CN117024239A - Preparation method of cyclopentadiene derivative - Google Patents
Preparation method of cyclopentadiene derivative Download PDFInfo
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- CN117024239A CN117024239A CN202311005226.6A CN202311005226A CN117024239A CN 117024239 A CN117024239 A CN 117024239A CN 202311005226 A CN202311005226 A CN 202311005226A CN 117024239 A CN117024239 A CN 117024239A
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000741 silica gel Substances 0.000 claims abstract description 62
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 62
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 claims abstract description 27
- 238000011049 filling Methods 0.000 claims abstract description 25
- -1 cyclopentadiene alcohol derivative Chemical class 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000000945 filler Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 230000018044 dehydration Effects 0.000 claims abstract description 18
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 73
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 8
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 8
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000619 316 stainless steel Inorganic materials 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 239000000376 reactant Substances 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 12
- 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 description 9
- 239000002994 raw material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- JUVIRLWRBKTGFR-UHFFFAOYSA-N 2,3,3,4-tetramethylcyclopenten-1-ol Chemical compound CC1CC(O)=C(C)C1(C)C JUVIRLWRBKTGFR-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- DPUIHFSJVKUFBK-UHFFFAOYSA-N 1,2,3,4,5-pentamethylcyclopenta-1,3-diene ruthenium Chemical compound [Ru].CC1C(C)=C(C)C(C)=C1C.CC1C(C)=C(C)C(C)=C1C DPUIHFSJVKUFBK-UHFFFAOYSA-N 0.000 description 1
- FOMWRSGYNRQRAM-UHFFFAOYSA-N 4,4,5,5-tetramethylcyclopent-2-en-1-one Chemical compound CC1(C(C=CC1=O)(C)C)C FOMWRSGYNRQRAM-UHFFFAOYSA-N 0.000 description 1
- OXJUCLBTTSNHOF-UHFFFAOYSA-N 5-ethylcyclopenta-1,3-diene;ruthenium(2+) Chemical compound [Ru+2].CC[C-]1C=CC=C1.CC[C-]1C=CC=C1 OXJUCLBTTSNHOF-UHFFFAOYSA-N 0.000 description 1
- ITKUCIRMDIMBMM-UHFFFAOYSA-L [Cl-].[Cl-].CC1=C(C)C(C)=C(C)C1[Zr+2]C1C(C)=C(C)C(C)=C1C Chemical compound [Cl-].[Cl-].CC1=C(C)C(C)=C(C)C1[Zr+2]C1C(C)=C(C)C(C)=C1C ITKUCIRMDIMBMM-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/10—Chlorides
- C07C2527/11—Hydrogen chloride
-
- 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
- C07C2531/025—Sulfonic acids
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of cyclopentadiene derivatives, which comprises the following steps: (1) Uniformly mixing silica gel with a polymerization inhibitor, a dehydration catalyst and a solvent, and drying to obtain loaded silica gel; (2) Sequentially adding the loaded silica gel and the molecular sieve into a filling column, and forming a loaded silica gel layer and a molecular sieve layer in the filling column; placing the filled filler column horizontally, wherein one end of the filler column, which is close to the load silica gel layer, is a feed inlet, and the other end of the filler column is a discharge outlet; (3) Adding a cyclopentadiene alcohol derivative solution and an alkane solvent from the feed inlet, maintaining negative pressure of the discharge outlet, and collecting a mixed solution flowing out of the discharge outlet; (4) Concentrating the mixed solution collected in the step (3), and removing the solvent to obtain the cyclopentadiene derivative. The preparation method can effectively improve the conversion rate of the reactants and inhibit the self-polymerization of the products, can obtain the products with high purity without purification, and has the yield of more than 83%.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of a cyclopentadiene derivative.
Background
Cyclopentadiene and its derivative are one kind of important chemical material for preparing metallocene metal compound. Typical metallocene compounds include ferrocene (II), bis (ethylcyclopentadienyl) ruthenium (II), bis (pentamethylcyclopentadienyl) ruthenium (II), bis (tetramethylcyclopentadienyl) zirconium (IV) dichloride, and the like, and these metallocene compounds are synthesized independently of cyclopentadiene and its derivatives.
Taking tetramethyl cyclopentadiene as an example, the traditional synthesis method is to reduce tetramethyl cyclopentenone into tetramethyl cyclopentenol by lithium aluminum hydride, and then obtain tetramethyl cyclopentadiene after catalytic dehydration by p-toluenesulfonic acid. In the reaction of the second catalytic dehydration, two major problems of insufficient conversion rate of raw materials and self-polymerization of products are often faced. Specifically, the water and diethyl ether generated by the reaction are not mutually soluble, and the solubility of the p-toluenesulfonic acid in water is far greater than that of the diethyl ether, so that the catalyst is distributed in a large amount in an aqueous phase, the effective concentration of the catalyst in an organic phase is reduced, the reaction is difficult to continue, and the conversion rate of raw materials is 75-85%. Although the reaction conversion is further improved by prolonging the reaction time, adding p-toluenesulfonic acid, and properly heating, these measures accelerate the self-polymerization of the product, severely affecting the yield.
In view of the above, there is a need for a process for preparing cyclopentadiene derivatives which can improve the conversion of the starting materials while also effectively avoiding the autopolymerization of the products.
Disclosure of Invention
The invention provides a preparation method of cyclopentadiene derivatives, which is characterized in that a reaction device is constructed by filling silica gel and molecular sieve loaded with a catalyst and a polymerization inhibitor into a filling column, the cyclopentadiene derivatives are prepared by the reaction device, the conversion rate of raw material cyclopentadiene alcohol derivatives can be effectively improved, meanwhile, the self-polymerization of product cyclopentadiene derivatives can be effectively avoided, the product with high purity can be obtained without purification, and the yield can be more than 83%.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of cyclopentadiene derivatives, which comprises the following steps:
(1) Uniformly mixing silica gel with a polymerization inhibitor, a dehydration catalyst and a solvent, and drying to obtain loaded silica gel;
(2) Sequentially adding the loaded silica gel and the molecular sieve into a filling column, and forming a loaded silica gel layer and a molecular sieve layer in the filling column; placing the filled filler column horizontally, wherein one end of the filler column, which is close to the load silica gel layer, is a feed inlet, and the other end of the filler column is a discharge outlet;
(3) Dissolving a cyclopentadiene alcohol derivative shown in a formula (I) in an ether solvent to obtain a cyclopentadiene alcohol derivative solution, then adding the cyclopentadiene alcohol derivative solution and an alkane solvent into a feed port of the filling column in sequence, maintaining negative pressure of a discharge port, and collecting a mixed solution flowing out of the discharge port;
(4) Concentrating the mixed solution collected in the step (3), and removing the solvent to obtain a cyclopentadiene derivative shown in the formula (II);
the structures of the above formula (I) and formula (II) are as follows:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, C to C20 alkyl groups.
Further, in the step (1), the silica gel is 300-400 mesh chromatographic silica gel.
Further, in the step (1), the polymerization inhibitor is selected from one or more of 2, 6-di-tert-butyl-p-cresol, p-cresol and hydroquinone.
Further, in the step (1), the dehydration catalyst is selected from one or more of p-toluenesulfonic acid, p-nitrobenzenesulfonic acid, benzenesulfonic acid and hydrochloric acid.
Further, in the step (1), the mass ratio of the silica gel to the polymerization inhibitor to the dehydration catalyst is 100:0.05-0.2:0.5-2, for example, in some preferred embodiments, the mass ratio is 100:0.1:1.
Further, in the step (1), the solvent is selected from one or more of diethyl ether, n-pentane, n-hexane, methyl tertiary butyl ether and isopropyl ether.
Further, in the step (2), the layer thickness ratio of the silica gel layer to the molecular sieve layer is 1:1-10.
Further, in the step (2), the material of the packing column is glass, 316 stainless steel or polypropylene.
Further, in the step (3), the ether solvent is one or more of diethyl ether, methyl tertiary butyl ether and isopropyl ether.
Further, in step (3), the molar ratio of cyclopentadienyl alcohol derivative to the dehydration catalyst in the cyclopentadienyl alcohol derivative solution is 20-100:1, such as 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, etc., including but not limited to the molar ratios listed above.
Further, in the step (3), the alkane solvent is selected from one or more of n-pentane, n-hexane and n-heptane.
Further, in the step (3), after the solution flowing out from the discharge port is detected by GC-MS, the collection is stopped.
Further, in the step (4), the negative pressure is 10-80kPa.
Further, the cyclopentadiene derivatives include, but are not limited to, tetramethyl cyclopentadiene, pentamethyl cyclopentadiene; i.e. R 1 -R 4 Is methyl, R 5 Is H or methyl.
Compared with the prior art, the invention has the beneficial effects that:
1. based on the problems of insufficient conversion rate of raw materials and self-polymerization of products in the process of preparing cyclopentadiene derivatives in the prior art, a reaction device is constructed by filling silica gel loaded with a catalyst and a polymerization inhibitor and a molecular sieve in a filling column, reactants enter the filling column from a feed inlet close to the loaded silica gel, a discharge outlet is connected with negative pressure to keep that materials can flow from the feed inlet to the discharge outlet, when the reactants flow through the loaded silica gel, the reactants are catalyzed and dehydrated to generate products, and the products are kept stable under the action of the polymerization inhibitor, so that the self-polymerization risk of the products is effectively reduced, after the products are eluted by an alkane solvent, water is adsorbed by the molecular sieve to obtain a mixed solution containing the products, and the products are obtained after the solvent is concentrated and removed; the reaction device is simple and high in applicability, the conversion rate of raw materials can be improved to 98%, the risk of self-polymerization of products can be effectively reduced, and the high-purity products can be obtained through direct concentration treatment of feed liquid collected by a discharge hole of the device.
2. The method for preparing the cyclopentadiene derivative has simple operation and high reaction efficiency, the yield of the target product can reach more than 83%, and the product with the purity of 99.9% can be obtained without post-treatment and purification.
Drawings
FIG. 1 is a schematic structural diagram of a packed column of a reaction apparatus, wherein (1) is a loaded silica gel, (2) is a molecular sieve, (3) is a feed inlet, and (4) is a discharge outlet.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items. The term "comprising" or "comprises" as used herein means that it may include or comprise other components in addition to the components described. The term "comprising" or "comprising" as used herein may also be replaced by "being" or "consisting of" closed.
As described in the background art, the existing cyclopentadiene and derivatives thereof have the problems of insufficient raw material conversion rate and self-polymerization of products in the preparation process, so that the purification process is complex and the yield is low.
In order to solve the technical problems, the embodiment of the invention provides a preparation method of a cyclopentadiene derivative, which comprises the following steps:
(1) Uniformly mixing silica gel with a polymerization inhibitor, a dehydration catalyst and a solvent, and drying to obtain loaded silica gel;
(2) Sequentially adding the loaded silica gel and the molecular sieve into a filling column, and forming a loaded silica gel layer and a molecular sieve layer in the filling column; placing the filled filler column horizontally, wherein one end of the filler column, which is close to the load silica gel layer, is a feed inlet, and the other end of the filler column is a discharge outlet, as shown in fig. 1;
(3) Dissolving a cyclopentadiene alcohol derivative shown in a formula (I) in an ether solvent to obtain a cyclopentadiene alcohol derivative solution, then adding the cyclopentadiene alcohol derivative solution and an alkane solvent into a feed port of the filling column in sequence, maintaining negative pressure of a discharge port, and collecting a mixed solution flowing out of the discharge port;
(4) Concentrating the mixed solution collected in the step (3), and removing the solvent to obtain a cyclopentadiene derivative shown in the formula (II);
the structures of the above formula (I) and formula (II) are as follows:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, C to C20 alkyl groups.
Based on the problems of insufficient conversion rate of raw materials and self-polymerization of products in the process of preparing cyclopentadiene derivatives in the prior art, a reaction device is constructed by filling silica gel loaded with a catalyst and a polymerization inhibitor and a molecular sieve in a filling column, reactants enter the filling column from a feed inlet close to the loaded silica gel, a discharge outlet is connected with negative pressure to keep that materials can flow from the feed inlet to the discharge outlet, when the reactants flow through the loaded silica gel, the reactants are catalyzed and dehydrated to generate products, and the products are kept stable under the action of the polymerization inhibitor, so that the self-polymerization risk of the products is effectively reduced, after the products are eluted by an alkane solvent, water is adsorbed by the molecular sieve to obtain a mixed solution containing the products, and the products are obtained after the solvent is concentrated and removed; the reaction device can effectively improve the conversion rate of raw materials and effectively reduce the risk of self-polymerization of the product, and can obtain the product with high purity and high yield without further purification treatment.
In some preferred embodiments of the invention, the silica gel may be 300-400 mesh chromatography silica gel, but the invention is not limited to the type of silica gel.
In some preferred embodiments of the invention, the polymerization inhibitor can be selected from one or more of 2, 6-di-tert-butyl-p-cresol, p-cresol and hydroquinone, and the polymerization inhibitor is modified on the surface of silica gel, so that the self-polymerization of the product is effectively reduced, and the yield is improved; in addition, the dehydration catalyst can be selected from one or more of p-toluenesulfonic acid, p-nitrobenzenesulfonic acid, benzenesulfonic acid and hydrochloric acid; the dehydration catalyst is modified on the surface of silica gel, so that reactants can be dehydrated to generate products under the action of the dehydration catalyst, and a large amount of the dehydration catalyst can be effectively prevented from being dissolved in water, thus the reaction is not affected, and the conversion rate of the reactants is improved.
More specifically, the mass ratio of the silica gel to the polymerization inhibitor to the dehydration catalyst is 100:0.05-0.2:0.5-2, for example, at a mass ratio of 100:0.1:1.
In some preferred embodiments of the present invention, in step (1), the solvent is selected from one or more of diethyl ether, n-pentane, n-hexane, methyl tert-butyl ether, isopropyl ether.
In some preferred embodiments of the invention, the layer thickness ratio of the loaded silica gel layer to the molecular sieve layer in the packing column is 1:1-10, e.g., 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc., including but not limited to the layer thickness ratios listed above; by regulating and controlling the layer thickness of the silica gel layer and the molecular sieve layer, the reaction is fully carried out, and meanwhile, the water in the product can be effectively removed.
In some preferred embodiments of the present invention, the material of the packing column may be glass, 316 stainless steel or polypropylene, but is not limited to the above materials, and has good acid and alkali resistance and does not react with reactants and products.
In some preferred embodiments of the present invention, in step (3), the ethereal solvent may be one or more of diethyl ether, methyl tert-butyl ether, isopropyl ether.
In some preferred embodiments of the invention, the molar ratio of cyclopentadienyl alcohol derivative in the cyclopentadienyl alcohol derivative solution to the dehydration catalyst added in step (1) is from 20 to 100:1, such as 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, etc., including but not limited to the molar ratios listed above.
In some preferred embodiments of the present invention, the alkane solvent is selected from one or more of n-pentane, n-hexane, n-heptane.
In some preferred embodiments of the invention, the collection is stopped after the effluent solution from the outlet is confirmed to be free of product by GC-MS detection.
In some preferred embodiments of the present invention, the negative pressure at the discharge port is 10-80kPa, such as 10kPa, 20kPa, 30kPa, 40kPa, 50kPa, 60kPa, 70kPa, 80kPa, etc., including but not limited to the negative pressure pressures listed above. The pressure of the negative pressure at the discharge port cannot be too high, and the reaction efficiency is affected if the flow speed is too slow due to the fact that the pressure is too high, for example, more than 80 kPa; but at the same time, the pressure cannot be too small, for example, if the pressure is smaller than 10kPa, the volatilization speed of the product is too high, and the yield is affected; therefore, the negative pressure at the discharge port is controlled in a proper range, so that the reaction efficiency is improved on the premise of not affecting the yield.
In some preferred embodiments of the present invention, cyclopentadiene derivatives include, but are not limited to, tetramethyl cyclopentadiene, pentamethyl cyclopentadiene.
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
Example 1
The embodiment provides a synthesis method of tetramethyl cyclopentadiene, which comprises the following steps:
(1) 861mg (5 mmol) of p-toluenesulfonic acid, 86.1mg of 2, 6-di-tert-butyl-p-cresol, 86.1g of silica gel and 43g of diethyl ether are weighed and mixed uniformly, and the solvent is evaporated to dryness to obtain the supported silica gel.
(2) Loading the loaded silica gel and the molecular sieve prepared in the step (1) into a filling column, and forming a loaded silica gel layer and a molecular sieve layer in the filling column, wherein the layer thickness ratio of the loaded silica gel layer to the molecular sieve layer is 1:2; and horizontally placing the filled filler column, wherein one end of the filler column, which is close to the load silica gel layer, is a feed inlet, and the other end of the filler column is a discharge outlet.
(3) Weighing 14.2g (100 mmol) of tetramethyl cyclopentenol, dissolving in 10g of diethyl ether, sequentially adding an diethyl ether solution of tetramethyl cyclopentenol and n-pentane from a feed inlet, maintaining a negative pressure at a discharge port to collect the solution, and stopping collecting the solution after confirming no product by GC-MS detection; the negative pressure of the discharge hole is 40kPa.
(4) The solution collected in step (3) was concentrated to obtain 10.2g (83.6 mmol) of a pale yellow liquid, and the yield was 83.6%.
The products were subjected to nuclear magnetism and GC-MS characterization tests, with the following results:
1 H NMR(400MHz,CDCl 3 ):δ(ppm)＝2.77(s,2H),1.96(s,6H),1.85(s,6H).
the purity of the product was 99.9% by GC-MS.
Example 2
The embodiment provides a synthesis method of pentamethylcyclopentadiene, which comprises the following steps:
(1) 861mg (5 mmol) of p-toluenesulfonic acid, 86.1mg of 2, 6-di-tert-butyl-p-cresol, 86.1g of silica gel and 43g of diethyl ether are weighed and mixed uniformly, and the solvent is evaporated to dryness to obtain the supported silica gel.
(2) Loading the loaded silica gel and the molecular sieve prepared in the step (1) into a filling column, and forming a loaded silica gel layer and a molecular sieve layer in the filling column, wherein the layer thickness ratio of the loaded silica gel layer to the molecular sieve layer is 1:2; and horizontally placing the filled filler column, wherein one end of the filler column, which is close to the load silica gel layer, is a feed inlet, and the other end of the filler column is a discharge outlet.
(3) Weighing 15.4g (100 mmol) of pentamethylcyclopentenol, dissolving in 10g of diethyl ether, sequentially adding the diethyl ether solution of pentamethylcyclopentenol and n-pentane from a feed inlet, maintaining a negative pressure at a discharge port to collect the solution, and stopping collecting the solution after confirming no product by GC-MS detection; the negative pressure of the discharge hole is 40kPa.
(4) The solution collected in step (3) was concentrated to obtain 11.6g (85.2 mmol) of a pale yellow liquid, and the yield was 85.2%.
The products were subjected to nuclear magnetism and GC-MS characterization tests, with the following results:
1 H NMR(400MHz,CDCl 3 ):δ(ppm)＝3.01(t,1H),2.21(s,6H),1.79(s,6H),0.46(d,2H).
the purity of the product was 98.8% by GC-MS.
Comparative example 1
This comparative example relates to the synthesis of tetramethyl cyclopentadiene, and differs from example 1 in that: in the step (1), the polymerization inhibitor 2, 6-di-tert-butyl-p-cresol is not added, and the specific operation is as follows:
(1) The p-toluenesulfonic acid 861mg (5 mmol), the silica gel 86.1g and the diethyl ether 43g are weighed and evenly mixed, and the solvent is evaporated to dryness to obtain the load silica gel.
(2) Loading the loaded silica gel and the molecular sieve prepared in the step (1) into a filling column, and forming a loaded silica gel layer and a molecular sieve layer in the filling column, wherein the layer thickness ratio of the loaded silica gel layer to the molecular sieve layer is 1:2; and horizontally placing the filled filler column, wherein one end of the filler column, which is close to the load silica gel layer, is a feed inlet, and the other end of the filler column is a discharge outlet.
(3) Weighing tetramethyl cyclopentenol (14.2 g,100 mmol) and dissolving in 10g diethyl ether, sequentially adding an diethyl ether solution of tetramethyl cyclopentenol and n-pentane from a feed inlet, maintaining a negative pressure at a discharge port to collect the solution, and stopping collecting the solution after confirming no product by GC-MS detection; the negative pressure of the discharge hole is 40kPa.
(4) Concentrating the solution collected in the step (3) to obtain a light yellow slightly viscous liquid.
The product is subjected to GC-MS characterization test, and the purity of the product is found to be about 88%, and the main impurities are dimers and multimers of the current product.
Comparative example 2
The comparative example relates to the synthesis of tetramethyl cyclopentadiene, which is prepared by a one-pot method, and comprises the following specific operations:
14.2g (100 mmol) of tetramethyl cyclopentenol, 861mg (5 mmol) of p-toluenesulfonic acid, 86.1mg of 2, 6-di-tert-butyl-p-cresol and 53g of diethyl ether are weighed into a reaction flask, stirred at room temperature for 0.5h, quenched with water, extracted with diethyl ether, and the organic phases are combined and concentrated to remove the solvent to obtain a pale yellow slightly viscous liquid.
The products were subjected to GC-MS characterization tests, and the test results showed that the purity of the products was 74% and that the main impurities were dimers and multimers of the current products.
Comparative example 3
This comparative example relates to the synthesis of tetramethyl cyclopentadiene, and differs from comparative example 2 in that: the reaction time is prolonged, and the specific operation is as follows:
14.2g (100 mmol) of tetramethyl cyclopentenol, 861mg (5 mmol) of p-toluenesulfonic acid, 86.1mg of 2, 6-di-tert-butyl-p-cresol and 53g of diethyl ether are weighed into a reaction bottle, stirred at room temperature for 2h, quenched with water, extracted with diethyl ether, and the organic phases are combined and concentrated to remove the solvent to obtain a dark yellow viscous liquid.
GC-MS characterization test is carried out on the product, and the test result shows that the main component in the product is dimers and multimers of tetramethyl cyclopentadiene, and no target product peak is found.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A process for the preparation of a cyclopentadiene derivative comprising the steps of:
(1) Uniformly mixing silica gel with a polymerization inhibitor, a dehydration catalyst and a solvent, and drying to obtain loaded silica gel;
(2) Sequentially adding the loaded silica gel and the molecular sieve into a filling column, and forming a loaded silica gel layer and a molecular sieve layer in the filling column; placing the filled filler column horizontally, wherein one end of the filler column, which is close to the load silica gel layer, is a feed inlet, and the other end of the filler column is a discharge outlet;
(3) Dissolving a cyclopentadiene alcohol derivative shown in a formula (I) in an ether solvent to obtain a cyclopentadiene alcohol derivative solution, then adding the cyclopentadiene alcohol derivative solution and an alkane solvent into a feed port of the filling column in sequence, maintaining negative pressure of a discharge port, and collecting a mixed solution flowing out of the discharge port;
(4) Concentrating the mixed solution collected in the step (3), and removing the solvent to obtain a cyclopentadiene derivative shown in the formula (II);
the structures of the above formula (I) and formula (II) are as follows:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, C to C20 alkyl groups.
2. The method according to claim 1, wherein in the step (1), the silica gel is a 300-400 mesh chromatography silica gel;
the polymerization inhibitor is selected from one or more of 2, 6-di-tert-butyl-p-cresol, p-cresol and hydroquinone;
the dehydration catalyst is selected from one or more of p-toluenesulfonic acid, p-nitrobenzenesulfonic acid, benzenesulfonic acid and hydrochloric acid;
the solvent is selected from one or more of diethyl ether, n-pentane, n-hexane, methyl tertiary butyl ether and isopropyl ether.
3. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the silica gel to the polymerization inhibitor to the dehydration catalyst is 100:0.05-0.2:0.5-2.
4. The method of claim 1, wherein in step (2), the layer thickness ratio of the loaded silica gel layer to the molecular sieve layer is 1:1-10.
5. The method according to claim 1, wherein in the step (2), the filler column is made of glass, 316 stainless steel or polypropylene.
6. The method according to claim 1, wherein in the step (3), the ether solvent is one or more of diethyl ether, methyl tert-butyl ether and isopropyl ether.
7. The method according to claim 1, wherein in the step (3), the molar ratio of the cyclopentadienyl alcohol derivative to the dehydration catalyst in the cyclopentadienyl alcohol derivative solution is 20 to 100:1.
8. The method according to claim 1, wherein in the step (3), the alkane solvent is one or more selected from n-pentane, n-hexane and n-heptane.
9. The method according to claim 1, wherein in the step (4), the negative pressure is 10 to 80kPa.
10. The process of claim 1, wherein R is 1 -R 4 Is methyl, R 5 Is H or methyl.
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