has general formula (I) structure
1=R
2=H, M
1=Cu), add 250mL N, N-dimethyl sulfoxide solvent, 1mol sodium iodide, bubbling air, flow rate control at 130 ℃ of following reaction stirred 2h, obtain the camphorquinone crude product at 8L/h, employing obtains the pure product of camphorquinone with the treatment process of embodiment 1, and its yield is 78.7%.
Embodiment 13
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 70mmol has general formula (I) structure
1=R
2=Cl, M
1=Fe), 500mL N, N-dimethyl sulfoxide solvent, 2mol sodium iodide, bubbling air, flow rate control at 110 ℃ of following reaction stirred 60min, obtain the camphorquinone crude product at 8L/h, employing obtains the pure product of camphorquinone with the treatment process of embodiment 1, and its yield is 92.7%.
Embodiment 14
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 70mmol has general formula (II) structure
1=R
2=Cl, M
2=Fe, X=Cl), 500mLN, N-dimethyl sulfoxide solvent, the 2mol sodium iodide, bubbling air, flow rate control is at 10L/h, at 100 ℃ of following reaction stirred 60min, obtain the camphorquinone crude product, adopt the treatment process with embodiment 1, obtain the pure product of camphorquinone, its yield is 84.4%.
Embodiment 15
In the 0.3mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 30mmol has general formula (II) structure
1=R
2=CH
3, M
2=Mn, X=Cl), 200mLN, N-dimethyl sulfoxide solvent, 0.6mol sodium iodide, bubbling air, flow rate control is at 8L/h, at 150 ℃ of following reaction stirred 3h, obtain the camphorquinone crude product, adopt the treatment process with embodiment 1, obtain the pure product of camphorquinone, its yield is 80.5%.
Embodiment 16
In the 0.5mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 25mmol has general formula (II) structure
1=R
2=CH
3, M
2=Fe, X=Cl), 250mL N, N-dimethyl sulfoxide solvent, the 1mol sodium iodide, bubbling air, flow rate control is at 7L/h, at 150 ℃ of following reaction stirred 1.5h, obtain the camphorquinone crude product, adopt the treatment process with embodiment 1, obtain the pure product of camphorquinone, its yield is 81.7%.
Embodiment 17
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 90mmol has general formula (III) structure
1=R
2=OCH
3, M
3=Mn, M
4=Mn), and 500mL N, the N-dimethyl sulfoxide solvent, the 2mol sodium iodide, bubbling air, flow rate control at 120 ℃ of following reaction stirred 3h, obtains the camphorquinone crude product at 10L/h, adopts the treatment process with embodiment 1, obtains the pure product of camphorquinone, and its yield is 77.6%.
Embodiment 18
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 90mmol has general formula (III) structure
1=R
2=CH
3, M
3=Mn, M
4=Fe), and 500mL N, the N-dimethyl sulfoxide solvent, the 2mol sodium iodide, bubbling air, flow rate control at 150 ℃ of following reaction stirred 3h, obtains the camphorquinone crude product at 15L/h, adopts the treatment process with embodiment 1, obtains the pure product of camphorquinone, and its yield is 79.2%.
Embodiment 19
In the 1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 80mmol has general formula (III) structure
1=R
2=H, M
3=Mn, M
4=Fe), and 500mL N, the N-dimethyl sulfoxide solvent, the 2mol sodium iodide, bubbling air, flow rate control at 140 ℃ of following reaction stirred 2h, obtains the camphorquinone crude product at 12L/h, adopts the treatment process with embodiment 1, obtains the pure product of camphorquinone, and its yield is 82.6%.
Embodiment 20
In the 0.8mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 50mmol has general formula (III) structure
1=R
2=H, M
3=Mn, M
4=Fe, X=acetate), 400mL N, N-dimethyl sulfoxide solvent, 1.6mol sodium iodide, bubbling air, flow rate control is at 11L/h, at 130 ℃ of following reaction stirred 3h, obtain the camphorquinone crude product, adopt the treatment process with embodiment 1, obtain the pure product of camphorquinone, its yield is 68.4%.
Embodiment 21
In the 0.1mol bromocamphor, add the catalysis of metalloporphyrin agent (R that 10mmol has general formula (III) structure
1=R
2=CH
3, M
3=Mn, M
4=Fe, X=Cl), 50mLN, N-dimethyl sulfoxide solvent, 0.2mol sodium iodide, bubbling air, flow rate control is at 8L/h, at 150 ℃ of following reaction stirred 3h, obtain the camphorquinone crude product, adopt the treatment process with embodiment 1, obtain the pure product of camphorquinone, its yield is 65.3%.
Claims (3)
1. the method for a preparing camphorquinone through catalysis of metalloporphyrin and oxidation in air, it is characterized in that in the 0.1-1mol bromocamphor adding molar percentage 0.01-0.1% and have the μ-oxygen-dinuclear metalloporphyrin of the monokaryon metalloporphyrin of general formula (I), (II) structure or general formula (III) structure as catalyzer, in the formula, M
1, M
2, M
3, M
4Be transition metal atoms, M
3And M
4Identical or different; R
1, R
2Be hydrogen, halogen, nitro or alkoxyl group, dentate X is a halogen, selects 50-500mL oil of mirbane or N for use, and the N-dimethyl sulfoxide (DMSO) is a solvent, selecting sodium iodide for use is radical initiator, and its consumption is 0.5-4 a times of bromocamphor molar percentage, bubbling air, flow rate control is at 5-15L/h, control reaction temperature is 100-160 ℃, and reaction 0.5-3h obtains the camphorquinone crude product, after adopting ordinary method to separate, purify, obtain the pure product of camphorquinone
General formula (I)
General formula (II)
General formula (III).
2. the method for preparing camphorquinone through catalysis of metalloporphyrin and oxidation in air according to claim 1 is characterized in that the monokaryon metalloporphyrin of described catalyzer for having general formula (I) structure.
3. the method for preparing camphorquinone through catalysis of metalloporphyrin and oxidation in air according to claim 1 and 2 is characterized in that the monokaryon metalloporphyrin of described catalyzer for having general formula (I) structure, wherein R
1=R
2=H, M
1=Fe.
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| CA2733528A1 (en) * | 2008-08-11 | 2010-02-18 | Fukutome, Hirofumi | Catalyst for the decomposition of lignin, method for the preparation of alcohols and organic acids, method for the preparation of lignin-decomposition products, catalyst for the decomposition of aromatic hydrocarbons, method for releasing hydrogen ions, as well as porphyrin |
| CN102992987B (en) * | 2012-12-13 | 2015-05-13 | 成都建中香料香精有限公司 | Synthesis method for camphorquinone and catalyst composition for synthesis method |
| CN111116334B (en) * | 2019-12-31 | 2023-01-03 | 南京远淑医药科技有限公司 | Novel synthesis method of camphorquinone |
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2006
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Non-Patent Citations (2)
| Title |
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| 樟脑醌的合成. 张浩波，王明亮.江苏化工，第33卷第5期. 2005 |
| 樟脑醌的合成. 张浩波，王明亮.江苏化工，第33卷第5期. 2005 * |
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