CN115745754A - Synthesis method of acetal - Google Patents

Synthesis method of acetal Download PDF

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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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贾肖飞
束喆
宗玲博
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Qingdao University of Science and Technology
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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

Synthesis method of acetal
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;
Figure BDA0003977444380000011
r is independently selected from hydrogen and C 1 ～C 10 Alkyl of (A), C 1 ～C 10 Alkoxy group of,
Figure BDA0003977444380000012
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:
Figure BDA0003977444380000021
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,
Figure BDA0003977444380000022
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;
Figure FDA0003977444370000011
r is independently selected from hydrogen and C 1 ～C 10 Alkyl of (A), C 1 ～C 10 Alkoxy group of,
Figure FDA0003977444370000012
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:
Figure FDA0003977444370000013
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,
Figure FDA0003977444370000014
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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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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