CN107973703B - Synthetic method of aryl olefin - Google Patents
Synthetic method of aryl olefin Download PDFInfo
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- CN107973703B CN107973703B CN201711252869.5A CN201711252869A CN107973703B CN 107973703 B CN107973703 B CN 107973703B CN 201711252869 A CN201711252869 A CN 201711252869A CN 107973703 B CN107973703 B CN 107973703B
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- reaction
- aryl
- acetal
- molecular sieve
- anethole
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- -1 aryl olefin Chemical class 0.000 title claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000010189 synthetic method Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000011973 solid acid Substances 0.000 claims abstract description 7
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 5
- 238000005580 one pot reaction Methods 0.000 claims abstract description 5
- 239000002168 alkylating agent Substances 0.000 claims abstract description 3
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- RUVINXPYWBROJD-ONEGZZNKSA-N trans-anethole Chemical compound COC1=CC=C(\C=C\C)C=C1 RUVINXPYWBROJD-ONEGZZNKSA-N 0.000 abstract description 42
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 9
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 229940011037 anethole Drugs 0.000 description 18
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 18
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 5
- IDEYZABHVQLHAF-GQCTYLIASA-N (e)-2-methylpent-2-enal Chemical compound CC\C=C(/C)C=O IDEYZABHVQLHAF-GQCTYLIASA-N 0.000 description 4
- IDEYZABHVQLHAF-UHFFFAOYSA-N 2-Methyl-2-pentenal Natural products CCC=C(C)C=O IDEYZABHVQLHAF-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000341 volatile oil Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 235000003069 Artemisia scoparia Nutrition 0.000 description 2
- 241001249148 Artemisia scoparia Species 0.000 description 2
- ZFMSMUAANRJZFM-UHFFFAOYSA-N Estragole Chemical compound COC1=CC=C(CC=C)C=C1 ZFMSMUAANRJZFM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZJVAWPKTWVFKHG-UHFFFAOYSA-N p-Methoxypropiophenone Chemical compound CCC(=O)C1=CC=C(OC)C=C1 ZJVAWPKTWVFKHG-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- WQEJBXWUAANQHU-UHFFFAOYSA-N 1-methoxy-2-[2-(2-methoxyphenyl)propan-2-yl]benzene Chemical compound COC1=CC=CC=C1C(C)(C)C1=CC=CC=C1OC WQEJBXWUAANQHU-UHFFFAOYSA-N 0.000 description 1
- KPPNOMMXCHIJKC-UHFFFAOYSA-N 1-methoxy-4-prop-1-enylbenzene Chemical compound COC1=CC=C(C=CC)C=C1.COC1=CC=C(C=CC)C=C1 KPPNOMMXCHIJKC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000002782 Foeniculum vulgare var dulce Nutrition 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000010617 anise oil Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- RUVINXPYWBROJD-ARJAWSKDSA-N cis-anethole Chemical compound COC1=CC=C(\C=C/C)C=C1 RUVINXPYWBROJD-ARJAWSKDSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010643 fennel seed oil Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 230000006289 propionylation Effects 0.000 description 1
- 238000010515 propionylation reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 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
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of aryl-containing substituted olefin, which is characterized in that aliphatic acetal is used as an alkylating agent to react with an aromatic compound, and the aryl-containing substituted olefin such as anise camphor and the like is directly obtained through a one-pot reaction at the normal pressure or the low pressure of 0.1-1.0MPa and the reaction temperature of 90-160 ℃ under the catalysis of a solid acid catalyst. The invention has the following characteristics: 1) is a new synthetic route, and the reaction is finished in one pot. 2) The aromatic compound serves as both a reactant and a solvent, and no other organic solvent is used. 3) The catalyst is solid acid such as H-Beta molecular sieve and metal ion modified molecular sieve thereof, and is catalytic amount. 4) The produced alcohol can be recycled for use in the synthesis of acetal after recovery. 5) The reaction may be carried out batchwise or in a tubular reactor or a fixed bed reactor. 6) The post-treatment is simple, no waste is generated in the reaction process, and the method is a green and environment-friendly synthetic route.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a synthesis method of aryl olefin, in particular to synthesis of anethole.
Background
The anethole (also called anethole or anethole) with the chemical name of 1-methoxy-4- (1-propenyl) benzene naturally exists in essential oil such as anise oil and fennel oil, and trans-isomer accounts for most of the essential oil. Has characteristic sweet fennel fragrance, and is mainly used for blending edible essence and toothpaste essence.
The traditional preparation method of the anise camphor is to obtain a crude product of the anise camphor from natural essential oil rich in the anise camphor through freezing crystallization and centrifugation, and then extract the crude product by a rectification method. For example, it is extracted from oleum Anisi Stellati and oleum Foeniculi (CN 102491884 and essence and perfume cosmetic, 2013, stage 02).
Due to the limited sources and amounts of natural essential oils, naturally produced anise camphor cannot meet the increasing demand. Therefore, the synthesized finished product has great market demand and commercial value. Its synthesis has been receiving wide attention.
CN103058835 describes a synthesis method of anethole, which comprises obtaining p-methoxypropiophenone by friedel-Crafts reaction of propionyl chloride and anisole, then obtaining corresponding alcohol by reduction with sodium borohydride, and then obtaining anethole by dehydration under acidic conditions of p-toluenesulfonic acid and the like. Because excessive aluminum trichloride is needed to be used for catalyzing the propionylation of anisole, the obtained p-methoxypropiophenone is reduced by using sodium borohydride, and the final dehydration reaction generates a large amount of waste to be discharged, so that the environmental protection problem is not small.
DE19742418974 discloses a two-step synthesis of anethole using anisole and propionaldehyde as starting materials. Firstly, anisole and propionaldehyde generate a mixture of bis (methoxyphenyl) propane under the action of an acid catalyst, and secondly, the condensation product generates elimination reaction at 200-300 ℃ and a certain vacuum degree in the presence of a catalytic amount of acid catalysts such as phosphoric acid and the like, and a crude product is distilled out. The conversion rate of the condensation compound is 67.3 percent, the selectivity of the anethole is about 41 percent, and the crude product contains part of unreacted condensation compound, trans-anethole, cis-anethole, ortho-trans-anethole and the like; it is stated that cleavage of the condensation mixture obtained by the renewed reaction of ortho-anethole with anisole gives about 8% of anethole. The disadvantages are that the reaction needs to take place at higher temperatures, the cracking of the condensation intermediates is incomplete; also obtain a considerable amount of o-anethole and other by-products; due to the long heating time of the cleavage process and the complexity of the process of recycling the ortho-anethole, considerable amounts of by-products, undesired isomers and other polymers are produced.
CN103755533 describes a method for synthesizing anethole from artemisia scoparia naphtha, which comprises isomerizing artemisia scoparia naphtha at 140-215 deg.C for 0.5-3h under the action of alkaline catalyst, isomerizing the estragole into anethole, and then obtaining the anethole by freezing crystallization, filtration and rectification.
CN106103398 discloses a process for the preparation of arylpropenes, especially 1-methoxy-4- (1-propenyl) benzene (anethole) involving thermal decomposition of the corresponding 1, 1-diarylpropane. Removing one aromatic hydrocarbon molecule by performing gas-phase thermal decomposition on 1, 1-diaryl propane under reduced pressure and at the temperature of 300-400 ℃ under the action of a boron-containing molecular sieve catalyst to obtain the anethole.
The materials used in the relevant processes are expensive or not easily available, or the three wastes in the process are seriously discharged, or the reaction conditions are harsh, and the like, so the exploration of the synthetic route of the anethole still arouses people's interest.
Disclosure of Invention
The invention aims to: provides a synthetic method of aryl-containing substituted olefin, in particular to a novel synthetic method of anethole.
The technical solution of the invention is as follows:
a synthetic method of aryl-containing substituted olefin is characterized in that aliphatic acetal is used as an alkylating agent to react with an aromatic compound, and the aryl-containing substituted olefin such as anise camphor and the like is directly obtained through one-pot reaction at the reaction temperature of 90-160 ℃ under the catalysis of a solid acid catalyst and under the normal pressure or the low pressure of 0.1-1.0MPa, wherein the specific reaction formula is as follows:
in a preferred embodiment of the invention, the aliphatic acetal is a C1-C12 aliphatic acetal.
In a preferred embodiment of the invention, the solid acid catalyst is molecular sieve H-Beta.
In a preferred embodiment of the invention, the reaction temperature is in the range of 110 to 140 ℃.
Due to the adoption of the technical scheme, the invention has the following characteristics:
1) is a new synthetic route, and the reaction is finished in one pot.
2) The aromatic compound serves as both a reactant and a solvent, and no other organic solvent is used.
3) The catalyst is solid acid such as H-Beta molecular sieve and metal ion modified molecular sieve thereof, and is catalytic amount.
4) The produced alcohol can be recycled for use in the synthesis of acetal after recovery.
5) The reaction may be carried out batchwise or in a tubular reactor or a fixed bed reactor.
6) The post-treatment is simple, no waste is generated in the reaction process, and the method is a green and environment-friendly synthetic route.
Detailed Description
The technical solution of the invention is further illustrated below with reference to specific examples, which are not to be construed as limiting the technical solution.
Example 1:
100ml autoclave, oil bath, electromagnetic stirring. Adding 18g of anisole into a kettle, and adding 3.9g of propionaldehyde dimethanol acetal; then 0.78g H-Beta molecular sieve powder is added. Carrying out oil bath at 120 ℃, and stirring for reaction for 3 hours; cooling to room temperature, filtering the material out of the catalyst, and detecting by gas chromatography. Acetal conversion 74%; the selectivity of the anise camphor is 52.4 percent, and the 2-methyl-2-pentenal content is 25.3 percent.
Example 2:
100ml autoclave, oil bath, electromagnetic stirring. Adding 30g of anisole into a kettle, and adding 4.5g of propionaldehyde dimethanol acetal; then 1.1g of Ce-Beta molecular sieve powder is added. Stirring and reacting for 4 hours at 130 ℃ in an oil bath; cooling to room temperature, filtering the reaction mass out of the catalyst, and detecting by gas chromatography. Acetal conversion 63.5%; the selectivity of the anise camphor is 61.2 percent, and the 2-methyl-2-pentenal is 15.1 percent.
Example 3:
100ml autoclave, oil bath, electromagnetic stirring. Adding 50g of anisole into a kettle, and adding 7.5g of propionaldehyde dimethanol acetal; then 3g of Ni-Y molecular sieve powder is added. Stirring and reacting for 5 hours at 135 ℃ in an oil bath; cooling to room temperature, filtering the reaction mass out of the catalyst, and detecting by gas chromatography. Acetal conversion 33.5%; the selectivity of the anise camphor is 24.6 percent, and the 2-methyl-2-pentenal content is 35.1 percent.
Example 4:
250ml three-mouth bottle, oil bath, electromagnetic stirring, installation of thermometer, condenser tube. 74g of anisole is added into a bottle, and 9.5g of propionaldehyde di-n-propanol acetal is added; then adding 2.8g H-Beta molecular sieve powder. Stirring and reacting for 4.5 hours at 132 ℃; cooling to room temperature, filtering the material out of the catalyst, and detecting by gas chromatography. Acetal conversion 39.3%; the selectivity of the anise camphor is 36.6 percent, and the 2-methyl-2-pentenal content is 27.4 percent.
Claims (1)
1. A synthetic method of aryl-containing substituted olefin is characterized in that aliphatic acetal is used as an alkylating agent to react with an aromatic compound, and aryl-containing substituted olefin is directly obtained through one-pot reaction under the catalysis of a solid acid catalyst and under the pressure of 0.1-1.0MPa and at the reaction temperature of 110-140 ℃, and the specific reaction formula is as follows:
wherein, R is1Methoxy, ethoxy, C1-C4 alkyl; r2A ═ C1-C10 alkyl group; r ═ n-propyl;
the solid acid catalyst is molecular sieve H-Beta.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711252869.5A CN107973703B (en) | 2017-12-01 | 2017-12-01 | Synthetic method of aryl olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711252869.5A CN107973703B (en) | 2017-12-01 | 2017-12-01 | Synthetic method of aryl olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107973703A CN107973703A (en) | 2018-05-01 |
| CN107973703B true CN107973703B (en) | 2021-02-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711252869.5A Active CN107973703B (en) | 2017-12-01 | 2017-12-01 | Synthetic method of aryl olefin |
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| Country | Link |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026951A (en) * | 1974-04-19 | 1977-05-31 | Haarmann & Reimer Gmbh | Process for the production of anethole |
| JP2014172834A (en) * | 2013-03-07 | 2014-09-22 | National Institute Of Advanced Industrial & Technology | Method for producing aromatic olefins |
| CN106103398A (en) * | 2014-01-17 | 2016-11-09 | 巴斯夫欧洲公司 | Process for the production of arylpropylene |
-
2017
- 2017-12-01 CN CN201711252869.5A patent/CN107973703B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026951A (en) * | 1974-04-19 | 1977-05-31 | Haarmann & Reimer Gmbh | Process for the production of anethole |
| JP2014172834A (en) * | 2013-03-07 | 2014-09-22 | National Institute Of Advanced Industrial & Technology | Method for producing aromatic olefins |
| CN106103398A (en) * | 2014-01-17 | 2016-11-09 | 巴斯夫欧洲公司 | Process for the production of arylpropylene |
Non-Patent Citations (1)
| Title |
|---|
| 缩醛与吲哚或苯并呋喃的烷基化反应;刘宁宁等;《有机化学》;20141231(第34期);2523-2528 * |
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