CN109369352B - Method for synthesizing aromatic acetal from styrene under visible light - Google Patents
Method for synthesizing aromatic acetal from styrene under visible light Download PDFInfo
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- CN109369352B CN109369352B CN201811481556.1A CN201811481556A CN109369352B CN 109369352 B CN109369352 B CN 109369352B CN 201811481556 A CN201811481556 A CN 201811481556A CN 109369352 B CN109369352 B CN 109369352B
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 42
- -1 aromatic acetal Chemical class 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 23
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002841 Lewis acid Substances 0.000 claims abstract description 6
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 4
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/54—Preparation of compounds having groups by reactions producing groups by addition of compounds to unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a new method for synthesizing aromatic acetal from styrene under visible light, which belongs to the technical field of organic synthesis and is characterized in that under the conditions of normal temperature, normal pressure and air atmosphere, mercaptan is utilized to prepare Ir/ZnIn catalyst2S4And the sulfenyl free radical generated under the action of visible light induces the reaction of styrene and alcohol to generate aryl acetal, the reaction does not need expensive aldehyde or ketone as a substrate, corrosive protonic acid or Lewis acid is not needed to be added, the product yield is high, the reaction condition is mild, and the method has the advantages of simple and easy operation and low cost, and is favorable for large-scale industrial popularization.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a novel method for synthesizing aromatic acetal from styrene under visible light.
Background
Aromatic aldehyde is an extremely important organic raw material, and is widely applied to industrial production of spices, medicines, foods, tobaccos, cosmetics, paints and the like. In addition, aromatic aldehyde aldehydes have special chemical stability, and thus are often used for protecting carbonyl groups in the synthesis of esters, sugars, steroids, and complex natural products. In view of the important industrial application value of aromatic aldehyde condensation products, many researches and researches on the synthesis of aromatic aldehyde condensation products have been carried out. Most of the existing methods for synthesizing aromatic acetals are methods for generating acetals by the condensation reaction between aldehydes or ketones and alcohols catalyzed by protonic acids or Lewis acids. However, these methods tend to have very large limitations: aldehydes and ketones are expensive, protons or lewis acid as a catalyst are corrosive and prone to side reactions such as peroxidation, high reaction temperature is required, and the use of organic solvents such as benzene and toluene causes great pollution to the environment. Therefore, it is highly desirable to develop a milder, more efficient, and more environmentally friendly method for synthesizing aryl acetals.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing aromatic acetal from styrene under visible light. The method utilizes Ir/ZnIn2S4 to catalyze mercaptan to generate sulfenyl free radicals for the first time under visible light, and enables styrene to react with alcohol to generate aryl acetal under the action of the sulfenyl free radicals.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing aromatic acetal from styrene under visible light comprises adding 8-10mg of catalyst Ir/ZnIn into a reaction tube2S4，Adding styrene and mercaptan (the molar ratio of the styrene to the mercaptan is 1.2:1-1: 1) and 4ml of alcohol in a certain proportion, and then irradiating the reaction tube for 8-15 hours at normal temperature and normal pressure in an air atmosphere under visible light. Mercaptan catalyst Ir/ZnIn2S4And generating sulfur radical under the action of visible light, reacting the generated sulfur radical with styrene to generate alkyl radical, and generating O in air2With the action of (3), peroxy radicals are generated, and the generated peroxy radicals react with alcohol to finally generate acetal. The method does not need to add protonic acid or Lewis acid, and the reaction time is 8-15 h.
The alcohol serves as both a reactant and a solvent in this reaction. The thiol generates a disulfide after the reaction is complete.
Wherein Ir/ZnIn2S4The synthesis is carried out by adopting a solvothermal method: ZnCl with the molar ratio of 1:1:12、InCl3•4H2Dissolving O and thioacetamide TAA in the mixed solution of DMF 30ml and glycol 30ml successively, and adding IrCl3•H2Stirring O for 30 min, reacting in an oven at 180 ℃ for 18h, filtering, washing and drying to obtain Ir/ZnIn2S4。
Ir/ZnIn2S4The photoproduction electrons and photoproduction holes generated under the excitation of visible light can catalyze mercaptan to generate sulfur-based free radicals, the generated sulfur-based free radicals react with styrene to generate new free radicals, the new free radicals and oxygen in the air act together to generate active intermediates, the active intermediates interact with alcohol, and finallyAryl acetals are formed and thiols are converted to disulfide compounds.
The invention has the following remarkable advantages:
(1) the alcohol used in the invention is used as a reactant and a solvent, so that the use of toxic organic solvents such as benzene, toluene and the like is avoided.
(2) The invention does not need to add corrosive protonic acid or Lewis acid, and avoids side reactions such as peroxidation and the like to a certain extent.
(3) The invention uses cheaper styrene to replace expensive aldehyde and ketone, can react at normal temperature and normal pressure, has simple and easy preparation method, high practical value and application prospect, and is beneficial to large-scale industrial popularization.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Adding 8-10mg of catalyst Ir/ZnIn into a reaction tube2S4Then adding 0.12mmol-0.10mmol of styrene, 0.1mmol of mercaptan and 4ml of alcohol, and then irradiating the reaction tube for 8-15h at normal temperature and normal pressure in an air atmosphere under visible light, wherein the reaction formula is as follows:
TABLE 1
As shown in Table 1, the visible light and Ir/ZnIn are used2S4It is feasible to catalyze mercaptan to generate sulfenyl free radical, and then make styrene and alcohol react to generate aryl acetal under the action of sulfenyl free radical, and the reaction has a certain substrate application range. Methanol and ethanol can react with styrene to generate corresponding acetalAnd the reaction yield is higher, but the yield of the target acetal is reduced along with the increase of the carbon chain of the alcohol.
The invention is proved by the above that the invention realizes the use of mercaptan in the catalyst Ir/ZnIn2S4And the sulfenyl free radical generated under the action of visible light induces the reaction of styrene and alcohol to generate aryl acetal, and the method has the advantages of high efficiency, environmental protection, simple operation and certain substrate application range.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. A method for synthesizing aromatic acetal from styrene under visible light is characterized in that: under the conditions of normal temperature, normal pressure and air atmosphere, utilizing mercaptan to make catalyst Ir/ZnIn2S4And the sulfenyl free radical generated under the action of visible light induces the reaction of styrene and alcohol to generate aryl acetal; the alcohol is any one of methanol, ethanol and propanol.
2. The method of claim 1, wherein: the alcohol serves as both a reactant and a solvent in this reaction.
3. The method of claim 1, wherein: the specific method comprises the following steps: adding 8-10mg of catalyst Ir/ZnIn into a reaction tube2S4Adding 0.12mmol-0.10mmol of styrene, 0.1mmol of mercaptan and 4ml of alcohol, then irradiating the reaction tube at normal temperature and normal pressure in air atmosphere under visible light to react, and reacting the mercaptan in the presence of catalyst Ir/ZnIn2S4And generating sulfur radical under the action of visible light, reacting the generated sulfur radical with styrene to generate alkyl radical, and generating O in air2With the action of (3), peroxy radicals are generated, and the generated peroxy radicals react with alcohol to finally generate acetal.
4. The method of claim 3, wherein: the thiol generates a disulfide after the reaction is complete.
5. The method of claim 3, wherein: the method does not need to add protonic acid or Lewis acid, and the irradiation reaction time is 8-15 h.
6. The method of claim 1, wherein: the Ir/ZnIn2S4The synthesis is carried out by adopting a solvothermal method: ZnCl with the molar ratio of 1:1:12、InCl3•4H2Dissolving O and thioacetamide TAA in the mixed solution of DMF 30ml and glycol 30ml successively, and adding IrCl3•H2Stirring O for 30 min, reacting in an oven at 180 ℃ for 18h, filtering, washing and drying to obtain Ir/ZnIn2S4。
7. The method of claim 6, wherein: IrCl3•H2O represents ZnIn2S4The molar fraction of (B) is 0.5-3 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811481556.1A CN109369352B (en) | 2018-12-05 | 2018-12-05 | Method for synthesizing aromatic acetal from styrene under visible light |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811481556.1A CN109369352B (en) | 2018-12-05 | 2018-12-05 | Method for synthesizing aromatic acetal from styrene under visible light |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109369352A CN109369352A (en) | 2019-02-22 |
| CN109369352B true CN109369352B (en) | 2021-07-27 |
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| CN201811481556.1A Expired - Fee Related CN109369352B (en) | 2018-12-05 | 2018-12-05 | Method for synthesizing aromatic acetal from styrene under visible light |
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2018
- 2018-12-05 CN CN201811481556.1A patent/CN109369352B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Cobalt(II) acetylacetonate covalently anchored onto magnetic mesoporous silica nanospheres as a catalyst for epoxidation of olefins;Xinzhe Li et al;《Materials Chemistry and Physics》;20150304;第156卷;第9-15页 * |
| Oxidation of olefins catalyzed by Iron (III) complexes of bis-benzimidazolyl;Gauri Ahuja et al;《Journal of Molecular Structure》;20120104;第1011卷;第166-171页 * |
| Palladium sparteine dichloride;Sigman, Matthew S et al;《e-EROS Encyclopedia of Reagents for Organic Synthesis》;20121231;第1-4页 * |
| THIOUREA, A CONVENIENT REAGENT FOR THE REDUCTIVE CLEAVAGE OF OLEF~ OZONOLYSIS PRODUCTS;Deepa Gupta et al;《Tetrahedron》;19800827;第38卷(第20期);第3013-3018页 * |
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