CN114181028A - Preparation method of phenylacetylene - Google Patents
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- CN114181028A CN114181028A CN202111572771.4A CN202111572771A CN114181028A CN 114181028 A CN114181028 A CN 114181028A CN 202111572771 A CN202111572771 A CN 202111572771A CN 114181028 A CN114181028 A CN 114181028A
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- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007256 debromination reaction Methods 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 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
- 230000007547 defect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 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
- VWFQXDQOONOJEQ-UHFFFAOYSA-N 1-ethynyl-2,3-dimethoxybenzene Chemical group COC1=CC=CC(C#C)=C1OC VWFQXDQOONOJEQ-UHFFFAOYSA-N 0.000 description 1
- MODAETKWQRGIHI-UHFFFAOYSA-N 1-ethynyl-9,10-diphenylanthracene Chemical class C12=CC=CC=C2C(C=2C=CC=CC=2)=C2C(C#C)=CC=CC2=C1C1=CC=CC=C1 MODAETKWQRGIHI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007269 dehydrobromination reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000891 luminescent agent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 239000003016 pheromone Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation 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
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07C1/26—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
- C07C1/30—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 by splitting-off the elements of hydrogen halide from a single molecule
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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 phenylacetylene, which comprises the steps of taking brominated styrol as a raw material and also serving as a reaction solvent, heating the system to react under the condition of a catalyst, stopping the reaction after detecting that the concentration of the brominated styrol is stable, filtering to remove insoluble substances, distilling the reaction liquid at normal pressure, collecting 140-143 ℃ fraction, namely a product, distilling the residual kettle residue under reduced pressure, and collecting 100-105 ℃ fraction for use in the next reaction. The method has the advantages of simple operation, mild conditions, less three wastes generated in the production process, low environmental protection pressure, low cost, high yield and the like, has wide application prospect, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of biological medicines, and particularly relates to a preparation method of phenylacetylene.
Background
Phenylacetylene is an important electronic chemical raw material and an organic synthesis intermediate, and the phenylacetylene derivative shows excellent reaction characteristics in the synthesis and application of medicaments, insect pheromone synthesis, electrode materials, chemiluminescent materials, new liquid crystal materials and the like, so that the phenylacetylene derivative is widely regarded. For example, dimethoxyphenylacetylene is a synthetic precursor of a natural drug; various substituted phenylacetylenes containing fluorine substituents are excellent liquid crystal material intermediates; various substituted phenylacetylenes can also be used for preparing good chemiluminescent materials.
The phenylacetylene is an intermediate necessary for preparing the symmetrical aryne linear condensed ring chemical luminescent agent, and the polymer polyphenylacetylene has the characteristics of light guide, electric conduction, paramagnetism, energy migration, conversion and the like, is soluble and meltable, has stable performance, and is a novel conductive high polymer material. Phenylacetylene from this company is mainly used to prepare 9, 10-diphenylethynyl anthracene series of compounds, which is the most commonly used class of phosphor molecules in POCl systems.
The preparation method of phenylacetylene has been reported and comprehensively analyzed, and 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.
Aiming at the defects of high safety and environmental protection pressure, high production cost, high equipment requirement and the like in the production process of the prior art, the preparation method of phenylacetylene disclosed by the invention has the advantages of simple operation, mild conditions, less three wastes generated in the production process, low environmental protection pressure, low cost and the like, is suitable for industrial production, and has wide market prospect.
Disclosure of Invention
The invention aims to overcome the defects of high safety and environmental protection pressure, high production cost, high equipment requirement and the like in the prior art and provide a preparation method of phenylacetylene.
The preparation method of the invention comprises the following steps:
(1) debromination reaction: taking bromo-styrol as a raw material and also serving as a reaction solvent, heating the system to react under the condition of a catalyst, keeping the temperature to react for more than 2 hours, stopping the reaction, and filtering to remove insoluble substances.
Synthetic reaction equation of phenylacetylene
(2) Collecting finished products: and (2) distilling the filtrate obtained in the step (1) at normal pressure, collecting the 140-143 ℃ fraction, namely the product phenylacetylene, and detecting the purity by using a gas chromatography to be more than 98%.
(3) The solvent is used mechanically: and (3) carrying out reduced pressure distillation on the residual kettle residue in the step (2), collecting the fraction at 100-105 ℃, namely the brominated styrol, and mechanically applying the fraction to the next batch of reaction.
The catalyst in the step (1) is one or more of zinc powder, iron powder, aluminum powder, magnesium powder, tetrabutylammonium bromide, di-n-butylamine, tri-n-butylamine, triethylamine, sodium hydroxide, potassium hydroxide, sodium amide, lithium amide, sodium methoxide and sodium ethoxide, and preferably the zinc powder and the iron powder.
And (2) carrying out heat preservation reaction on the system in the step (1) for more than 2 hours, and preferably carrying out reaction for 4-6 hours.
And (3) carrying out reduced pressure distillation, wherein the pressure is required to be lower than-0.08 MP, and preferably-0.08 to-0.1 MPa.
Compared with the prior art, the invention has the beneficial effects that:
1. the method has the advantages of simple operation, advanced process, less three wastes generated in the production process, low environmental protection pressure and almost clean production.
2. The method has the advantages of mild reaction conditions, low requirements on equipment, low production cost and suitability for industrial production.
3. The product yield is more than 80 percent, even can be higher than 90 percent, and the GC purity is more than 98 percent.
Detailed Description
The advantageous effects of the present invention will now be further described by the following examples, which should be understood as being for illustrative purposes only and not limiting the scope of the present invention, and that changes and modifications apparent to those of ordinary skill in the art in light of the present invention are also included within the scope of the present invention.
The first embodiment is as follows:
183g (1mol) of bromostyrol and 39g (0.6mol) of zinc powder are added into a 250ml three-neck flask, the mixture is stirred uniformly under the protection of nitrogen, the mixture is heated to 100 ℃ and is kept for reaction for 6 hours, the reaction is stopped, the filtration is carried out, a filter cake is drained, the filtrate is distilled under normal pressure, 88.2g of distillate at 140 ℃ to 143 ℃ is collected, namely, the product phenylacetylene, the yield is 86.5 percent, and the GC purity is 98.8 percent. And carrying out reduced pressure distillation on the residual kettle residue under the pressure of-0.095 MP, and collecting 17.3g of fraction at 100-105 ℃, namely the brominated styrol, and applying the next batch of experiment.
Example two:
183g (1mol) of bromostyrol and 33.6g (0.6mol) of iron powder are added into a 250ml three-neck flask, the mixture is stirred uniformly under the protection of nitrogen, the mixture is heated to 100 ℃ and is kept warm for reacting for 6 hours, the reaction is stopped, the filtration is carried out, a filter cake is pumped to be dry, the filtrate is distilled under normal pressure, 82.1g of fraction at 140 ℃ to 143 ℃ is collected, namely phenylacetylene is the product, the yield is 80.5%, and the GC purity is 98.1%. And carrying out reduced pressure distillation on the residual kettle residue under the pressure of-0.095 MP, and collecting 19.5g of fraction at 100-105 ℃, namely the brominated styrol, and applying the next batch of experiment.
Example three:
183g (1mol) of bromostyrol and 39g (0.6mol) of zinc powder are added into a 250ml three-neck flask, the mixture is stirred uniformly under the protection of nitrogen, the mixture is heated to 120 ℃ and is kept for reaction for 6 hours, the reaction is stopped, the filtration is carried out, a filter cake is drained, the filtrate is distilled under normal pressure, 90.3g of distillate at 140-143 ℃ is collected, namely phenylacetylene is obtained, the yield is 88.5%, and the GC purity is 98.9%. And carrying out reduced pressure distillation on the residual kettle residue under the pressure of-0.095 MP, and collecting 16.8g of fraction at 100-105 ℃, namely the brominated styrol, and applying the next batch of experiment.
Example four:
183g (1mol) of bromostyrol and 39g (0.6mol) of zinc powder are added into a 250ml three-neck flask, the mixture is stirred uniformly under the protection of nitrogen, the mixture is heated to 120 ℃ and kept for reaction for 8 hours, the reaction is stopped, the filtration is carried out, a filter cake is drained, the filtrate is distilled under normal pressure, 92.0g of distillate at 140-143 ℃ is collected, namely phenylacetylene is obtained, the yield is 90.2%, and the GC purity is 99.1%. And carrying out reduced pressure distillation on the residual kettle residue under the pressure of-0.095 MP, and collecting 13.1g of fraction at 100-105 ℃, namely the brominated styrol, and applying the next batch of experiment.
Example five:
183g (1mol) of bromostyrol and 80g (2.1mol) of sodium amide are added into a 250ml three-neck flask, the mixture is stirred uniformly under the protection of nitrogen, the mixture is heated to 120 ℃ and is kept for 4 hours of reaction, the reaction is stopped, the filtration is carried out, a filter cake is drained, the filtrate is distilled under normal pressure, 88.3g of distillate at 140 ℃ to 143 ℃ is collected, namely the product phenylacetylene, the yield is 86.6 percent, and the GC purity is 98.9 percent. And carrying out reduced pressure distillation on the residual kettle residue under the pressure of-0.095 MP, and collecting 18.8g of fraction at 100-105 ℃, namely the brominated styrol, and applying the next batch of experiment.
Example six:
183g (1mol) of bromostyrol, 39g (0.6mol) of zinc powder and 28g (0.5mol) of potassium hydroxide are added into a 250ml three-neck flask, are uniformly stirred under the protection of nitrogen, are heated to 120 ℃ and are subjected to heat preservation reaction for 6 hours, the reaction is stopped, filtration is carried out, a filter cake is pumped to dryness, filtrate is subjected to atmospheric distillation, 92.6g of 140-143 ℃ fraction is collected, namely phenylacetylene is obtained, the yield is 90.8%, and the GC purity is 99.5%. And carrying out reduced pressure distillation on the residual kettle residue under the pressure of-0.095 MP, collecting 12.6g of fraction at 100-105 ℃, namely the brominated styrol, and applying the next batch of experiment.
It should be understood that the above experimental examples are only examples for clearly illustrating the present invention, and are not intended to limit the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (7)
1. A preparation method of phenylacetylene comprises the following steps:
(1) debromination reaction: taking bromo-styrol as a raw material and also serving as a reaction solvent, heating the system to react under the condition of a catalyst, keeping the temperature to react for more than 2 hours, stopping the reaction, and filtering to remove insoluble substances; the catalyst is one or more of zinc powder, iron powder, aluminum powder, magnesium powder, tetrabutylammonium bromide, di-n-butylamine, tri-n-butylamine, triethylamine, sodium hydroxide, potassium hydroxide, sodium amide, lithium amide, sodium methoxide and sodium ethoxide;
(2) collecting finished products: distilling the filtrate obtained in the step (1) at normal pressure, and collecting the 140-143 ℃ fraction, namely the phenylacetylene product;
(3) the solvent is used mechanically: and (3) carrying out reduced pressure distillation on the residual kettle residue in the step (2), collecting the fraction at 100-105 ℃, namely the brominated styrol, and mechanically applying the fraction to the next batch of reaction.
2. The method of claim 1, wherein the catalyst is zinc powder or iron powder.
3. The preparation method according to claim 1, wherein the system in the step (1) is heated for reaction at a temperature ranging from 50 ℃ to 250 ℃.
4. The preparation method according to claim 1, wherein the system in the step (1) is heated for reaction at a temperature ranging from 120 ℃ to 140 ℃.
5. The preparation method according to claim 1, wherein the system in the step (1) is subjected to heat preservation reaction for 4-6 hours.
6. The method of claim 1, wherein the reduced pressure distillation in step (3) is performed at a pressure of less than-0.08 MP.
7. The process according to claim 1, wherein the reduced pressure distillation in the step (3) is carried out at a pressure of-0.08 to-0.1 MP.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56133227A (en) * | 1980-03-24 | 1981-10-19 | Sanyo Chem Ind Ltd | Preparation of phenylacetylene |
| JPS62145030A (en) * | 1985-12-18 | 1987-06-29 | Denki Kagaku Kogyo Kk | Production of phenylacetylene compound |
| CN112457148A (en) * | 2020-12-03 | 2021-03-09 | 珠海固瑞泰复合材料有限公司 | Method for synthesizing high-purity MDPES (methyl diphenylsulfone) raw material phenyl acetylene in one step |
| CN112608209A (en) * | 2020-12-03 | 2021-04-06 | 珠海固瑞泰复合材料有限公司 | Green method for synthesizing MDPES raw material phenylacetylene without solvent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56133227A (en) * | 1980-03-24 | 1981-10-19 | Sanyo Chem Ind Ltd | Preparation of phenylacetylene |
| JPS62145030A (en) * | 1985-12-18 | 1987-06-29 | Denki Kagaku Kogyo Kk | Production of phenylacetylene compound |
| CN112457148A (en) * | 2020-12-03 | 2021-03-09 | 珠海固瑞泰复合材料有限公司 | Method for synthesizing high-purity MDPES (methyl diphenylsulfone) raw material phenyl acetylene in one step |
| CN112608209A (en) * | 2020-12-03 | 2021-04-06 | 珠海固瑞泰复合材料有限公司 | Green method for synthesizing MDPES raw material phenylacetylene without solvent |
Non-Patent Citations (3)
| Title |
|---|
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