CN109608314A - Novel cyclopentane catalytic oxidation method with mild reaction conditions - Google Patents
Novel cyclopentane catalytic oxidation method with mild reaction conditions Download PDFInfo
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- CN109608314A CN109608314A CN201811466356.9A CN201811466356A CN109608314A CN 109608314 A CN109608314 A CN 109608314A CN 201811466356 A CN201811466356 A CN 201811466356A CN 109608314 A CN109608314 A CN 109608314A
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- Prior art keywords
- pentamethylene
- tetra
- chlorphenyl
- metalloporphyrin
- cyclopentanol
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title abstract description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 title abstract 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 42
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims abstract description 22
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 50
- 238000006555 catalytic reaction Methods 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 5
- 150000004032 porphyrins Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- VGGFAUSJLGBJRZ-UHFFFAOYSA-N hydroperoxycyclopentane Chemical compound OOC1CCCC1 VGGFAUSJLGBJRZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 24
- XJJWWOUJWDTXJC-UHFFFAOYSA-N [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 XJJWWOUJWDTXJC-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- 229910001220 stainless steel Inorganic materials 0.000 description 13
- 239000010935 stainless steel Substances 0.000 description 13
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 239000005457 ice water Substances 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 description 10
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- -1 cycloalkyl alcohol Chemical compound 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- 102000002004 Cytochrome P-450 Enzyme System Human genes 0.000 description 1
- 108010015742 Cytochrome P-450 Enzyme System Proteins 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036301 sexual development Effects 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A method for catalyzing and oxidizing cyclopentane comprises the following steps: mixing metalloporphyrin and cyclopentane at 100-150 deg.c and O2Reacting for 2-48 h under the condition of the pressure of 0.6-2 MPa, and then carrying out post-treatment and separation on the reaction liquid to obtain oxidation products of glutaric acid, cyclopentanol and cyclopentanone; the new method for catalytic oxidation of cyclopentane has the advantages of low reaction temperature, less catalyst consumption and O2The novel method for catalyzing and oxidizing the cyclopentane has the advantages of being an oxidant, environment-friendly, capable of oxidizing the cyclopentane into cyclopentanol, cyclopentanone and glutaric acid in high selectivity, simple to operate, free of organic solvent, high in selectivity of the glutaric acid, low in cyclopentyl hydrogen peroxide content and the like.
Description
(1) technical field
The present invention relates to a kind of pentamethylene catalysis oxidation new methods that reaction condition is mild, belong to catalysis organic synthesis field.
(2) background technique
Cycloalkane is a kind of cyclic annular hydro carbons being widely present in oil product, is made at present mainly as fuel and solvent
With utility value is low, and converting corresponding cycloalkyl alcohol, naphthenic one and alkyl acid by catalysis oxidation for it will mention significantly
The utility value of high cycloalkane.The catalysis oxidation of cycloalkane is concentrated mainly on the catalysis oxidation of hexamethylene, oxidation product at present
Cyclohexanol and cyclohexanone further aoxidize the important intermediate adipic acid of available production nylon -66 and nylon-6, and market needs
Ask big (Angew.Chem.Int.Edit., 2016,55:12873；J.Am.Chem.Soc.,2016,138:2426；
Ind.Eng.Chem.Res.,2015,54:2425；Appl.Surf.Sci.,2017,402:436.).To other rings such as pentamethylene
The catalysis oxidation Study on Transformation of alkane is relatively fewer, especially with clean O2Pentamethylene is aoxidized for oxidizer catalytic.Pentamethylene
The product of catalysis oxidation mainly has cyclopentanol, cyclopentanone and glutaric acid, is important chemical intermediate.Therefore, with O2For oxygen
Agent catalysis oxidation pentamethylene has important industrial application meaning.
Model compound of the metalloporphyrin as cytochrome P-450 is widely used in all kinds of organic syntheses of bionic catalysis
Reaction, especially oxidation reaction (New J.Chem., 2017,41:8214；Catal.Commun.,2017,99:100；New
J.Chem.,2017,41:7987；Chem.Lett., 2017,46:1311), few, high catalytic efficiency, knot with catalyst amount
Structure is easy to adjust, bio-compatibility is good, the advantages such as environmentally protective.Therefore, the present invention is catalyzed O using metalloporphyrin as catalyst2Oxygen
Change pentamethylene, preparing cyclopentanol, cyclopentanone and glutaric acid has important industrial application value and social effect, and it is environmentally protective,
Meet current chemical industry sexual development compatible with ecological environment, the current demand of sustainable development.
(3) summary of the invention
The purpose of the present invention is to provide a kind of pentamethylene catalysis oxidation new methods that reaction condition is mild.This method is with gold
Category porphyrin is catalyst, O2For oxidant, realized under condition of no solvent.
Technical scheme is as follows:
A kind of method of pentamethylene catalysis oxidation, the method are as follows:
By metalloporphyrin (catalyst), pentamethylene (raw material) mix, 100~150 DEG C of temperature (preferably 110~120 DEG C),
O22~48h (preferably 4~10h) is reacted under conditions of 0.6~2MPa of pressure (preferably 1~1.6MPa), reaction solution is after later
Reason, isolated oxidation product glutaric acid, cyclopentanol, cyclopentanone；
After the metalloporphyrin and pentamethylene mixing, the concentration of metalloporphyrin is in 10~60ppm, preferably 20~50ppm；
The metalloporphyrin is selected from 5,10,15,20- tetra- (p- chlorphenyl) Cobalt Porphyrins (II), 5,10,15,20- tetra- (p- chlorine
Phenyl) PORPHYRIN IRON (II), 5,10,15,20- tetra- (p- chlorphenyl) Manganese Porphyrins (II), 5,10,15,20- tetra- (p- chlorphenyl) porphyrins
Nickel (II), 5,10,15,20- tetra- (m- chlorphenyl) Cobalt Porphyrins (II), 5,10,15,20- tetra- (o- chlorphenyl) Cobalt Porphyrins (II), 5,
10,15,20- tetra- (m- chlorphenyl) Manganese Porphyrins (II) and 5, it is any one in 10,15,20- tetra- (o- chlorphenyl) Manganese Porphyrins (II)
Kind, preferably 5,10,15,20- tetra- (p- chlorphenyl) Cobalt Porphyrins (II)；
Specifically, the method for the post-processing are as follows: after reaction, be cooled to room temperature (20~30 DEG C), mistake to reaction solution
Filter, filter cake is washed with pentamethylene, and is dried in vacuo at 60 DEG C, and glutaric acid (white solid) is obtained；Filtrate carries out rectifying, collects
129~131 DEG C of fraction is cyclopentanone, and the fraction for collecting 140~141 DEG C is cyclopentanol, while unreacted ring is recycled in rectifying
Pentane.
Present invention reaction can carry out in the stainless steel autoclave with tetrafluoroethene liner.
The beneficial effects are mainly reflected as follows: the pentamethylene catalysis oxidation new method reaction temperature being related to is low, catalysis
Agent dosage is few, and with O2It is environmentally protective for oxidant, can it is highly selective by pentamethylene be oxidized to cyclopentanol, cyclopentanone and
Glutaric acid.The pentamethylene catalysis oxidation new method also has easy to operate, does not use organic solvent, glutaric acid selectivity is high, ring
The advantages such as amyl peroxy hydrogen content is low.
(4) specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
Embodiment 1
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 1.0mg
Base) Cobalt Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 110 DEG C, is passed through O2To 1.0MPa, in
110 DEG C, 1.0MPa O28.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 3.21g, as
Glutaric acid, yield 3.4%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 2.53g, as cyclopentanone, yield
4.2%；Take 140 DEG C~141 DEG C fraction 1.15g, as cyclopentanol, yield 1.9%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Embodiment 2
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 1.0mg
Base) Cobalt Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 120 DEG C, is passed through O2To 1.0MPa, in
120 DEG C, 1.0MPa O28.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 5.32g, as
Glutaric acid, yield 5.6%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 4.32g, as cyclopentanone, yield
5.1%；Take 140 DEG C~141 DEG C fraction 2.86g, as cyclopentanol, yield 4.7%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Embodiment 3
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 0.5mg
Base) Cobalt Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 120 DEG C, is passed through O2To 1.0MPa, in
120 DEG C, 1.0MPa O28.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 4.32g, as
Glutaric acid, yield 4.6%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 3.82g, as cyclopentanone, yield
6.4%；Take 140 DEG C~141 DEG C fraction 1.89g, as cyclopentanol, yield 3.1%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Embodiment 4
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 3.0mg
Base) Cobalt Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 120 DEG C, is passed through O2To 1.0MPa, in
120 DEG C, 1.0MPa O28.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 5.21g, as
Glutaric acid, yield 5.5%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 4.11g, as cyclopentanone, yield
6.9%；Take 140 DEG C~141 DEG C fraction 2.62g, as cyclopentanol, yield 4.3%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Embodiment 5
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 1.0mg
Base) Cobalt Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 120 DEG C, is passed through O2To 0.6MPa, in
120 DEG C, 0.6MPa O28.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 2.86g, as
Glutaric acid, yield 3.1%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 1.72g, as cyclopentanone, yield
2.9%；Take 140 DEG C~141 DEG C fraction 0.86g, as cyclopentanol, yield 1.4%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Embodiment 6
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 1.0mg
Base) Cobalt Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 120 DEG C, is passed through O2To 2.0MPa, in
120 DEG C, 2.0MPa O28.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 4.98g, as
Glutaric acid, yield 5.3%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 4.15g, as cyclopentanone, yield
6.9%；Take 140 DEG C~141 DEG C fraction 1.2g, as cyclopentanol, yield 2.0%；Unreacted pentamethylene is recycled in rectifying simultaneously.
Embodiment 7
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 1.0mg
Base) Cobalt Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 150 DEG C, is passed through O2To 1.0MPa, in
150 DEG C, 1.0MPa O28.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 5.82g, as
Glutaric acid, yield 6.2%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 1.20g, as cyclopentanone, yield
2.0%；Take 140 DEG C~141 DEG C fraction 0.86g, as cyclopentanol, yield 1.4%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Embodiment 8
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 1.0mg
Base) Cobalt Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 120 DEG C, is passed through O2To 1.0MPa, in
120 DEG C, 1.0MPa O22.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 0.36g, as
Glutaric acid, yield 0.4%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 1.26g, as cyclopentanone, yield
2.1%；Take 140 DEG C~141 DEG C fraction 0.83g, as cyclopentanol, yield 1.4%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Embodiment 9
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 1.0mg
Base) Cobalt Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 120 DEG C, is passed through O2To 1.0MPa, in
120 DEG C, 1.0MPa O248.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 6.28g, as
Glutaric acid, yield 6.7%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 2.12g, as cyclopentanone, yield
3.5%；Take 140 DEG C~141 DEG C fraction 1.65g, as cyclopentanol, yield 2.7%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Embodiment 10
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (m- chlorobenzene of 1.0mg
Base) Cobalt Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 120 DEG C, is passed through O2To 1.0MPa, in
120 DEG C, 1.0MPa O28.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 5.46g, as
Glutaric acid, yield 5.8%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 3.89g, as cyclopentanone, yield
6.5%；Take 140 DEG C~141 DEG C fraction 1.23g, as cyclopentanol, yield 2.0%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Embodiment 11
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 2.5mg
Base) Manganese Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 120 DEG C, is passed through O2To 1.0MPa, in
120 DEG C, 1.0MPa O210.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 4.98g, as
Glutaric acid, yield 5.2%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 4.12g, as cyclopentanone, yield
6.9%；Take 140 DEG C~141 DEG C fraction 2.62g, as cyclopentanol, yield 4.3%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Embodiment 12
In the stainless steel autoclave that 100mL has tetrafluoroethene liner, by 5,10,15,20- tetra- (p- chlorobenzene of 2.5mg
Base) Manganese Porphyrin (II) is dissolved in 50.0g pentamethylene, close autoclave.Stirring is warming up to 120 DEG C, is passed through O2To 1.6MPa, in
120 DEG C, 1.6MPa O210.0h is stirred to react under pressure, stirring is cooled to room temperature in ice-water bath.Autoclave is opened, gained is anti-
Mixture is answered to filter, obtained solid is washed through 3 × 10mL pentamethylene, is dried in vacuo at 60 DEG C, is obtained white solid 5.01g, as
Glutaric acid, yield 5.3%.Filtering gained filtrate rectifying, takes 129 DEG C~131 DEG C fraction 4.32g, as cyclopentanone, yield
7.2%；Take 140 DEG C~141 DEG C fraction 1.63g, as cyclopentanol, yield 2.7%；Unreacted ring penta is recycled in rectifying simultaneously
Alkane.
Claims (6)
1. a kind of method of pentamethylene catalysis oxidation, which is characterized in that the method are as follows:
Metalloporphyrin, pentamethylene are mixed, in 100~150 DEG C of temperature, O22~48h is reacted under conditions of 0.6~2MPa of pressure,
Reaction solution is post-treated later, isolated oxidation product glutaric acid, cyclopentanol, cyclopentanone；
After the metalloporphyrin and pentamethylene mixing, the concentration of metalloporphyrin is in 10~60ppm；
The metalloporphyrin is selected from 5,10,15,20- tetra- (p- chlorphenyl) Cobalt Porphyrins (II), 5,10,15,20- tetra- (p- chlorphenyls)
PORPHYRIN IRON (II), 5,10,15,20- tetra- (p- chlorphenyl) Manganese Porphyrins (II), 5,10,15,20- tetra- (p- chlorphenyl) Porphyrin Nickels
(II), 5,10,15,20- tetra- (m- chlorphenyl) Cobalt Porphyrins (II), 5,10,15,20- tetra- (o- chlorphenyl) Cobalt Porphyrins (II), 5,
10,15,20- tetra- (m- chlorphenyl) Manganese Porphyrins (II) and 5, it is any one in 10,15,20- tetra- (o- chlorphenyl) Manganese Porphyrins (II)
Kind.
2. the method for pentamethylene catalysis oxidation as described in claim 1, which is characterized in that reaction temperature is 110~120 DEG C.
3. the method for pentamethylene catalysis oxidation as described in claim 1, which is characterized in that O2Pressure is 1~1.6MPa.
4. the method for pentamethylene catalysis oxidation as described in claim 1, which is characterized in that the reaction time is 4~10h.
5. the method for pentamethylene catalysis oxidation as described in claim 1, which is characterized in that the metalloporphyrin and pentamethylene are mixed
After conjunction, the concentration of metalloporphyrin is in 20~50ppm.
6. the method for pentamethylene catalysis oxidation as described in claim 1, which is characterized in that the method for the post-processing are as follows: anti-
It after answering, is cooled to room temperature, filters, filter cake is washed with pentamethylene, and is dried in vacuo at 60 DEG C, obtains penta 2 to reaction solution
Acid；Filtrate carries out rectifying, and the fraction for collecting 129~131 DEG C is cyclopentanone, and the fraction for collecting 140~141 DEG C is cyclopentanol, together
When rectifying recycle unreacted pentamethylene.
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Cited By (2)
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| CN112174789A (en) * | 2019-07-04 | 2021-01-05 | 南京延长反应技术研究院有限公司 | Catalyst-free cyclopentane oxidation strengthening system and process |
| CN113649073A (en) * | 2021-08-11 | 2021-11-16 | 浙江工业大学 | Method for catalytic oxidation of cycloparaffin by metalloporphyrin bimetallic center 2D MOFs |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237355A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Preparation method for cyclopentanol and cyclopentanone by oxidation of cyclopentane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237355A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Preparation method for cyclopentanol and cyclopentanone by oxidation of cyclopentane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112174789A (en) * | 2019-07-04 | 2021-01-05 | 南京延长反应技术研究院有限公司 | Catalyst-free cyclopentane oxidation strengthening system and process |
| CN113649073A (en) * | 2021-08-11 | 2021-11-16 | 浙江工业大学 | Method for catalytic oxidation of cycloparaffin by metalloporphyrin bimetallic center 2D MOFs |
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