CN115745754A - Synthesis method of acetal - Google Patents
Synthesis method of acetal Download PDFInfo
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- CN115745754A CN115745754A CN202211535462.4A CN202211535462A CN115745754A CN 115745754 A CN115745754 A CN 115745754A CN 202211535462 A CN202211535462 A CN 202211535462A CN 115745754 A CN115745754 A CN 115745754A
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- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 title claims abstract description 12
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000001308 synthesis method Methods 0.000 title description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 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 42
- 239000002808 molecular sieve Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002560 nitrile group Chemical group 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- -1 sulfonic group Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001589 carboacyl group Chemical group 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000013207 UiO-66 Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002077 nanosphere Substances 0.000 claims description 2
- 239000013384 organic framework Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 3
- 239000000758 substrate Substances 0.000 abstract description 15
- 239000003426 co-catalyst Substances 0.000 abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000007037 hydroformylation reaction Methods 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 24
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 15
- 238000006359 acetalization reaction Methods 0.000 description 13
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000010926 purge Methods 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 125000004036 acetal group Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing acetal. In particular to olefin and H under the action of Rh/phosphine ligand complex and molecular sieve co-catalyst 2 Application of a one-pot method for preparing acetal by heating CO and organic alcohol, belonging to the technical field of organic chemistry. The Rh/phosphine ligand complex and the molecular sieve cocatalyst provided by the invention are used in the series hydroformylation/acetalation reaction of olefin, and have high catalytic rate, substrate applicability and high regioselectivity.
Description
Technical Field
The invention relates to a method for synthesizing acetal. In particular to a method for preparing a catalyst by olefin and CO/H under the action of Rh/phosphine ligand complex and molecular sieve CO-catalyst 2 The application of the acetal reaction prepared by heating organic alcohol in one pot belongs to the technical field of organic chemistry.
Technical Field
Hydroformylation refers to olefins and CO/H 2 The aldehyde is generated under the action of the catalyst. The hydroformylation of olefins is an industrially important process for the synthesis of aldehydes, which are valuable fine chemicals and also important synthesis intermediates. In the further synthesis of aldehydes, protection of the aldehyde group is often required. The "one-pot" synthesis of olefin functional groups to acetals can be achieved by a "hydroformylation-acetalization" cascade of olefins. The acetal groups synthesized are very inert to oxidizing agents, reducing agents and bases. Meanwhile, the acetal group can be deprotected under acidic conditions to obtain an aldehyde group. The method has important synthesis for olefin substrates containing functional groupsMeaning. Therefore, the 'hydroformylation-acetalation' series reaction effectively avoids the process of separating and purifying aldehyde intermediates, and better conforms to the principles of green chemical atom economy and low energy consumption. Acetals are frequently used as solvents, perfumes, detergents or additives in oils and fuels, and to protect sensitive aldehyde groups from side reactions in organic synthesis. However, the hydroformylation-acetalization reaction of olefin in series developed so far has disadvantages of low catalyst activity and poor selectivity of the target product. These problems limit the further industrial application of this reaction. Therefore, the development of a high-activity and high-selectivity catalytic system has important academic and application values.
Disclosure of Invention
1. A method for synthesizing acetal is characterized in that the method comprises the following steps: shown as a general formula 1, under the action of Rh/phosphine ligand complex and molecular sieve cocatalyst, olefins I and H 2 Heating CO and organic alcohol for reaction; after the reaction is completed, centrifugally separating the molecular sieve, and carrying out reduced pressure distillation to obtain acetal II shown in the general formula 1;
Wherein R is x Are respectively and independently selected from hydrogen, hydroxyl, sulfonic group, halogen, nitrile group and C 1 ~C 10 Alkyl of (A), C 1 ~C 10 Alkoxy group of (C) 1 ~C 10 Alkanoyl of (2), C 1 ~C 10 One of the ester groups of (a);
2. the method of claim 1, wherein the phosphine ligand of step (1) is selected from one of the following structures:
R 1 are respectively selected from hydrogen, sulfonic group, halogen, nitrile group and C 1 ~C 10 Alkyl of (A), C 1 ~C 10 Alkoxy group of,
Wherein: r x Are respectively and independently selected from hydrogen, sulfonic group, halogen, nitrile group and C 1 ~C 10 Alkyl of (A), C 1 ~C 10 Alkoxy group of (C) 1 ~C 10 Alkanoyl of (2), C 1 ~C 10 Ester group of (A) or (C) 1 ~C 10 A sulfonate group of (a);
3. the method according to claim 1, wherein the organic solvent is one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, ethylene glycol, 1, 3-propanediol, and glycerol;
4. the method according to claim 1, wherein the molecular sieves are respectively selected from one or more of MCM-41, ZSM-5, beta-Zeolite, ZSM-35 (100), ZSM-35 (10) and ZSM-23, ZSM-22, ZSM-11, KIT-6, SBA-15, MCM-22, MCM-48, SSZ-13, UIO-66, tiSi molecular sieve TS-1, SAPO-34, SAPO-11, silica nanospheres, mesoporous silica, multi-stage pore silica microspheres, solid silica, carbon molecular sieves, 3A molecular sieves, 4A molecular sieves, 5A molecular sieves, 13X molecular sieves, Y molecular sieves, COF organic framework materials and S-1 all-silica molecular sieves;
5. the method of claim 1, wherein the reaction temperature is 60 to 200 ℃;
6. the process of claim 1, wherein H is 2 The pressure/CO is between 3/3bar and 100/100bar.
Compared with the prior art, the invention has the following remarkable effects:
1. the Rh/phosphine ligand complex and the molecular sieve cocatalyst provided by the invention are used for acetalation of 1-olefin, and both have high catalytic rate (TON as high as 43000) and substrate applicability.
2. The Rh/phosphine ligand complex and the molecular sieve cocatalyst provided by the invention are used for acetalation of 1-olefin, and both have high regioselectivity (l/b = 30.5-99.8).
Detailed Description
The present invention will be described more fully hereinafter with reference to the following examples.
Example 1
The Rh/phosphine ligand complex and molecular sieve co-catalyst used in the following examples were prepared by the following reaction procedure:
in a glove box, phosphine ligand (1.16 mg), rh (acac) (CO) 2 (0.1 mg), molecular sieve (40.0 mg), organic alcohol (5.0 mL), into the autoclave, stirring to obtain Rh/phosphine ligand complex and molecular sieve co-catalyst.
Example 2
Rh/phosphine ligand complex and molecular sieve co-catalyst for the catalysis of 1-pentene (substrate: catalyst =1 × 10) 4 ) Acetalization reaction with EtOH
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1 mg), ZSM-35 (10) (40.0 mg), etOH (5.0 mL), 1-pentene (0.42 mL), decane (16. Mu.L) were added to the autoclave, and the mixture was stirred with H 2 Purging three times, then charging CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was allowed to decrease to room temperature, and the gas phase was measured after centrifugal separation. The yield was 97%, the l/b ratio was 77.1 and the TON value was 10000.
Example 3
Rh/phosphine ligand complex and molecular sieve cocatalyst catalyzed 1-hexene (substrate: catalyst =1 × 10) 4 ) Acetalization reaction with EtOH
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1 mg), ZSM-35 (10) (40.0 mg), etOH (5.0 mL), 1-hexene (0.47 mL), decane (16. Mu.L) were added to the autoclave and stirred, and the mixture was stirred with H 2 Purging three times, then charging with CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was allowed to decrease to room temperature, and the gas phase was measured after centrifugal separation. The yield was 98%, the l/b ratio was 51.2 and the TON value was 9970.
Example 4
Rh/phosphine ligand complex and molecular sieve co-catalyst for 1-heptene (substrate: catalyst =1 × 10) 4 ) Acetalization reaction with EtOH
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1 mg), ZSM-35 (10) (40.0 mg), etOH (5.0 mL), 1-heptene (0.54 mL), decane (16. Mu.L) were added to the autoclave and stirred, and the mixture was stirred with H 2 Purging three times, then charging CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was allowed to decrease to room temperature, and the gas phase was measured after centrifugal separation. The yield was 94%, the l/b ratio was 56.4 and the TON value was 9950.
Example 5
Rh/phosphine ligand complex and molecular sieve co-catalyst for the catalysis of 1-octene (substrate: catalyst =1 × 10) 4 ) Acetalization reaction with EtOH
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1 mg), ZSM-35 (10) (40.0 mg), etOH (5.0 mL), 1-octene (0.60 mL), decane (16. Mu.L) were added to the autoclave and stirred, the mixture was stirred with H 2 Purging three times, then charging CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was allowed to decrease to room temperature, and the gas phase was measured after centrifugal separation. The yield was 93%, the l/b ratio was 33.1 and the TON value was 9950.
Example 6
Rh/phosphine ligand complex and molecular sieve co-catalyst catalysis of 1-nonene (substrate: catalyst =1 × 10) 4 ) Acetalization reaction with EtOH
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1 mg), ZSM-35 (10) (40.0 mg), etOH (5.0 mL), 1-nonene (0.66 mL), decane (16. Mu.L) were added to the autoclave and stirred, and the mixture was stirred with H 2 Purging three times, then charging CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was allowed to decrease to room temperature, and the gas phase was measured after centrifugal separation. The yield was 92%, the l/b ratio was 33.8 and the TON value was 9780.
Example 7
Rh/phosphine ligand complex and molecular sieve co-catalyst to catalyze 1-decene (substrate: catalyst =1 × 10) 4 ) Acetalization reaction with EtOH
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1 mg), ZSM-35 (10) (40.0 mg), etOH (5.0 mL), 1-decene (0.66 mL), decane (16. Mu.L) were added to the autoclave and stirred, and the mixture was stirred with H 2 Purging three times, then charging CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was decreased to room temperature, and the gas phase was measured after centrifugal separation. The yield was 84%, the l/b ratio was 30.5 and the TON value was 9930.
Example 8
Rh/phosphine ligand complex and molecular sieve co-catalyst catalysis of cyclohexene (substrate: catalyst =1 × 10) 4 ) Acetalization reaction with EtOH
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1 mg), ZSM-35 (10) (40.0 mg), etOH (5.0 mL), cyclohexene (0.39 mL), decane (16. Mu.L) were added to the autoclave and stirred, and the mixture was stirred with H 2 Purging three times, then charging CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was allowed to decrease to room temperature, and the gas phase was measured after centrifugal separation. The yield was 84% and the TON value was 9160.
Example 9
Rh/phosphine ligand complex and molecular sieve cocatalyst catalyzed 1-hexene (substrate: catalyst =1 × 10) 4 ) Acetalization with MeOH
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1 mg), ZSM-35 (10) (40.0 mg), meOH (5.0 mL), 1-hexene (0.47 mL), decane (16. Mu.L) were added to the autoclave and stirred, and the mixture was stirred with H 2 Purging three times, then charging CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was allowed to decrease to room temperature, and the gas phase was measured after centrifugal separation. The yield was 98%, the l/b ratio was 75.5 and the TON value was 9790.
Example 10
Rh/phosphine ligand complex and molecular sieve co-catalyst to catalyze 1-hexene (substrate: catalyst =1 × 10) 4 ) And n acetalization reaction of PrOH
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1mg),ZSM-35(10)(40.0mg), n PrOH (5.0 mL), 1-hexene (0.47 mL), decane (16. Mu.L) were added to the autoclave and stirred, and the mixture was quenched with H 2 Purging three times, then charging CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was allowed to decrease to room temperature, and the gas phase was measured after centrifugal separation. The yield was 93%, the l/b ratio was 99.8 and the TON value was 10000.
Example 11
Rh/phosphine ligand complex and molecular sieve co-catalyst to catalyze 1-hexene (substrate: catalyst =1 × 10) 4 ) And n acetalization reaction of BuOH
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1mg),ZSM-35(10)(40.0mg), n BuOH (5.0 mL), 1-hexene (0.47 mL), decane (16. Mu.L) were added to the autoclave and stirred, and the mixture was taken with H 2 Purging three times, then charging CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was decreased to room temperature, and the gas phase was measured after centrifugal separation. The yield was 91%, the l/b ratio was 77.0 and the TON value was 10000.
Example 12
Rh/phosphine ligand complex and molecular sieve co-catalyst to catalyze 1-hexene (substrate: catalyst =1 × 10) 4 ) And (CH) 2 OH) 2 Acetalation reaction of
In a glove box, BINAPa (1.16 mg), rh (acac) (CO) 2 (0.1mg),ZSM-35(10)(40.0mg),(CH 2 OH) 2 (5.0 mL), 1-hexene (0.47 mL), decane (16. Mu.L) were added to the autoclave and stirred, and the mixture was stirred with H 2 Purging three times, then charging with CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was allowed to decrease to room temperature, and the gas phase was measured after centrifugal separation. The yield was 99%, the l/b ratio was 86.3 and the TON value was 10000.
Example 13
Rh/phosphine ligand complex and molecular sieve co-catalyst to catalyze 1-hexene (substrate: catalyst =5 × 10) 4 ) Acetalization with MeOH
In a glove box, BINAPa (0.23 mg), rh (acac) (CO) 2 (0.02 mg), ZSM-35 (10) (40.0 mg), meOH (5.0 mL), 1-hexene (0.47 mL), decane (16. Mu.L) were added to the autoclave and stirred, and the mixture was stirred with H 2 Purging three times, then charging with CO (20 bar) and H 2 (20 bar). Then the high-pressure reaction kettle is stirred and reacted for 24 hours at the temperature of 120 ℃ in an oil bath. After the reaction was completed, the temperature was allowed to decrease to room temperature, and the gas phase was measured after centrifugal separation. The yield was 82%, the l/b ratio was 84.6 and the TON value was 43000.
The above examples are only used to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding claims.
Claims (6)
1. A method for synthesizing acetal is characterized in that the method comprises the following steps: shown as a general formula 1, under the action of Rh/phosphine ligand complex and molecular sieve cocatalyst, olefins I and H 2 Heating CO and organic alcohol for reaction; after the reaction is completed, centrifugally separating the molecular sieve, and carrying out reduced pressure distillation to obtain acetal II shown in the general formula 1;
Wherein R is x Are respectively and independently selected from hydrogen, hydroxyl, sulfonic group, halogen, nitrile group and C 1 ~C 10 Alkyl of (A), C 1 ~C 10 Alkoxy group of (C) 1 ~C 10 Alkanoyl of (2), C 1 ~C 10 One of the ester groups of (a).
2. The method of claim 1, wherein the phosphine ligand of step (1) is selected from one of the following structures:
R 1 are respectively selected from hydrogen, sulfonic group, halogen, nitrile group and C 1 ~C 10 Alkyl of (2), C 1 ~C 10 Alkoxy group of,
Wherein: r is x Are respectively and independently selected from hydrogen, sulfonic group, halogen, nitrile group and C 1 ~C 10 Alkyl of (A), C 1 ~C 10 Alkoxy group of (1), C 1 ~C 10 Alkanoyl of (2), C 1 ~C 10 Ester group of (A) or (C) 1 ~C 10 A sulfonate group of (a).
3. The method according to claim 1, wherein the organic solvent is one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, ethylene glycol, 1, 3-propanediol, and glycerol.
4. The method according to claim 1, wherein the molecular sieves are respectively selected from one or more of MCM-41, ZSM-5, beta-Zeolite, ZSM-35 (100), ZSM-35 (10) and ZSM-23, ZSM-22, ZSM-11, KIT-6, SBA-15, MCM-22, MCM-48, SSZ-13, UIO-66, tiSi molecular sieve TS-1, SAPO-34, SAPO-11, silica nanospheres, mesoporous silica, multi-stage pore silica microspheres, solid silica, carbon molecular sieves, 3A molecular sieves, 4A molecular sieves, 5A molecular sieves, 13X molecular sieves, Y molecular sieves, COF organic framework materials and S-1 all-silica molecular sieves.
5. The process of claim 1, wherein the reaction temperature is 60 to 200 ℃.
6. The method of claim 1, wherein H is 2 The pressure/CO is between 3/3bar and 100/100bar.
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CN103304386A (en) * | 2013-06-07 | 2013-09-18 | 青岛科技大学 | Method for preparing acetal through alkene hydroformylation-acetalation one-pot method |
CN107866282A (en) * | 2016-09-23 | 2018-04-03 | 华东师范大学 | A kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction |
CN113583045A (en) * | 2021-09-02 | 2021-11-02 | 成都欣华源科技有限责任公司 | Catalyst composition containing bidentate phosphine ligand and application thereof |
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CN103304386A (en) * | 2013-06-07 | 2013-09-18 | 青岛科技大学 | Method for preparing acetal through alkene hydroformylation-acetalation one-pot method |
CN107866282A (en) * | 2016-09-23 | 2018-04-03 | 华东师范大学 | A kind of application containing aminophosphine ligand in olefin hydroformylation cascade reaction |
CN113583045A (en) * | 2021-09-02 | 2021-11-02 | 成都欣华源科技有限责任公司 | Catalyst composition containing bidentate phosphine ligand and application thereof |
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