CN113443951A - Preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene - Google Patents
Preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene Download PDFInfo
- Publication number
- CN113443951A CN113443951A CN202110896375.0A CN202110896375A CN113443951A CN 113443951 A CN113443951 A CN 113443951A CN 202110896375 A CN202110896375 A CN 202110896375A CN 113443951 A CN113443951 A CN 113443951A
- Authority
- CN
- China
- Prior art keywords
- tetramethyl
- metal
- cyclopentadiene
- catalyst
- preparation
- 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
- VNPQQEYMXYCAEZ-UHFFFAOYSA-N 1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound CC1=C(C)C(C)=C(C)C1 VNPQQEYMXYCAEZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 25
- ARUAYSANQMCCEN-UHFFFAOYSA-N 2,3,4,5-tetramethylcyclopent-2-en-1-one Chemical compound CC1C(C)C(=O)C(C)=C1C ARUAYSANQMCCEN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- -1 2,3,4, 5-tetramethyl-2-cyclopentadienyl alcohol Chemical compound 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 230000009471 action Effects 0.000 claims abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000001914 filtration Methods 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000006386 neutralization reaction Methods 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- UNZRJDBPLYRKGJ-UHFFFAOYSA-N 2,3,4,5-tetramethylcyclopent-2-en-1-ol Chemical compound CC1C(C)C(C)=C(C)C1O UNZRJDBPLYRKGJ-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 229910010082 LiAlH Inorganic materials 0.000 description 4
- 239000012280 lithium aluminium hydride Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- SIWVGXQOXWGJCI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-ethenylbenzenesulfonic acid Chemical compound C=CC1=CC=CC=C1C=C.OS(=O)(=O)C1=CC=CC=C1C=C SIWVGXQOXWGJCI-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- C07C2531/08—Ion-exchange resins
-
- 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
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene, which comprises the following steps: A) carrying out hydrogenation reaction on a metal supported catalyst, 2,3,4, 5-tetramethyl-2-cyclopentenone and a solvent under the condition of hydrogen to obtain 2,3,4, 5-tetramethyl-2-cyclopentadienyl alcohol; the metal-supported catalyst comprises a solid carrier and a metal supported on the solid carrier; the metal elements are selected from one or two of VIII main group elements; B) under the action of strong acid resin catalyst, 2,3,4, 5-tetramethyl-2-cyclopentadiene alcohol is dehydrated to obtain 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene. The method only needs simple filtration and removal after the hydrogenation reaction is finished, does not generate solid waste liquid, does not need to add acid for neutralization, does not generate waste acid water and the like which are difficult to treat, and has high product yield.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene.
Background
1,2,3, 4-tetramethyl-1, 3-cyclopentadiene is an important intermediate for metallocene catalyst synthesis and is one of the most important sources of cyclopentadiene rings. Currently, 2,3, 4-tetramethyl-1, 3-cyclopentadiene is mainly used as a raw material 2,3,4, 5-tetramethyl-2-cyclopentenone, and a target product is obtained after reduction and dehydration in sequence. Wherein, the reducing agent used in the reduction process is generally lithium aluminum hydride, and the dehydrating agent used in the dehydration process is mostly sulfuric acid.
In the above preparation method, lithium aluminum hydride is expensive and is heated or contacted with moisture, water, alcohol, acid, etc., and an exothermic reaction occurs and releases hydrogen to cause combustion and explosion, and a violent reaction in contact with a strong oxidant may also cause explosion, which has a certain risk. After the reaction, a quenching agent is required to be added for inactivation, a large amount of solid is generated in the inactivation process, a large amount of acid is required to be added for reaction, the solid is dissolved, and meanwhile, a large amount of waste acid water is generated. The product can be separated only by adopting an extraction and liquid separation mode, and the operation is complex and complicated.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a simpler and more environmentally friendly method for preparing 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene, and the yield of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene is higher.
The invention provides a preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene, which comprises the following steps:
A) carrying out hydrogenation reaction on a metal supported catalyst, 2,3,4, 5-tetramethyl-2-cyclopentenone and a solvent under the condition of hydrogen to obtain 2,3,4, 5-tetramethyl-2-cyclopentadienyl alcohol;
the metal-supported catalyst comprises a solid carrier and a metal supported on the solid carrier; the metal elements are selected from one or two of VIII main group elements;
B) under the action of strong acid resin catalyst, 2,3,4, 5-tetramethyl-2-cyclopentadiene alcohol is dehydrated to obtain 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene.
Preferably, the solid support comprises Al2O3、SiO2、TiO2Molecular sieves, activated carbon or carbon materials;
the metal is selected from one or two of Pd, Rh, Rt, Ni and Co;
the content of metal in the metal-supported catalyst is 0.8 wt% -2 wt%.
Preferably, the mass ratio of the metal-supported catalyst to the 2,3,4, 5-tetramethyl-2-cyclopentenone is 10-25 mg:50 g.
Preferably, the solvent comprises one or more of ethanol, methanol, isopropanol, diethyl ether, hexane, cyclohexane, benzene, toluene, xylene and ethylbenzene.
Preferably, the using amount ratio of the 2,3,4, 5-tetramethyl-2-cyclopentenone to the solvent is 10-50 g: 150 mL.
Preferably, the temperature of the hydrogenation reaction is 80-250 ℃.
Preferably, the pressure of the hydrogenation reaction is 1-5 MPa.
Preferably, the strongly acidic resin-based catalyst includes a small pore resin, a carbonic acid resin or a large pore strong acid resin.
Preferably, the mass ratio of the mass of the strong acid resin catalyst to the mass of the 2,3,4, 5-tetramethyl-2-cyclopentadienol is 1-5: 100.
preferably, the temperature of the dehydration reaction is 30-50 ℃.
The invention provides a preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene, which comprises the following steps: A) carrying out hydrogenation reaction on a metal supported catalyst, 2,3,4, 5-tetramethyl-2-cyclopentenone and a solvent under the condition of hydrogen to obtain 2,3,4, 5-tetramethyl-2-cyclopentadienyl alcohol; the metal-supported catalyst comprises a solid carrier and a metal supported on the solid carrier; the metal elements are selected from one or two of VIII main group elements; B) under the action of strong acid resin catalyst, 2,3,4, 5-tetramethyl-2-cyclopentadiene alcohol is dehydrated to obtain 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene. Compared with the method that lithium aluminum hydride is used as a reducing agent, the method has the advantages that 2,3,4, 5-tetramethyl-2-cyclopentenone is subjected to reduction reaction to prepare the 2,3,4, 5-tetramethyl-2-cyclopentadienol, the hydrogen and the metal supported catalyst are adopted, the hydrogen and the metal supported catalyst are removed by simple filtration after the reaction is finished, solid waste liquid is not generated, acid is not required to be added for neutralization, waste acid water and the like which are difficult to treat are not generated, and the catalyst has high catalytic efficiency and high selectivity. Meanwhile, hydrogen is used as a hydrogenation source, and the process is more energy-saving and environment-friendly.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene, which comprises the following steps:
A) carrying out hydrogenation reaction on a metal supported catalyst, 2,3,4, 5-tetramethyl-2-cyclopentenone and a solvent under the condition of hydrogen to obtain 2,3,4, 5-tetramethyl-2-cyclopentadienyl alcohol;
the metal-supported catalyst comprises a solid carrier and a metal supported on the solid carrier; the metal elements are selected from one or two of VIII main group elements;
B) under the action of strong acid resin catalyst, 2,3,4, 5-tetramethyl-2-cyclopentadiene alcohol is dehydrated to obtain 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene.
The method comprises the steps of firstly carrying out hydrogenation reaction on a metal supported catalyst, 2,3,4, 5-tetramethyl-2-cyclopentenone and a solvent under the condition of hydrogen to obtain the 2,3,4, 5-tetramethyl-2-cyclopentadienol.
In the present invention, the metal-supported catalyst comprises a solid support and a metal supported on the solid support; the metal elements are selected from one or two of the VIII main group elements.
In certain embodiments of the invention, the solid support comprises Al2O3、SiO2、TiO2Molecular sieves, activated carbon or carbon materials.
In certain embodiments of the invention, the metal is selected from one or two of Pd, Rh, Rt, Ni and Co.
In certain embodiments of the invention, the metal in the metal-supported catalyst is present in an amount of 0.8 wt% to 2 wt%. In certain embodiments, the metal in the metal-supported catalyst is present in an amount of 2 wt% or 1.5 wt%. The source of the metal-supported catalyst is not particularly limited, and the metal-supported catalyst can be generally commercially available or can be self-made.
In certain embodiments of the present invention, the metal-supported catalyst is selected from Co/TiO2A catalyst.
In certain embodiments of the present invention, the mass ratio of the metal-supported catalyst to the 2,3,4, 5-tetramethyl-2-cyclopentenone is 10-25 mg:50 g. In certain embodiments, the mass ratio of the metal-supported catalyst to the 2,3,4, 5-tetramethyl-2-cyclopentenone is 10 mg:50g, 11 mg:50g, 12 mg:50g, 13 mg:50g, 14 mg:50g, 15 mg:50g, 16 mg:50g, 17 mg:50g, 18 mg:50g, 19 mg:50g, 20 mg:50g, 21 mg:50g, 22 mg:50g, 23 mg:50g, 24 mg:50g or 25mg:50 g.
In certain embodiments of the invention, the solvent comprises one or more of ethanol, methanol, isopropanol, diethyl ether, hexane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
In certain embodiments of the present invention, the 2,3,4, 5-tetramethyl-2-cyclopentenone and the solvent are used in a ratio of 10 to 50 g: 150 mL.
In some embodiments of the present invention, before the hydrogenation reaction of the metal-supported catalyst, 2,3,4, 5-tetramethyl-2-cyclopentenone and the solvent, the method further comprises: mixing the metal supported catalyst, 2,3,4, 5-tetramethyl-2-cyclopentenone and solvent. In certain embodiments of the invention, the method of blending is stirred blending. The stirring method is not particularly limited in the present invention, and a stirring method known to those skilled in the art may be used.
In certain embodiments of the present invention, the temperature of the hydrogenation reaction is 80 to 250 ℃. In certain embodiments, the temperature of the hydrogenation reaction is 80 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 150 ℃, 170 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃.
In certain embodiments of the invention, the pressure of the hydrogenation reaction is 1 to 5 MPa. In certain embodiments of the invention, the hydrogenation reaction is carried out in a high temperature, high pressure reactor.
In certain embodiments of the present invention, the hydrogenation reaction is followed by filtration to yield 2,3,4, 5-tetramethyl-2-cyclopentadienol.
After 2,3,4, 5-tetramethyl-2-cyclopentadienyl alcohol is obtained, 2,3,4, 5-tetramethyl-2-cyclopentadienyl alcohol is subjected to dehydration reaction under the action of a strong acid resin catalyst to obtain 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene.
In certain embodiments of the present invention, the strong acid resinous catalyst comprises Amberlyst-15 ion exchange resin catalyst, Amberlyst-36 ion exchange resin catalyst, or dandong pearl type H cation exchange resin catalyst, and the like. In the present invention, the source of the strongly acidic resin catalyst is not particularly limited, and the catalyst may be generally commercially available.
In some embodiments of the present invention, the mass ratio of the mass of the strong acid resin catalyst to the mass of the 2,3,4, 5-tetramethyl-2-cyclopentadienol is 1 to 5: 100.
in some embodiments of the present invention, the temperature of the dehydration reaction is 30 to 50 ℃.
In some embodiments of the present invention, after the dehydration reaction, the method further comprises: removing the solvent to obtain the 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene. In certain embodiments of the invention, the method of removing the solvent is rotary evaporation.
In certain embodiments of the present invention, prior to removing the solvent, further comprising: filtering, washing and combining organic phases.
The preparation method of the 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene provided by the invention can meet the requirement of preparing the catalyst without complicated post-treatment processes such as rectification and the like.
Compared with the method that lithium aluminum hydride is used as a reducing agent, the method has the advantages that 2,3,4, 5-tetramethyl-2-cyclopentenone is subjected to reduction reaction to prepare the 2,3,4, 5-tetramethyl-2-cyclopentadienol, the hydrogen and the metal supported catalyst are adopted, the hydrogen and the metal supported catalyst are removed by simple filtration after the reaction is finished, solid waste liquid is not generated, acid is not required to be added for neutralization, waste acid water and the like which are difficult to treat are not generated, and the catalyst has high catalytic efficiency and high selectivity. Meanwhile, hydrogen is used as a hydrogenation source, and the process is more energy-saving and environment-friendly.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to describe the preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene in detail, but should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all commercially available.
Example 1
Co/TiO2Preparation of the catalyst:
0.5mmol/L of CoC is taken4H6O4·4H2O, 500mg of TiO2Adding 5mL of deionized water, stirring for 30min, and adding 4mmol of NaBH4Stirring evenly, dripping 10mL of HCl with the concentration of 0.3mol/L, standing for 24 hours, centrifugally separating out solid,washing and drying to obtain Co/TiO2Catalyst, wherein the content of Co is 2 wt%.
A300 mL high-temperature high-pressure reactor was used, and 12mg of a metal-supported catalyst, 50g of 2,3,4, 5-tetramethyl-2-cyclopentenone, and 150mL of cyclohexane were added under a hydrogen atmosphere and stirred uniformly. Heating and pressurizing at 120 deg.C under 3 MPa. Hydrogenation reaction is carried out. After the reaction is completed, reducing the temperature and the pressure, taking out a product (2,3,4, 5-tetramethyl-2-cyclopentenol), filtering and placing in a round-bottom flask;
a dehydration reaction of 2,3,4, 5-tetramethyl-2-cyclopentenol to 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene was carried out by adding an H-type cation exchange resin catalyst of Dandong pearl to 2,3,4, 5-tetramethyl-2-cyclopentenol in a round-bottomed flask. The reaction temperature is 50 ℃, samples are taken every half an hour, and gas chromatography is used for detecting whether the 2,3,4, 5-tetramethyl-2-cyclopentenol is completely reacted or not. After completion of the reaction, the strongly acidic resin catalyst was filtered and washed, and the organic phases were combined and the solvent was removed by rotary evaporation to obtain 37.5g of a pale yellow product (i.e., 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene).
The obtained yellowish product was characterized by a nuclear magnetic spectrum, and the results are shown in fig. 1. FIG. 1 is a nuclear magnetic hydrogen spectrum of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene of example 1 of the present invention,1HNMR(CDCl3，ppm)：2.71(2H，s，CH2)，1.90(6H，s，CH3)，1.79(6H，s，CH3)。
the calculation shows that the yield of the 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene is 85 percent, and the purity is 90 percent. The catalyst can meet the requirement of preparing the catalyst without complicated post-treatment processes such as rectification and the like.
Example 2
The difference from example 1 is that the mass ratio of the metal-supported catalyst to the 2,3,4, 5-tetramethyl-2-cyclopentenone is 18 mg:50g, a pale yellow product (i.e., 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene) was obtained.
The calculation shows that the yield of the 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene is 80 percent, and the purity is 90 percent. The catalyst can meet the requirement of preparing the catalyst without complicated post-treatment processes such as rectification and the like.
Example 3
Compared with example 1, the mass ratio of the metal-supported catalyst to the 2,3,4, 5-tetramethyl-2-cyclopentenone is 25mg:50g, a pale yellow product (i.e., 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene) was obtained.
The calculation shows that the yield of the 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene is 87 percent, and the purity is 90 percent. The catalyst can meet the requirement of preparing the catalyst without complicated post-treatment processes such as rectification and the like.
Example 4
The hydrogenation reaction was carried out at a temperature of 150 ℃ as compared with example 1 to give a pale yellow product (i.e., 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene).
The calculation shows that the yield of the 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene is 85 percent, and the purity is 90 percent. The catalyst can meet the requirement of preparing the catalyst without complicated post-treatment processes such as rectification and the like.
Example 5
By changing the pressure of the hydrogenation reaction to 4MPa as compared with example 1, a pale yellow product (i.e., 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene) was obtained.
The calculation shows that the yield of the 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene is 85 percent, and the purity is 89 percent. The catalyst can meet the requirement of preparing the catalyst without complicated post-treatment processes such as rectification and the like.
Example 6
Compared with example 1, the metal supported catalyst is changed, and CoC of 0.3mmol/L is taken4H6O4·4H2O, 500mg of TiO2Adding 5mL of deionized water, stirring for 30min, and adding 4mmol of NaBH4Uniformly stirring, dropwise adding 10mL of HCl with the concentration of 0.3mol/L, standing for 24 hours, centrifugally separating out solids, washing and drying to obtain Co/TiO2Catalyst with a Co content of 1.5 wt% gave a pale yellow product (i.e. 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene).
The calculation shows that the yield of the 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene is 75 percent, and the purity is 90 percent. The catalyst can meet the requirement of preparing the catalyst without complicated post-treatment processes such as rectification and the like.
Comparative example 1
500mL round bottom Schlenk bottle 5g LiAlH was added4240mL of cyclohexane, stirred, and the mixture cooled to 0 ℃ in a cold water bath. 50g of 2,3,4, 5-tetramethyl-2-cyclopentenone was dropwise added to the mixed solution over 60 min.
After the reaction was complete, the ice-water bath was removed and replaced with an oil bath. The sample is placed in an environment of 30 ℃, the sample is taken every half an hour, and gas chromatography-mass spectrometry is used for detecting whether the 2,3,4, 5-tetramethyl-2-cyclopentenone completely reacts. After the reaction is completed, 30mL of water is dripped into the reaction kettle, and the rest LiAlH is inactivated and decomposed4Producing solids and bubbles. 30mL of a 33 wt% dilute sulfuric acid solution was added and stirred for 10min until the solids in the solution were dissolved out. The solution was neutralized with saturated sodium bicarbonate until the pH of the solution was 7, separated and extracted, the organic phases were combined and placed in a round bottom flask.
A dehydration reaction of 2,3,4, 5-tetramethyl-2-cyclopentenol to 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene was carried out by adding an H-type cation exchange resin catalyst of Dandong pearl to 2,3,4, 5-tetramethyl-2-cyclopentenol in a round-bottomed flask. Sampling at 50 deg.C for half an hour, and detecting whether 2,3,4, 5-tetramethyl-2-cyclopentenol has completely reacted by GC. After the reaction was completed, the strongly acidic resin catalyst was filtered and washed, and the organic phases were combined. According to the concepts of simplification, economy and the like, the solvent is removed by rotary evaporation to obtain 35g of light yellow product, the calculated yield is 80%, and the purity is 85%.
Comparative example 2
500mL round bottom Schlenk bottle 5g LiAlH was added4240mL of cyclohexane, stirred, and the mixture cooled to 0 ℃ in a cold water bath. 50g of 2,3,4, 5-tetramethyl-2-cyclopentenone was dropwise added to the mixed solution over 60 min.
After the reaction was complete, the ice-water bath was removed and replaced with an oil bath. Placing the sample at 30 deg.C, sampling every half an hour, and detecting 2,3,4 by GCWhether the reaction of 5-tetramethyl-2-cyclopentenone is complete or not. After the reaction is completed, 30mL of water is dripped into the reaction kettle, and the rest LiAlH is inactivated and decomposed4Producing solids and bubbles. 60mL of a 33 wt% dilute sulfuric acid solution was added and stirred for 10min until the solids in the solution were dissolved away, while the complete conversion of 2,3,4, 5-tetramethyl-2-cyclopentenol was detected by GC. The solution was then neutralized with saturated sodium bicarbonate until the solution pH was 7, separated and extracted, the organic phases combined and placed in a round bottom flask. Solvent removal using rotary evaporation gave 20g of a pale yellow product in 40% calculated yield and 85% purity.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene comprises the following steps:
A) carrying out hydrogenation reaction on a metal supported catalyst, 2,3,4, 5-tetramethyl-2-cyclopentenone and a solvent under the condition of hydrogen to obtain 2,3,4, 5-tetramethyl-2-cyclopentadienyl alcohol;
the metal-supported catalyst comprises a solid carrier and a metal supported on the solid carrier; the metal elements are selected from one or two of VIII main group elements;
B) under the action of strong acid resin catalyst, 2,3,4, 5-tetramethyl-2-cyclopentadiene alcohol is dehydrated to obtain 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene.
2. The method of claim 1, wherein the solid support comprises Al2O3、SiO2、TiO2Molecular sieves, activated carbon or carbon materials;
the metal is selected from one or two of Pd, Rh, Rt, Ni and Co;
the content of metal in the metal-supported catalyst is 0.8 wt% -2 wt%.
3. The preparation method according to claim 1, wherein the mass ratio of the metal-supported catalyst to the 2,3,4, 5-tetramethyl-2-cyclopentenone is 10 to 25mg:50 g.
4. The method of claim 1, wherein the solvent comprises one or more of ethanol, methanol, isopropanol, diethyl ether, hexane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
5. The preparation method according to claim 1, wherein the 2,3,4, 5-tetramethyl-2-cyclopentenone and the solvent are used in a ratio of 10-50 g: 150 mL.
6. The preparation method according to claim 1, wherein the temperature of the hydrogenation reaction is 80-250 ℃.
7. The preparation method according to claim 1, wherein the pressure of the hydrogenation reaction is 1 to 5 MPa.
8. The production method according to claim 1, wherein the strongly acidic resin-based catalyst comprises a small pore resin, a carbonic acid resin or a large pore strong acid resin.
9. The method according to claim 1, wherein the mass ratio of the mass of the strongly acidic resin catalyst to the mass of the 2,3,4, 5-tetramethyl-2-cyclopentadienol is 1 to 5: 100.
10. the method according to claim 1, wherein the temperature of the dehydration reaction is 30 to 50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110896375.0A CN113443951A (en) | 2021-08-05 | 2021-08-05 | Preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110896375.0A CN113443951A (en) | 2021-08-05 | 2021-08-05 | Preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113443951A true CN113443951A (en) | 2021-09-28 |
Family
ID=77818174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110896375.0A Pending CN113443951A (en) | 2021-08-05 | 2021-08-05 | Preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113443951A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100121332A (en) * | 2009-05-08 | 2010-11-17 | 주식회사 엘지화학 | Method for production of cyclopentadiene derivatives and composition for preparing cyclopentadiene derivatives |
| CN103261133A (en) * | 2010-12-21 | 2013-08-21 | 弗门尼舍有限公司 | Hydrogenation of esters or carbonyl groups with tetradentate amino/imino-hioether based ruthenium complexes |
| CN106866331A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of method that cyclopentadiene or dicyclopentadiene are prepared by furfuryl alcohol |
| CN107750243A (en) * | 2015-06-17 | 2018-03-02 | 弗门尼舍有限公司 | Use FE/ tridentate ligand complex compound hydrogenation of aldehydes or assimilation compound |
| CN111253201A (en) * | 2020-03-12 | 2020-06-09 | 山东京博中聚新材料有限公司 | Preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene |
-
2021
- 2021-08-05 CN CN202110896375.0A patent/CN113443951A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100121332A (en) * | 2009-05-08 | 2010-11-17 | 주식회사 엘지화학 | Method for production of cyclopentadiene derivatives and composition for preparing cyclopentadiene derivatives |
| CN103261133A (en) * | 2010-12-21 | 2013-08-21 | 弗门尼舍有限公司 | Hydrogenation of esters or carbonyl groups with tetradentate amino/imino-hioether based ruthenium complexes |
| CN107750243A (en) * | 2015-06-17 | 2018-03-02 | 弗门尼舍有限公司 | Use FE/ tridentate ligand complex compound hydrogenation of aldehydes or assimilation compound |
| CN106866331A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of method that cyclopentadiene or dicyclopentadiene are prepared by furfuryl alcohol |
| CN111253201A (en) * | 2020-03-12 | 2020-06-09 | 山东京博中聚新材料有限公司 | Preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene |
Non-Patent Citations (1)
| Title |
|---|
| M. C. AGUIRRE: ""MORPHOLOGICAL AND STRUCTURAL FEATURES OF CO/TIO2 CATALYSTS PREPARED BY DIFFERENT METHODS AND THEIR PERFORMANCE IN THE LIQUID PHASE HYDROGENATION OF α, β UNSATURATED ALDEHYDES"", 《 JOURNAL OF THE CHILEAN CHEMICAL SOCIETY》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shafaghat et al. | Catalytic hydrodeoxygenation of simulated phenolic bio-oil to cycloalkanes and aromatic hydrocarbons over bifunctional metal/acid catalysts of Ni/HBeta, Fe/HBeta and NiFe/HBeta | |
| CN100467432C (en) | Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol | |
| CN104355975B (en) | A kind of method of acetone two step synthesis methyl iso-butyl ketone (MIBK) | |
| CN102746087A (en) | Method for preparing cyclohexane by catalyzing and hydrogenising benzene at room temperature | |
| CN108126748B (en) | Alkaline monolithic catalyst with regular pore channels and preparation method and application thereof | |
| CN112341312A (en) | Method for preparing cyclohexanol and derivative thereof by selective hydrogenolysis of lignin | |
| JP6483861B2 (en) | Metal composite catalyst, its production method and utilization in the production of D, L-menthol | |
| CN109704902A (en) | Ionic liquid-catalyzed method of deoxidation during a kind of lignin derivative hydrogenation deoxidation | |
| CN113443951A (en) | Preparation method of 1,2,3, 4-tetramethyl-1, 3-cyclopentadiene | |
| CN110002970B (en) | Production method and production system of sandalwood ether | |
| CN101195600B (en) | Method for producing 4-hydroxyindole | |
| CN112010730A (en) | Green preparation method of diphenylmethane | |
| CN109174159B (en) | Fixed-point deuterium adding photocatalyst | |
| CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN116535315A (en) | Product separation method for preparing methyl glycolate from dimethyl oxalate | |
| CN112517067B (en) | Solid acid and preparation method thereof, solid acid-loaded microchannel reactor and preparation method thereof, and method for preparing hydroxycitronellal | |
| CN109046405A (en) | A kind of iodine supported catalyst, preparation method and a kind of preparation method of all-trans-vitamin A acetate | |
| CN109678655B (en) | Application of nickel-iron hydrotalcite catalyst in preparation of benzyl alcohol | |
| CN110075910A (en) | A kind of method of modifying for ethyl alcohol and benzene alkylation reaction IM-5 molecular sieve catalyst | |
| CN211645084U (en) | Separation of isoamyl alcohol and isoamyl acetate purification device | |
| CN102755909A (en) | Catalyst for preparing cyclohexane by benzene hydrogenation and preparation method thereof | |
| CN102190563A (en) | Method for preparing alpha-phenethyl alcohol by using supported zirconium oxide as catalyst | |
| CN107930693B (en) | Modified resin catalyst and method for removing residual formaldehyde in 3-methyl-3-butene-1-alcohol solution | |
| CN109337714A (en) | The preparation method of low naphthalene high boiling aromatic hydrocarbon solvent for rubber resin plasticizer | |
| CN112210055A (en) | Polymer with hollow core-shell structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210928 |
|
| RJ01 | Rejection of invention patent application after publication |