CN112457148A - Method for synthesizing high-purity MDPES (methyl diphenylsulfone) raw material phenyl acetylene in one step - Google Patents
Method for synthesizing high-purity MDPES (methyl diphenylsulfone) raw material phenyl acetylene in one step Download PDFInfo
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- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002994 raw material Substances 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- -1 methyl diphenylsulfone Chemical compound 0.000 title abstract description 7
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- SHKKTLSDGJRCTR-UHFFFAOYSA-N 1,2-dibromoethylbenzene Chemical compound BrCC(Br)C1=CC=CC=C1 SHKKTLSDGJRCTR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000004821 distillation Methods 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002309 gasification Methods 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000000526 short-path distillation Methods 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 2
- 238000004508 fractional distillation Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000004451 qualitative analysis Methods 0.000 claims description 2
- 238000004445 quantitative analysis Methods 0.000 claims description 2
- 238000010183 spectrum analysis Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007269 dehydrobromination reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000007529 inorganic bases Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000891 luminescent agent Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of biological medicine, in particular to a method for synthesizing high-purity MDPES (methyl diphenylsulfone) raw material phenylacetylene in one step, which comprises the following steps: in a solvent, 1, 2-dibromoethylbenzene and alkali are stirred and mixed uniformly, then the temperature is raised to 40-160 ℃ for complete reaction, bromide is removed by filtration, and then filtrate is distilled and separated, wherein one group of separated substances is a recyclable solvent, the other group of separated substances is a product phenylacetylene, and the GC purity is more than 98%; according to the invention, the solvents are mixed and stirred, the temperature is raised to 40-160 ℃ after stirring for complete reaction, bromide is removed by filtration, the GC purity is greatly improved by distilling and separating filtrate, the GC purity is higher than 98%, the steps for synthesizing phenyl acetylene are shortened, the utilization rate of phenyl acetylene raw materials is high, the solvent can be recovered, the product yield is high, the product purity is higher, and the product is more environment-friendly, so that the industrial production requirements are met, and the method is more suitable for popularization and application.
Description
Technical Field
The invention relates to the technical field of biological medicines, in particular to a method for synthesizing high-purity MDPES (methyl diphenylsulfone) raw material phenylacetylene in one step.
Background
Phenylacetylene, also known as phenylacetylene, is an organic compound and is flammable when exposed to open fire, high temperature and an oxidant; the combustion produces the stimulation smog. Due to the unsaturation of carbon-carbon triple bonds, the aryl substituted aryl can be used as a high molecular monomer for preparing polymers, and can be used as a luminescent and electroluminescent material due to the conjugation, so that the aryl substituted aryl is an essential intermediate for preparing a symmetrical arynyl linear fused ring chemical luminescent agent.
The most important role of phenylacetylene is to prepare polymer resins, which are also known as addition polymerization resins. Resins synthesized by polymerization (polyaddition) reactions. Formed from molecules containing double or triple bonds or bifunctional molecules formed by ring opening of cyclic molecules. The general linear polymer has thermoplasticity, and the polyphenylacetylene has the characteristics of photoconduction, electric conduction, paramagnetic energy migration, conversion and the like, has stable performance, is a novel conductive polymer material, and the phenylacetylene derivative polymer is widely used for liquid crystal materials, luminescent materials, nonlinear optical materials, gas separation membranes, magnetic materials and the like. Phenyl acetylene is also an important organic synthesis intermediate, and has very wide application prospect in the fields of biomedicine, medicine, pesticide and the like. The phenylacetylene of the company is mainly used for preparing a silicon alkyne resin high-end composite material and MDPES (modified poly-phenylethynyl amine), and the silicon alkyne resin high-end composite material and MDPES are widely applied to the fields of military nuclear power, aerospace and aviation, integrated circuit boards, 5G high-frequency communication and the like.
The preparation method of phenylacetylene has been reported and has no patent protection, and the comprehensive analysis mainly comprises the following four routes:
(1): adding bromine into styrene, and removing hydrogen bromide from lithium amide. Its advantage is high output rate up to 90%. However, lithium amide needs to be prepared by reacting metal lithium with liquid ammonia, and the conditions are harsh, so that industrial production is difficult to realize.
(2): beta-bromostyrene and potassium hydroxide solid are melted and reacted to prepare the catalyst. The method is a high-temperature reaction under a strong alkali condition, has high requirements on equipment materials, is relatively serious in equipment corrosion, high in energy consumption, serious in pollution and poor in production operation feasibility. The yield is low and is less than 50 percent.
(3): adding bromine into styrene for bromination, removing hydrogen bromide by potassium hydroxide at high temperature in a methanol system, and distilling by water vapor to obtain the styrene. The dehydrobromination reaction in the route is violent in heat release, so that the material is easy to spray, the safety production risk is high, a large amount of high-concentration high-salinity sewage is generated by steam distillation, and the environmental protection pressure is high. The yield is low, and the product purity is not high, about 96 percent.
(4): the aryl halide and the derivatives thereof are used as raw materials, noble metals such as rhodium, platinum, palladium, nickel, ketone and the like are used as catalysts, and the aryl halide is prepared by Sonogashira reaction or improved Sonogashira coupling reaction. The method adopts a pyridine/triethylamine mixed solvent which is difficult to remove, and the post-treatment comprises the complex processes of removing the solvent by decompression, washing, filtering, column chromatography separation, concentration, recrystallization and the like, thus being not beneficial to industrial production and environmental protection requirements. And the use of noble metals such as palladium and the like has high cost, and the industrial application of the catalyst is seriously limited.
The application of the phenylacetylene is very wide, but the safety and environmental protection pressure in the production process is high, the price cost of raw materials is very high, the purity of the produced product is low, the low purity of the product greatly influences the quality of the product, and the popularization and application of the phenylacetylene are severely limited due to the low purity of the product and other factors, so that the method for developing the phenylacetylene which is economical, practical, excellent in quality and low in price and is environment-friendly has very important practical significance, and the method for synthesizing the high-purity MDPES raw material phenylacetylene in one step is provided.
SUMMARY OF THE PATENT FOR INVENTION
The invention aims to provide a method for synthesizing high-purity MDPES (methyl diphenylsulfone) raw material phenylacetylene in one step, and solves the problem that the popularization and application of the conventional phenylacetylene are seriously limited by factors such as high safety and environmental protection pressure, high price cost, low quality purity and the like in production of the phenylacetylene.
In order to achieve the purpose, the invention provides the following technical scheme: the one-step synthesis process of high purity MDPES material phenylacetylene includes the following steps:
step 1: in the solvent, 1, 2-dibromo ethyl benzene and alkali are stirred and mixed evenly, heated to 40-160 ℃ for reaction to be complete, and filtered to remove bromide;
step 2: and (3) distilling and separating the filtrate, wherein one group of separated substances are recyclable solvents, the other group of separated substances are the product phenylacetylene, and the GC purity is more than 98%.
Preferably, in step 1, the solvent of the reaction system is dichloroethane, chloroform, tetrachloromethane, tetrahydrofuran, ethyl acetate, dimethyl carbonate, petroleum ether, hexane, heptane, toluene, chlorobenzene, DMF, DME, sulfolane, or the like. Including a single solvent and a mixture of two or more solvents.
Preferably, in step 1, the base is inorganic or organic base such as triethylamine, sodium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium amide, sodium methoxide, sodium ethoxide, and the like, and includes single base and mixed bases of two or more.
Preferably, in the step 1, the reaction temperature is 40 ℃ to 160 ℃, and preferably the reaction temperature is the boiling point and the condensation reflux temperature of each solvent.
Preferably, in the step 1, the molar ratio of the 1, 2-dibromoethylbenzene to the base is 1: 1-10, and the preferred molar ratio is 1: 2.1.
preferably, in step 2, the distillation separation method is a distillation separation method such as vacuum distillation, atmospheric distillation, vacuum rectification, atmospheric rectification, pressure rectification, short path distillation, thin film distillation, and the like, and includes a single distillation method and two or more mixed distillation separation methods, preferably a vacuum distillation separation method.
Preferably, in step 2, distillation separation is performed by fractional distillation using the difference in boiling point of the polymer or by recrystallization to purify the polymer.
Preferably, in step 2, the purity of the product is analyzed after gasification, and the product is used in combination with red light and spectral analysis or mass spectrometry to achieve high accuracy by using chromatography as a means for separating complex samples.
Preferably, in step 2, the product purity is detected by a gas chromatograph, and during detection, the compound is qualitatively analyzed according to the peak emergence time and sequence shown in the figure, and the compound is quantitatively analyzed according to the peak height and area size.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the solvents are mixed and stirred, the temperature is raised to 40-160 ℃ after stirring, the reaction is carried out till the reaction is complete, bromide is removed by filtering, and then the filtrate is distilled, separated and purified, so that the GC purity is greatly improved and is more than 98%, so that the steps of synthesizing phenyl acetylene are shortened, the utilization rate of the phenyl acetylene raw material is higher, the product yield is higher, the solvents can be recycled, the purity of the products after production is higher and the products are more environment-friendly, the quality of the products is effectively improved, the phenyl acetylene meets the requirements of industrial mass production better, and the phenyl acetylene is more suitable for popularization and application.
Synthetic reaction equation of phenylacetylene
Drawings
FIG. 1 is a table of analysis results of an embodiment of the present invention;
FIG. 2 is a table of two analysis results of the patent example of the present invention;
FIG. 3 is a table of analysis results of the patent example of the present invention;
FIG. 4 is a table of analysis results of an embodiment of the present invention;
FIG. 5 is a table of the results of a fifth analysis of examples of the present invention;
FIG. 6 is a table of six analysis results of the patented example of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by a person skilled in the art based on the embodiments in the patent of the invention without any inventive work belong to the protection scope of the patent of the invention.
Referring to fig. 1 to 6, the present invention provides a technical solution: the one-step synthesis process of high purity MDPES material phenylacetylene includes the following steps:
step 1: in a solvent, 1, 2-dibromoethylbenzene and alkali are stirred and mixed uniformly, then the temperature is raised to 40-160 ℃ for complete reaction, bromide is removed by filtration, the solvent of a reaction system in the step 1 is dichloroethane, chloroform, tetrachloromethane, tetrahydrofuran, ethyl acetate, dimethyl carbonate, petroleum ether, hexane, heptane, toluene, chlorobenzene, DMF, DME, sulfolane and other solvents, the solvent comprises a single solvent and two or more mixed solvents, the alkali in the step 1 is inorganic and organic alkali such as triethylamine, sodium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium amide, sodium methoxide, sodium ethoxide and the like, the alkali comprises a single alkali and two or more mixed alkalis, the reaction temperature in the step 1 is 40-160 ℃, the preferred reaction temperature is the boiling point and the condensation reflux temperature of each solvent, the molar ratio of the 1, 2-dibromoethylbenzene to the alkali in the step 1 is 1: 1-10, the preferred molar ratio is 1: 2.1;
step 2: distilling and separating the filtrate, wherein one group of the separated substances is a recyclable solvent, the other group of the separated substances is a product phenylacetylene, the GC purity is more than 98%, the distillation and separation method in the step 2 is a distillation and separation method such as reduced pressure distillation, atmospheric distillation, pressurized distillation, short-path distillation, thin film distillation and the like, and comprises a single distillation method and two or more than two mixed distillation and separation methods, preferably the reduced pressure distillation and separation method, the distillation and separation in the step 2 utilizes a method of carrying out fractionation or recrystallization by utilizing different boiling points of polymers, and then carrying out refining and purification, in the step 2, the product purity is analyzed after gasification and is matched with a red light and absorption spectrum method or a mass spectrometry method, the chromatography is used as a means for separating complex samples to achieve higher accuracy, the product purity in the step 2 is detected by a gas chromatograph, and the peak-out time and sequence are shown in the figure during, and (4) carrying out qualitative analysis on the compound, and carrying out quantitative analysis on the compound according to the height and the area of the peak.
The first embodiment is as follows:
160ml of dichloroethane, 52.8g (0.2mol) of 1, 2-dibromoethylbenzene, 20.24g (0.2mol) of triethylamine and 11.78g (0.21mol) of potassium hydroxide are added into a 500ml three-neck flask, the mixture is stirred uniformly, heated and refluxed until the residue of the 1, 2-dibromoethylbenzene is less than or equal to 0.5 percent of the raw material, then the mixture is filtered, filter cakes are washed by dichloroethane, and then the filtrates are combined and distilled under reduced pressure to obtain phenylacetylene with the yield of 96.2 percent and the GC purity of 99.26 percent.
Example two:
160ml of tetrahydrofuran, 52.8g (0.2mol) of 1, 2-dibromoethylbenzene and 22.68g (0.42mol) of sodium methoxide are added into a 500ml three-neck flask, the mixture is stirred uniformly, heated and refluxed until the residue of the 1, 2-dibromoethylbenzene is less than or equal to 0.5 percent, filtered, filter cakes are washed by tetrahydrofuran, and then the filtrates are combined and distilled under reduced pressure to obtain phenylacetylene with the yield of 97.5 percent and the GC purity of 99.14 percent.
Example three:
160ml of petroleum ether, 52.8g (0.2mol) of 1, 2-dibromoethyl benzene and 22.68g (0.42mol) of sodium methoxide are added into a 500ml three-neck flask and stirred uniformly, and the mixture is heated and refluxed until the residue of the 1, 2-dibromoethyl benzene is less than or equal to 0.5 percent. The filtration was carried out, the filter cake was washed with petroleum ether, and then the filtrates were combined and distilled under reduced pressure to give phenylacetylene in a yield of 91.3% with a GC purity of 99.56%.
Example four:
160ml of heptane, 52.8g (0.2mol) of 1, 2-dibromoethylbenzene, 26.64g (0.2mol) of potassium carbonate and 11.78g (0.21mol) of potassium hydroxide are added into a 500ml three-neck flask, the mixture is uniformly stirred and heated to reflux until the residue of the raw material 1, 2-dibromoethylbenzene is less than or equal to 0.5%. Filtration was carried out, the filter cake was washed with heptane, and then the filtrates were combined and distilled under reduced pressure to give phenylacetylene in a yield of 86.4% with a GC purity of 99.70%.
Example five:
160ml of toluene, 52.8g (0.2mol) of 1, 2-dibromoethylbenzene and 23.56g (0.42mol) of potassium hydroxide are added into a 500ml three-neck flask, the mixture is stirred uniformly, heated and refluxed until the residue of the 1, 2-dibromoethylbenzene is less than or equal to 0.5 percent, filtered, the filter cake is washed by toluene, and then the filtrate is combined and rectified to obtain phenylacetylene with the yield of 90.2 percent and the GC purity of 99.48 percent.
Example six:
160ml of sulfolane, 52.8g (0.2mol) of 1, 2-dibromoethyl benzene and 16.8g (0.42mol) of sodium hydroxide are added into a 500ml three-neck flask, the mixture is stirred uniformly, heated and refluxed until the residue of the 1, 2-dibromoethyl benzene is less than or equal to 0.5 percent, the mixture is filtered, a filter cake is washed by sulfolane, and then the filtrates are combined and distilled under reduced pressure to obtain phenylacetylene with the yield of 85.6 percent and the GC purity of 98.24 percent.
Although embodiments of the present patent have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the present patent, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The method for synthesizing high-purity MDPES raw material phenylacetylene in one step is characterized by comprising the following steps of: the method comprises the following steps:
step 1: in the solvent, 1, 2-dibromo ethyl benzene and alkali are stirred and mixed evenly, heated to 40-160 ℃ for reaction to be complete, and filtered to remove bromide;
step 2: and (3) distilling and separating the filtrate, wherein one group of separated substances are recyclable solvents, the other group of separated substances are the product phenylacetylene, and the GC purity is more than 98%.
2. The one-step method for synthesizing high-purity MDPES raw material phenylacetylene as claimed in claim 1, which is characterized in that: in the step 1, the solvent of the reaction system is dichloroethane, chloroform, tetrachloromethane, tetrahydrofuran, ethyl acetate, dimethyl carbonate, petroleum ether, hexane, heptane, toluene, chlorobenzene, DMF, DME, sulfolane and the like, and comprises a single solvent and a mixed solvent of two or more.
3. The one-step method for synthesizing high-purity MDPES raw material phenylacetylene as claimed in claim 1, which is characterized in that: in the step 1, the alkali is inorganic or organic alkali such as triethylamine, sodium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium amide, sodium methoxide, sodium ethoxide and the like, and comprises single alkali and mixed alkali of two or more.
4. The one-step method for synthesizing high-purity MDPES raw material phenylacetylene as claimed in claim 1, which is characterized in that: in the step 1, the reaction temperature is 40 ℃ to 160 ℃, and the preferable reaction temperature is the boiling point and the condensation reflux temperature of each solvent.
5. The one-step method for synthesizing high-purity MDPES raw material phenylacetylene as claimed in claim 1, which is characterized in that: in the step 1, the molar ratio of the 1, 2-dibromoethylbenzene to the alkali is 1: 1-10, preferably 1: 2.1.
6. the one-step method for synthesizing high-purity MDPES raw material phenylacetylene as claimed in claim 1, which is characterized in that: in the step 2, the distillation separation method is a distillation separation method such as vacuum distillation, atmospheric distillation, vacuum rectification, atmospheric rectification, pressurized rectification, short-path distillation, thin film distillation and the like, and comprises a single distillation method and two or more mixed distillation separation methods, preferably a vacuum distillation separation method.
7. The one-step method for synthesizing high-purity MDPES raw material phenylacetylene as claimed in claim 1, which is characterized in that: in the step 2, distillation separation is carried out by utilizing the difference of the boiling points of the polymers to carry out fractional distillation or by utilizing a recrystallization method to carry out purification.
8. The one-step method for synthesizing high-purity MDPES raw material phenylacetylene as claimed in claim 1, which is characterized in that: in step 2, the purity of the product needs to be analyzed after gasification, and the product is used in combination with a red light and spectral analysis method or a mass spectrometry method, and the chromatography is used as a means for separating complex samples, so that high accuracy is achieved.
9. The one-step method for synthesizing high-purity MDPES raw material phenylacetylene as claimed in claim 1, which is characterized in that: in the step 2, the purity of the product is detected by a gas chromatograph, qualitative analysis is carried out on the compound according to the peak emergence time and sequence shown in the figure during detection, and quantitative analysis is carried out on the compound according to the height and the area of the peak.
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| CN114181028A (en) * | 2021-12-21 | 2022-03-15 | 山东博苑医药化学股份有限公司 | Preparation method of phenylacetylene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62145030A (en) * | 1985-12-18 | 1987-06-29 | Denki Kagaku Kogyo Kk | Production of phenylacetylene compound |
| CN108191917A (en) * | 2018-01-09 | 2018-06-22 | 中国科学技术大学 | A kind of opto-electronic conversion molecule of auto-control and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62145030A (en) * | 1985-12-18 | 1987-06-29 | Denki Kagaku Kogyo Kk | Production of phenylacetylene compound |
| CN108191917A (en) * | 2018-01-09 | 2018-06-22 | 中国科学技术大学 | A kind of opto-electronic conversion molecule of auto-control and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181028A (en) * | 2021-12-21 | 2022-03-15 | 山东博苑医药化学股份有限公司 | Preparation method of phenylacetylene |
| CN114181028B (en) * | 2021-12-21 | 2023-10-24 | 山东博苑医药化学股份有限公司 | Preparation method of phenylacetylene |
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