CN116969821A - Method for photo-thermal catalysis of hydration carbonylation reaction of 4-tert-butyl phenylacetylene by using carbon nano tube - Google Patents
Method for photo-thermal catalysis of hydration carbonylation reaction of 4-tert-butyl phenylacetylene by using carbon nano tube Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 32
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 27
- 230000036571 hydration Effects 0.000 title claims abstract description 27
- ZSYQVVKVKBVHIL-UHFFFAOYSA-N 1-tert-butyl-4-ethynylbenzene Chemical group CC(C)(C)C1=CC=C(C#C)C=C1 ZSYQVVKVKBVHIL-UHFFFAOYSA-N 0.000 title claims description 31
- 238000006555 catalytic reaction Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 239000012363 selectfluor Substances 0.000 claims abstract description 24
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 22
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 18
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 230000006315 carbonylation Effects 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 75
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 13
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 8
- -1 aryl alkyne Chemical class 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002730 mercury Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NHUBNHMFXQNNMV-UHFFFAOYSA-N 2-ethynylpyridine Chemical compound C#CC1=CC=CC=N1 NHUBNHMFXQNNMV-UHFFFAOYSA-N 0.000 description 1
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical group NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Natural products CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FFFMSANAQQVUJA-UHFFFAOYSA-N but-1-ynylbenzene Chemical compound CCC#CC1=CC=CC=C1 FFFMSANAQQVUJA-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 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
- C07C45/26—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydration of carbon-to-carbon triple bonds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for catalyzing aryl acetylene hydration carbonylation reaction by utilizing photo-thermal effect of carbon nano tubes, belonging to the technical field of catalysts. The method utilizes a photochemistry synthesis method, uses a xenon lamp as a light source, uses Carbon Nanotubes (CNTs) as a photo-thermal material, uses tetrabutylammonium bromide and a selective fluorine reagent Selectfluor as additives, and realizes hydration carbonylation of aryl alkyne under the action of Al, and when the reaction is carried out for 6 hours, the separation yield of carbonyl products is up to 81 percent. The method utilizes photocatalysis to efficiently realize alkyne carbonylation under the mild conditions of no acid and strong oxidant.
Description
Technical Field
The invention relates to a green chemical synthesis method, in particular to a method for catalyzing aryl acetylene hydration carbonylation reaction under the condition of milder conditions by utilizing the photo-thermal effect of carbon nano tubes, belonging to the technical field.
Background
The carbonylation reaction is used as a method for forming carbon-oxygen bonds, and has high application value in the total synthesis of natural products. Aryl carboxylic acid, aryl amino acid, aryl ester and their derivatives can be prepared from carbonyl chemical precursors such as aryl ethyl ketone, aryl acetaldehyde and the like, and the prepared chemicals are also very synthesized into a plurality of natural products and medicamentsAn important intermediate. Berthelot 1860 discovered the hydration of acetylene in sulfuric acid. At the same time, kutscheroff found that mercury salt catalyzed alkyne hydration reactions were able to generate propyne gases, and the concept of alkyne hydration began to appear. The industrial production of acetic acid in germany started in 1916, namely, the hydration of acetylene to acetaldehyde, followed by the catalytic air oxidation of manganese. Acetylene was initially prepared from water and calcium carbide, but after 1940, CH 4 The thermal cracking process of (2) gradually replaces the energy-intensive decomposition process of carbide, becoming a source for producing acetylene. The method of hydrating acetylene has been used for large scale production of a variety of industrial chemicals. In 1938, the hydrated carbonylation of terminal alkynes in organic media was discovered, until 1970, acetylene was still an important organic feedstock for the production of vinyl derivatives, acrylates and alkyne chemicals.
In various traditional synthesis methods of carbonyl compounds, the catalytic addition reaction of water and alkyne is also called hydration reaction, and the synthesis method takes unsaturated hydrocarbon precursors as raw materials, and has the advantages of simplicity and high efficiency. However, most alkyne hydration reactions reported use catalysts that are catalyzed on the basis of toxic or expensive transition metals. For example, the classical Kucherov reaction is that in HgSO 4 -H 2 SO 4 Under catalysis, alkyne and water undergo nucleophilic addition reaction to generate aldehyde or ketone, and the reaction is easy, but the use of mercury salt is very harmful to human beings and the environment. With the high global economy and science and technology but serious pollution, toxic mercury waste treatment has been an inherent problem of hydration reactions, alkyne hydration processes based on metals other than mercury have been studied for many years to develop new, more efficient alkyne hydration processes. Accordingly, scientists have been striving to develop safer, easier to handle alkyne carbonylation reactions.
With the rapid development of global economy and technology, humans are increasingly aware of the importance of sustainable development. Many synthetic chemists are focusing on the direction of green chemistry. With the advent and rapid development of photocatalytic free radical reactions, people began to think about replacing traditional organic reactions with more environmentally friendly photochemical processes.
Disclosure of Invention
The invention solves the technical problems that: the method does not use strong acid and strong alkali, has mild conditions, can be carried out at normal temperature and normal pressure, and synthesizes carbonylation products in a green and efficient way.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for catalyzing 4-tert-butyl phenylacetylene hydration carbonylation reaction by utilizing photo-thermal effect of carbon nano tube comprises the following specific steps:
weighing tetrabutylammonium bromide and aluminum sheet, adding the tetrabutylammonium bromide and the aluminum sheet into a container, adding 4-tert-butylphenylacetylene and acetonitrile, dissolving, taking a fluorine reagent Selectfluor, dissolving in water, adding the fluorine reagent Selectfluor into the mixed solution, adding the carbon nano tube, and stirring the reaction under the irradiation of a xenon lamp to obtain a target product, wherein the reaction route is as follows:
preferably, tetrabutylammonium bromide and an aluminum sheet are weighed and added into a glass bottle together, 4-tertiary butyl phenylacetylene and acetonitrile are added, the mixture is dissolved, a fluorine reagent Selectfluor is taken and dissolved in water, then the mixture is added into the mixture and added into a carbon nano tube, the reaction is stirred under the irradiation of a xenon lamp, the TLC plate is used for detecting the reaction progress, acetonitrile is removed by spin evaporation after the reaction is finished, ethyl acetate is added for extraction, an organic phase is washed three times by anhydrous sodium sulfate for drying, the organic phase is collected and concentrated on the spin evaporation, the obtained crude product is separated and purified by a silica gel chromatographic column, and the ethyl acetate/normal hexane is used as an eluent to obtain a pure target product.
Preferably, the volume ratio of acetonitrile to water is 1:1.
preferably, the conversion of the reaction substrate can be completed by illumination reaction for 6 hours at normal temperature and normal pressure.
Preferably, after the reaction is completed, the temperature of the reaction system can reach 40 ℃.
Preferably, the molar ratio of 4-tert-butylphenylacetylene, tetrabutylammonium bromide and Selectfluor is: 1:5:3. wherein the mass ratio of the carbon nano tube to the Selectfluor is as follows: 5:2.
preferably, 2mmol of tetrabutylammonium bromide is weighed in a glove box, and added into a glass bottle together with a 1cm×1cm piece of aluminum sheet, then 52.5 μl of 0.4mmol of 4-tert-butylphenylacetylene and 8mL of acetonitrile are added, dissolved, 0.425g of 1.2mmol of Selectfluor is dissolved in 8mL of aqueous solution, then the above mixed solution is added and 1g of 8-15nm carbon nanotube is added, the reaction is stirred under irradiation of a xenon lamp, the progress of the reaction is detected by TLC plate, acetonitrile is distilled off by spin, then ethyl acetate is added for extraction, and the organic phase is washed three times with water, dried by anhydrous sodium sulfate, the organic phase is collected and concentrated on spin distillation, the obtained crude product is separated and purified by a silica gel chromatographic column, the pure target product is obtained by using ethyl acetate/n-hexane as eluent, and the separation yield is 81% and the HPLC yield is 96.5%.
The invention has the beneficial effects that:
(1) A research method for catalyzing aryl alkyne hydration reaction by utilizing photo-thermal effect of carbon nano tube is disclosed, the carbon nano tube can absorb light with almost all wavelengths, has good heat transfer performance, CNTs have very large length-diameter ratio, thus the heat exchange performance along the length direction is very high, the heat exchange performance along the opposite vertical direction is relatively low, and the carbon nano tube can synthesize high anisotropic heat conduction material through proper orientation. In addition, the carbon nano tube has higher heat conductivity, and the heat conductivity of the composite material can be possibly improved greatly as long as a trace amount of carbon nano tube is doped in the composite material.
(2) The method is simple and easy to operate, and the carbon nano tube is directly used as a photo-thermal material to catalyze the hydration carbonylation reaction of the 4-tert-butyl phenylacetylene at normal temperature and normal pressure. The method can obtain the separation yield of the target ketone product of 81% in a short time.
(3) The method can directly utilize sunlight as a light source, has good yield under gram-scale reaction, and provides possibility for the method to be applied to mass production in the future.
(4) The aluminum of the invention is replaced by copper, zinc and other metals, the conversion rate of the catalytic 4-tertiary butyl phenylacetylene hydration carbonylation reaction effect is extremely low, or the tetrabutylammonium bromide of the invention is replaced by tetrabutylammonium iodide, tetrabutylammonium tetrafluoroborate and the like, the conversion rate of the catalytic 4-tertiary butyl phenylacetylene hydration carbonylation reaction effect is extremely low, the combination of the invention has the catalytic 4-tertiary butyl phenylacetylene hydration carbonylation reaction, and the separation yield of the high target ketone product is 81 percent. The yield of catalytic methyl 4-formate phenylacetylene was only 71% as in example 2.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 shows the applied nuclear magnetic pattern (A) and the high-efficiency liquid phase pattern (B) of the photo-thermal catalysis 4-tert-butylphenylacetylene hydration carbonylation reaction of carbon nano-tubes.
FIG. 2 shows the application of carbon nanotube photo-thermal catalysis of 4-methyl formate phenylacetylene hydration carbonylation reaction (A), nuclear magnetic resonance chart (B) and high efficiency liquid phase chart (C).
FIG. 3 shows the application of carbon nanotube in photo-thermal catalysis of hydration carbonylation of 4-tert-butylphenylacetylene.
Detailed Description
Example 1
2mmol of tetrabutylammonium bromide was weighed in a glove box and added to a glass bottle together with a 1 cm. Times.1 cm piece of aluminum, followed by 52.5. Mu.L (0.4 mmol) of 4-tert-butylphenylacetylene and 8mL of acetonitrile, and dissolved. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of an aqueous solution, and then added to the above mixed solution and 1g of carbon nanotubes (Qianfeng, 8-15 nm) were added. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. The conversion of the reaction substrate can be completed after the illumination reaction for 6 hours at normal temperature and normal pressure. After the reaction is finished, the temperature of the reaction system can reach 40 ℃.
After the reaction was completed, acetonitrile was removed by spin-evaporation, followed by extraction with ethyl acetate, and the organic phase was washed three times with water. After drying over anhydrous sodium sulfate, the organic phase was collected and concentrated on rotary evaporation, and the crude product obtained was concentrated. Purification by silica gel chromatography (eluting with ethyl acetate/n-hexane) afforded the pure target product in 81% isolation and 96.5% HPLC yield.
FIG. 1 shows the applied nuclear magnetic pattern (A) and the high-efficiency liquid phase pattern (B) of the photo-thermal catalysis 4-tert-butyl phenylacetylene hydration carbonylation reaction of carbon nano tubes, and the structure of the product and the conversion rate of the product are respectively proved.
Example 2
2mmol of tetrabutylammonium bromide was weighed in a glove box and added to a glass bottle together with a 1 cm. Times.1 cm piece of aluminum, followed by addition of 64mmg (0.4 mmol) of 4-methyl phenylacetylene formate and 8mL of acetonitrile and dissolution. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of water and 1g of carbon nanotubes was added, followed by addition to the above mixed solution. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. After the reaction was completed, acetonitrile was removed by spin-evaporation, followed by extraction with ethyl acetate, and the organic phase was washed three times with water. After drying over anhydrous sodium sulfate, the organic phase was collected and concentrated on rotary evaporation, and the crude product obtained was concentrated. Purification by silica gel chromatography (eluting with ethyl acetate/n-hexane) afforded the pure target product in 71% isolated yield and 83% HPLC yield.
FIG. 2 shows the application of carbon nanotube photo-thermal catalysis of 4-methyl formate phenylacetylene hydration carbonylation reaction (A), nuclear magnetic resonance chart (B) and high efficiency liquid phase chart (C), respectively demonstrating the structure of the product and the conversion rate of the product.
Comparative example
1. 0.644g (2 mmol,5 equiv) of tetrabutylammonium bromide was weighed in a glove box, added to a glass bottle together with a 1 cm. Times.1 cm piece of aluminum, and then 52.5. Mu.L of 4-tert-butylphenylacetylene and 8mL of acetonitrile were added and dissolved. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of water and 0.5g and 1.5g of carbon nanotubes were added, respectively, and then added to the above mixed solution. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. It was found by examination that too many or too few carbon nanotubes affect the conversion efficiency of the reaction, resulting in a decrease in the conversion efficiency. When 0.5g of carbon nanotubes was used, 8 hours were required to achieve the full conversion of the substrate, while when 1.5g was used, 6.5 hours were required to achieve the full conversion of the substrate.
2. 0.644g (2 mmol,5 equiv) of tetrabutylammonium bromide was weighed in a glove box and added to a glass bottle together with a 1 cm. Times.1 cm piece of aluminum, followed by the addition of 46.8mmg of 4-aminophenylacetylene and 8mL of acetonitrile, and dissolved. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of water and 1g of carbon nanotubes was added, followed by addition to the above mixed solution. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. The reaction was found to be non-taking place by detection, and the target product was not detected.
3. 0.644g (2 mmol,5 equiv) of tetrabutylammonium bromide was weighed in a glove box and added to a glass bottle together with a 1 cm. Times.1 cm piece of aluminum, followed by 41.2mmg of 2-ethynylpyridine and 8mL of acetonitrile, and dissolved. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of water and 1g of carbon nanotubes was added, followed by addition to the above mixed solution. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. It was found by detection that the reaction did not occur and the target product was not detected, and the reaction system was not suitable for alkynes containing nitrogen heterocycles.
4. 0.644g (2 mmol,5 equiv) of tetrabutylammonium bromide was weighed in a glove box, added to a glass bottle together with a 1 cm. Times.1 cm piece of aluminum, and then 52mmg of 1-phenyl-1-butyne and 8mL of acetonitrile were added and dissolved. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of water and 1g of carbon nanotubes was added, followed by addition to the above mixed solution. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. By detection, the reaction was not occurred, no target product was detected, and the reaction system was not suitable for non-terminal alkynes.
5. 0.644g (2 mmol,5 equiv) of tetrabutylammonium bromide was weighed in a glove box and placed in a glass bottle together with a 1 cm. Times.1 cm piece of aluminum, followed by 71.22mmg of 4-acetylenyl and 8mL of acetonitrile, and dissolved. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of water and 1g of carbon nanotubes was added, followed by addition to the above mixed solution. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. After the reaction is finished, the product is separated and purified, and the target product is obtained with only 39 percent of yield.
6. 2mmol of tetrabutylammonium bromide was weighed in a glove box and added to a glass bottle together with a 1 cm. Times.1 cm piece of copper, followed by 52.5. Mu.L (0.4 mmol) of 4-tert-butylphenylacetylene and 8mL of acetonitrile, and dissolved. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of an aqueous solution, and then added to the above mixed solution and 1g of carbon nanotubes (Qianfeng, 8-15 nm) were added. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. As a result, it was found that no reaction occurred.
7. 2mmol of tetrabutylammonium bromide was weighed in a glove box and added to a glass bottle together with a 1 cm. Times.1 cm zinc sheet, followed by 52.5. Mu.L (0.4 mmol) of 4-tert-butylphenylacetylene and 8mL of acetonitrile, and dissolved. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of an aqueous solution, and then added to the above mixed solution and 1g of carbon nanotubes (Qianfeng, 8-15 nm) were added. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. As a result, it was found that the formation of the target product was not monitored.
9. 0.738g (2 mmol,5 equiv) of tetrabutylammonium iodide was weighed in a glove box, added to a glass bottle together with a 1 cm. Times.1 cm piece of aluminum, and then 52.5. Mu.L of 4-tert-butylphenylacetylene and 8mL of acetonitrile were added and dissolved. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of water and 1g of carbon nanotubes was added, followed by addition to the above mixed solution. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. After the reaction was completed, the conversion of the target product was only 37.5%.
10. 0.658g (2 mmol,5 equiv) of tetrabutylammonium tetrafluoroborate was weighed in a glove box, added to a glass bottle together with a 1 cm. Times.1 cm piece of aluminum, and then 52.5. Mu.L of 4-t-butylphenylacetylene and 8mL of acetonitrile were added and dissolved. 0.425g (1.2 mmol,3 equiv) of SelectFluor was dissolved in 8mL of water and 1g of carbon nanotubes was added, followed by addition to the above mixed solution. The reaction was stirred under irradiation of a xenon lamp, and progress of the reaction was detected by TLC plate. After the reaction, the conversion of the target product was only 19.6%.
Claims (7)
1. A method for catalyzing hydration carbonylation of 4-tertiary butyl phenylacetylene by utilizing photo-thermal effect of carbon nano tubes is characterized by comprising the following specific steps:
weighing tetrabutylammonium bromide and aluminum sheet, adding the tetrabutylammonium bromide and the aluminum sheet into a container, adding 4-tert-butylphenylacetylene and acetonitrile, dissolving, taking a fluorine reagent Selectfluor, dissolving in water, adding the fluorine reagent Selectfluor into the mixed solution, adding the carbon nano tube, and stirring the reaction under the irradiation of a xenon lamp to obtain a target product, wherein the reaction route is as follows:
2. the method for catalyzing the hydration carbonylation reaction of 4-tertiary butyl phenylacetylene by utilizing the photo-thermal effect of carbon nano tubes according to claim 1, wherein the method comprises the following steps: the preparation method comprises the steps of weighing tetrabutylammonium bromide and an aluminum sheet, adding the tetrabutylammonium bromide and the aluminum sheet into a glass bottle, adding 4-tert-butylphenylacetylene and acetonitrile, dissolving, taking a fluorine reagent Selectfluor, dissolving in water, adding the mixed solution and adding a carbon nano tube, stirring the reaction under the irradiation of a xenon lamp, detecting the reaction progress by using a TLC plate, removing acetonitrile by spin evaporation after the reaction is finished, adding ethyl acetate for extraction, washing an organic phase for three times, drying by anhydrous sodium sulfate, collecting the organic phase, concentrating on the spin evaporation, separating and purifying the obtained crude product by using a silica gel chromatographic column, and obtaining a pure target product by using ethyl acetate/normal hexane as an eluent.
3. The method for catalyzing the hydration carbonylation reaction of 4-tertiary butyl phenylacetylene by utilizing the photo-thermal effect of carbon nano tubes according to claim 2, wherein the method comprises the following steps: the volume ratio of acetonitrile to water is 1:1.
4. the method for catalyzing the hydration carbonylation reaction of 4-tertiary butyl phenylacetylene by utilizing the photo-thermal effect of carbon nano tubes according to claim 2, wherein the method comprises the following steps: the conversion of the reaction substrate can be completed after the illumination reaction for 6 hours at normal temperature and normal pressure.
5. The method for catalyzing the hydration carbonylation reaction of 4-tertiary butyl phenylacetylene by utilizing the photo-thermal effect of carbon nano tubes according to claim 2, wherein the method comprises the following steps: after the reaction is finished, the temperature of the reaction system can reach 40 ℃.
6. The method for catalyzing the hydration carbonylation reaction of 4-tertiary butyl phenylacetylene by utilizing the photo-thermal effect of carbon nano tubes according to claim 1, wherein the method comprises the following steps: the molar ratio of 4-tert-butylphenylacetylene, tetrabutylammonium bromide and Selectfluor is: 1:5:3, wherein the mass ratio of the carbon nano tube to the Selectfluor is 5:2.
7. the method for catalyzing the hydration carbonylation reaction of 4-tertiary butyl phenylacetylene by utilizing the photo-thermal effect of carbon nano tubes according to claim 1, wherein the method comprises the following steps: 2mmol of tetrabutylammonium bromide was weighed in a glove box together with a piece of 1cm×1cm aluminum sheet into a glass bottle, then 52.5 μl of 0.4mmol of 4-tert-butylphenylacetylene and 8mL of acetonitrile were added, dissolved, 0.425g of 1.2mmol of Selectfluor was dissolved in 8mL of aqueous solution, then the above mixed solution was added and 1g of 8-15nm carbon nanotube was added, the reaction was stirred under irradiation of a xenon lamp, and the progress of the reaction was detected by TLC plate, after the completion of the reaction, acetonitrile was distilled off by spin, ethyl acetate was then added for extraction, and the organic phase was washed three times with water, dried by anhydrous sodium sulfate, the obtained crude product was concentrated on spin evaporation, separated and purified by silica gel column, with ethyl acetate/n-hexane as eluent, to obtain the pure target product in a yield of 81%, isolated yield by HPLC 96.5%.
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