CN115677624A - Method for preparing styrene oxide through benzene glycol cyclization - Google Patents
Method for preparing styrene oxide through benzene glycol cyclization Download PDFInfo
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- CN115677624A CN115677624A CN202211424702.3A CN202211424702A CN115677624A CN 115677624 A CN115677624 A CN 115677624A CN 202211424702 A CN202211424702 A CN 202211424702A CN 115677624 A CN115677624 A CN 115677624A
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- styrene oxide
- cyclization
- benzene glycol
- reaction
- betaine
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 93
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000007363 ring formation reaction Methods 0.000 title claims abstract description 20
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract description 16
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 claims abstract description 9
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 229960003237 betaine Drugs 0.000 claims description 11
- -1 betaine compound Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- 229940094506 lauryl betaine Drugs 0.000 claims description 4
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229940117986 sulfobetaine Drugs 0.000 claims description 3
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- WKALLSVICJPZTM-UHFFFAOYSA-N 3-[decyl(dimethyl)azaniumyl]propane-1-sulfonate Chemical compound CCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O WKALLSVICJPZTM-UHFFFAOYSA-N 0.000 claims 1
- QZRAABPTWGFNIU-UHFFFAOYSA-N 3-[dimethyl(octyl)azaniumyl]propane-1-sulfonate Chemical compound CCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O QZRAABPTWGFNIU-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 47
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- HPEUEJRPDGMIMY-IFQPEPLCSA-N molybdopterin Chemical compound O([C@H]1N2)[C@H](COP(O)(O)=O)C(S)=C(S)[C@@H]1NC1=C2N=C(N)NC1=O HPEUEJRPDGMIMY-IFQPEPLCSA-N 0.000 abstract 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLRGEJWRGPHNPU-UHFFFAOYSA-N (2,3-diethoxyphenyl)-diphenylphosphane Chemical compound CCOC1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1OCC XLRGEJWRGPHNPU-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 2
- TYIOVYZMKITKRO-UHFFFAOYSA-N 2-[hexadecyl(dimethyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O TYIOVYZMKITKRO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LAZPBGZRMVRFKY-HNCPQSOCSA-N Levamisole hydrochloride Chemical compound Cl.C1([C@H]2CN3CCSC3=N2)=CC=CC=C1 LAZPBGZRMVRFKY-HNCPQSOCSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000921 anthelmintic agent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000001524 citrus aurantium oil Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229960003734 levamisole hydrochloride Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical class CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses a method for preparing styrene oxide by cyclizing benzene glycol, which comprises the following steps: in the presence of betaine compounds, benzene glycol and DTPP are subjected to cyclization reaction to prepare styrene oxide; wherein the addition amount of betaine compounds is 0.1-1% of the weight of phenylethanediol. The invention provides a brand new epoxyphenylethane synthesis route, the process is simple, the reaction condition is mild, and betaine compounds are adopted as the cocatalyst, so that the oriented reaction of DTPP and phenylethanediol can be promoted, and the epoxyphenylethane can be generated with high conversion rate and high selectivity.
Description
Technical Field
The invention relates to an organic synthesis method, in particular to a method for preparing styrene oxide by cyclizing benzene glycol.
Background
Styrene oxide (styrene oxide), also known as styrene oxide, is an important organic synthesis intermediate and is widely applied to organic synthesis, pharmaceutical preparation, perfume production and the like; can be used as epoxy resin diluent, UV-absorbent, flavoring agent, etc., such as beta-phenylethyl alcohol prepared by hydrogenation of styrene oxide is the main component of oleum Rosae Rugosae, oleum Caryophylli, and neroli oil, and can be widely used in preparing food, tobacco, and cosmetic essence; the oxirane is also an important intermediate for synthesizing levamisole hydrochloride, which is a broad-spectrum anthelmintic drug used by both human and animals. Because the market price of the styrene oxide is high and the market demand is increased year by year in recent years, the synthesis research of the styrene oxide is of great significance.
At present, the main synthesis process of styrene oxide is a halogen alcohol method, and styrene and sodium bromide are generally used as raw materials, hydrogen peroxide is used as an oxidant, and the styrene oxide is prepared by bromine alcoholization and oil phase separation under an acidic environment and then by saponification reaction under an alkaline condition. The process is simple to operate and low in cost, but can generate a large amount of high-salinity wastewater.
In recent years, a large number of reports have been made on a method for producing styrene oxide by selective oxidation of styrene as a raw material with a novel oxygen source under the action of a specific catalyst.
Patent CN101463020A discloses a method for synthesizing styrene oxide by directly oxidizing styrene, which uses Ag- γ -ZrP as a catalyst, acetonitrile as a solvent, tert-butyl hydroperoxide as an oxygen source, the reaction temperature is 70-90 ℃, the conversion rate of styrene is 92%, and the selectivity of styrene oxide is 96%. But the catalyst is difficult to prepare and expensive, so the process cost is high, and the large-scale production has certain difficulty.
Patent CN101434587A provides an oxygen oxidation process. Styrene, hydrogen, oxygen, a catalyst and a solvent are mixed into a heterogeneous system for reaction at a certain temperature (0-180 ℃) and pressure (0.1-3.0 MPa), wherein the catalyst is a microporous titanium silicon material, but the preparation process is complicated, the conversion rate of the styrene is low (less than 20 percent), and the industrial production is difficult.
CN1557553A uses MCM series molecular sieve as catalyst, H 2 O 2 As an oxidant, the conversion rate of styrene and the selectivity of styrene oxide respectively reach 40 percent and 60 percent. Due to the acidic action of the molecular sieve catalyst, the ring opening phenomenon of the styrene oxide is serious, and the industrial requirement cannot be met at present.
In conclusion, molecular oxygen is used as an oxygen source, the temperature of the styrene epoxidation reaction is high, the catalyst is difficult to prepare and expensive, and the reaction conversion rate is low; other peroxides are used as oxygen sources, and catalytic reaction is carried out by catalysts such as sulfuric acid and the like, or equipment corrosion and environmental pollution exist; or in an acid environment, the polymerization of styrene and the ring-opening property of styrene oxide lead to poor product selectivity; or the explosion risk brought by peroxide is higher.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing styrene oxide by cyclizing benzene glycol.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing styrene oxide through cyclization of benzene glycol comprises the following steps:
in the presence of betaine compounds, benzene glycol and compounds shown in a formula I are subjected to cyclization reaction to prepare styrene oxide;
wherein the addition amount of betaine compounds is 0.1-1% of the mass of phenylethanediol.
The compound shown in the formula I, namely diethoxy triphenylphosphine, is abbreviated as DTPP in the invention. The raw material can be prepared by any method disclosed in the prior art, such as Synthesis and antimicrobial activity of N-benzyl (2R) -2-acetamido-3-oxysuststated pro-pionamide derivatives, DOI:10.1016/j.bmc.2008.08.055, and can also be directly purchased as a finished product in the market.
In the preparation method, the phenylethanediol is quickly combined with DTPP to form a five-membered cyclic compound; and the betaine compounds can enhance reaction mass transfer on one hand, and the double ionic groups can induce five-membered rings to remove triphenylphosphine oxide TPPO to generate styrene oxide on the other hand, so that the high-yield preparation of the styrene oxide under mild conditions is realized.
The above reaction process expression is as follows:
in a preferred embodiment, the betaine-type compound is a carboxybetaine, preferably having a total carbon number of C 12 -C 22 More preferably one or more of lauryl betaine, cetyl dimethyl betaine, tetradecyl dimethyl betaine, and octadecyl dimethyl betaine.
In a preferred embodiment, the betaine compound is a sulfobetaine, preferably one or more of thiobetaine 8, thiobetaine 10, hexadecylsulfobetaine, tetradecylsulfobetaine.
In a preferred embodiment, the cyclization reaction temperature is from 50 to 100 ℃, preferably from 60 to 70 ℃;
preferably, the pressure of the cyclization reaction is atmospheric pressure;
preferably, the cyclization reaction time is 2-12h.
In a preferred embodiment, the molar ratio of the phenylethanediol to the compound of formula I is 1 (1-1.1).
In a preferred embodiment, the cyclization reaction is carried out in an organic solvent selected from one or more of toluene, ethylbenzene, cumene, xylene.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method has simple steps, normal reaction pressure, reaction temperature of 50-100 ℃, mild reaction conditions and reduced requirements on reaction equipment.
2. According to the invention, betaine compounds are used as auxiliaries, so that reaction mass transfer is enhanced, and the reaction rate is increased; meanwhile, the directional reaction of DTPP and phenylethanediol is promoted, the generation of byproducts is reduced, and the yield of the phenylethaneoxide is more than or equal to 99 percent.
3. The method adopts a neutral condition for reaction, avoids using an acid-base catalyst, has high reaction selectivity, and simultaneously has less corrosion to equipment and environmental pollution.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
Unless otherwise specified, the main raw materials and reagents involved in the present invention were purchased from commercially available products. Among them, diethoxytriphenylphosphine (DTPP) was purchased from Bojia biomedical science and technology, inc., changzhou, CAS number 18509-25-6.
The Gas Chromatography (GC) method employed in the present invention is specifically as follows:
the instrument model is as follows: shimadzu GC-2010-plus
Parameters are as follows: chromatographic column DB-5, column temperature: the initial temperature was 50 deg.C, the temperature was raised to 300 deg.C, and the temperature was maintained for 10min. Sample inlet temperature: 280 ℃, detector temperature: 300 ℃, air flow: 400ml/min, hydrogen flow: 40ml/min, tail gas blowing flow: 30ml/min, pressure: 77.7kPa.
[ example 1 ]
Styrene oxide was prepared as follows:
138.2g of benzene glycol (1 mol), 350.39g of DTPP (1 mol) and 0.14g of lauryl betaine are added into a 1L reaction bottle, 184.3g of toluene solvent is then added, the temperature is raised to 50 ℃ under stirring, the reaction is kept at the temperature, samples are taken at intervals during the heat preservation process for GC analysis, after 10 hours of reaction under normal pressure, the conversion rate of the benzene glycol is 99.0%, and the selectivity of the styrene oxide based on the benzene glycol is 99.1%.
[ example 2 ]
Styrene oxide was prepared as follows:
138.2g of benzene glycol (1 mol), 385.43g of DTPP (1.1 mol) and 1.38g of hexadecyl dimethyl betaine are added into a 2L reaction bottle, 460.7g of toluene solvent is then added, the temperature is raised to 100 ℃ under stirring, the reaction is kept at a constant temperature, samples are taken at intervals during the heat preservation process for GC analysis, after 4 hours of reaction at normal pressure, the conversion rate of the benzene glycol is 99.8 percent, and the selectivity of the styrene oxide based on the benzene glycol is 99.3 percent.
[ example 3 ]
Styrene oxide was prepared as follows:
138.2g (1 mol) of benzene glycol, 367.91g of DTPP (1.05 mol) and 0.28g of tetradecyldimethyl betaine are added into a 2L reaction bottle, 276.4g of toluene solvent is then added, the temperature is raised to 80 ℃ under stirring, the reaction is kept at the constant temperature, samples are taken at intervals during the heat preservation process, GC analysis is carried out, after 5 hours of reaction under normal pressure, the conversion rate of the benzene glycol is 99.0%, and the selectivity of the styrene oxide based on the benzene glycol is 99.2%.
[ example 4 ]
Styrene oxide was prepared as follows:
138.2g of benzene glycol (1 mol), 367.91g of DTPP (1.05 mol) and 0.69g of thiobetaine 10 are added into a 2L reaction bottle, 368.6g of toluene solvent is then added, the temperature is raised to 60 ℃ under stirring, the reaction is kept at a constant temperature, samples are taken at intervals during the heat preservation process, GC analysis is carried out, after 4 hours of reaction under normal pressure, the conversion rate of the benzene glycol is 98.9%, and the selectivity of the styrene oxide based on the benzene glycol is 99.3%.
[ example 5 ]
Styrene oxide was prepared as follows:
138.2g of benzene glycol (1 mol), 367.91g of DTPP (1.05 mol) and 1.38g of hexadecyl sulfobetaine are added into a 2L reaction bottle, 276.4g of toluene solvent is then added, the temperature is raised to 80 ℃ under stirring, the reaction is kept at the constant temperature, samples are taken at intervals during the heat preservation process, GC analysis is carried out, after the reaction is carried out for 3 hours under normal pressure, the conversion rate of the benzene glycol is 99.3 percent, and the selectivity of the styrene oxide based on the benzene glycol is 99.4 percent.
Comparative example 1
Prepared by referring to substantially the same method as in example 1 except that lauryl betaine was not added during the reaction.
After 12h of reaction at normal pressure, the conversion of styrene glycol was 95.6% and the selectivity of styrene oxide based on styrene glycol was 85.2%.
Comparative example 2
Styrene oxide was prepared according to a similar method as in patent CN 102311408A:
adding 104.2g of styrene (1 mol) into a 1L reaction bottle, stirring and heating to 80 ℃, then dropwise adding 600.8g of 30% sodium bromide solution, 102g of 35% hydrogen peroxide solution and 98g of 50% sulfuric acid solution, completing dropwise adding of the three materials within 2h, and continuing to perform heat preservation reaction for 4h; standing and layering after sampling and detecting are qualified, transferring the oil phase into another 1L reaction bottle, stirring and heating to 40 ℃, dropwise adding 100g of 40% sodium hydroxide solution within 2h, continuing to perform heat preservation reaction for 5h, standing and layering after sampling and detecting are qualified, and collecting the oil phase. The conversion of styrene was 97.5% by GC analysis and the selectivity of styrene oxide based on styrene was 78.8%.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (6)
1. The method for preparing styrene oxide through cyclization of benzene glycol is characterized by comprising the following steps:
in the presence of betaine compounds, benzene glycol and compounds shown in a formula I are subjected to cyclization reaction to prepare styrene oxide;
wherein the addition amount of betaine compounds is 0.1-1% of the mass of phenylethanediol.
2. The method for preparing styrene oxide through benzene glycol cyclization according to claim 1, wherein the betaine compound is carboxyl betaine, preferably with total carbon number of C 12 -C 22 More preferably one or more of lauryl betaine, cetyl dimethyl betaine, tetradecyl dimethyl betaine, and octadecyl dimethyl betaine.
3. The method for preparing styrene oxide through cyclization of benzene glycol according to claim 1, wherein the betaine compound is sulfobetaine, preferably one or more of sulfobetaine 8, sulfobetaine 10, hexadecylsulfobetaine and tetradecylsulfbetaine.
4. The method for preparing styrene oxide through benzene glycol cyclization according to any one of claims 1-3, wherein the cyclization reaction temperature is 50-100 ℃, preferably 60-70 ℃;
preferably, the pressure of the cyclization reaction is atmospheric pressure;
preferably, the cyclization reaction time is 2-12h.
5. The method for preparing styrene oxide through cyclization of benzene glycol according to claim 4, wherein the molar ratio of the benzene glycol to the compound shown in formula I is 1 (1-1.1).
6. The method for preparing styrene oxide through cyclization of benzene glycol according to claim 4, wherein the cyclization reaction is carried out in an organic solvent, and the organic solvent is one or more selected from toluene, ethylbenzene, cumene and xylene.
Priority Applications (1)
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| KELLY JEFFERY W等: "Bis(neopentyloxy)triphenylphosphorane: A Versatile, Nonalkylating Cyclodehydration Reagent", 《J.ORG. CHEM.》, vol. 51, no. 26, pages 5490 - 5492, XP000650475, DOI: 10.1021/jo00376a103 * |
| PHILIP L. ROBINSON等: "Diethoxytriphenylphosphorane: A Mild, Regioselective Cyclodehydrating Reagent for Conversion of Diols to Cyclic Ethers. Stereochemistry, Synthetic Utility, and Scope", 《J. AM. CHEM. SOC.》, vol. 107, pages 5210 - 5219 * |
| PHILIP L.ROBINSON等: "THE SYNTHETIC UTILITY OF DIOXYPHOSPHORANES IN ORGANIC SYNTHESIS", 《PHOSPHORUS AND SULFUR AND THE RELATED ELEMENTS》, vol. 26, pages 15 - 24 * |
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