CN114835577B - Aldehyde synthesis method - Google Patents
Aldehyde synthesis method Download PDFInfo
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- CN114835577B CN114835577B CN202210641129.5A CN202210641129A CN114835577B CN 114835577 B CN114835577 B CN 114835577B CN 202210641129 A CN202210641129 A CN 202210641129A CN 114835577 B CN114835577 B CN 114835577B
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- 238000001308 synthesis method Methods 0.000 title abstract description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 15
- LPDDKAJRWGPGSI-UHFFFAOYSA-N (3-methyl-4-oxobut-2-enyl) acetate Chemical compound CC(=O)OCC=C(C)C=O LPDDKAJRWGPGSI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- -1 propenyl diethyl ether Chemical compound 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000012267 brine Substances 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- HIEAVKFYHNFZNR-UHFFFAOYSA-N pentadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCOP(O)(O)=O HIEAVKFYHNFZNR-UHFFFAOYSA-N 0.000 description 3
- 229950009390 symclosene Drugs 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- URVYVINLDPIJEH-UHFFFAOYSA-N (4-chloro-3-methylbut-2-enyl) acetate Chemical compound CC(=O)OCC=C(C)CCl URVYVINLDPIJEH-UHFFFAOYSA-N 0.000 description 1
- VUQIEMOGCCDRND-UHFFFAOYSA-N 1-chloro-2-methylbut-3-en-2-ol Chemical compound ClCC(O)(C)C=C VUQIEMOGCCDRND-UHFFFAOYSA-N 0.000 description 1
- QZYCIZBUCPJIGT-UHFFFAOYSA-N 4-chloro-3-methylbut-2-en-1-ol Chemical compound ClCC(C)=CCO QZYCIZBUCPJIGT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical class [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 229960000342 retinol acetate Drugs 0.000 description 1
- 235000019173 retinyl acetate Nutrition 0.000 description 1
- 239000011770 retinyl acetate Substances 0.000 description 1
- QGNJRVVDBSJHIZ-QHLGVNSISA-N retinyl acetate Chemical compound CC(=O)OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C QGNJRVVDBSJHIZ-QHLGVNSISA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
- C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
-
- 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
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
-
- 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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- 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 aldehyde, which comprises the following steps: step one, synthesizing an intermediate 1, and step two: synthesis of intermediate 2, step three: synthesis of 4-acetoxy-2-methyl-2-butene-1-aldehyde. The synthesis method solves the problems of high production cost, more three wastes and difficult treatment after the 4-acetoxyl-2-methyl-2-butene-1-aldehyde is synthesized by the prior art route.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a synthesis method of aldehyde.
Background
With the continuous development of the current technology, 4-acetoxyl-2-methyl-2-butene-1-aldehyde (five-carbon aldehyde for short) is a key intermediate for synthesizing vitamin A acetate and carotenoid by a C15+C5 route characterized by Wittig-Homer reaction, and the structural formula is as follows:
Representative routes of major industrialization at present are: 1) Isoprene is taken as a starting material, and is subjected to addition reaction with hypochlorous acid generated by hydrolyzing trichloroisocyanuric acid to obtain a mixture of 1-chloro-2-methyl-3-buten-2-ol and 4-chloro-3-methyl-2-buten-1-ol, after desolventizing, the mixture is subjected to esterification reaction and propenyl rearrangement with acetic anhydride to obtain 1-acetoxyl-4-chloro-3-methyl-2-butene, and finally the mixture is subjected to salt formation reaction and sulfuric acid hydrolysis reaction with urotropine to obtain pentacarbon aldehyde.
The process route is longer, the product yield is low (only about 36%), a large amount of raw materials such as isoprene, trichloroisocyanuric acid, acetic anhydride, urotropine, sulfuric acid, acetone, methylene dichloride, toluene and the like are needed in the synthesis process, the atom utilization rate is low, the production cost is high, the amount of the generated three wastes is large, the treatment difficulty is high (the waste products comprise isocyanuric acid residues generated by the reaction of the trichloroisocyanuric acid and water, a large amount of ammonia nitrogen compounds are generated after the urotropine is salified, and more high COD waste water is generated by the operation of extracting and washing for many times).
2): The target product of pentacarbon aldehyde is obtained by using butylene glycol as a starting material and through esterification, rearrangement, carbonylation and decarboxylation. The process involves dangerous reactions: carbonylation (hydrogen+carbon monoxide) and high temperature and pressure, high requirements for equipment and personnel operation, and expensive rhodium metal as a key catalyst. Therefore, a green and efficient five-carbon aldehyde synthesis process route is developed, the economic benefit of enterprises is improved, and the method is of great significance in industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a synthesis method of aldehyde, which can solve the problems of high production cost, more three wastes and difficult treatment after 4-acetoxyl-2-methyl-2-butene-1-aldehyde is synthesized by the prior art route.
The aim of the invention can be achieved by the following technical scheme:
a method of synthesizing an aldehyde, the method comprising the steps of:
Step one, synthesizing an intermediate 1.
Step two: synthesis of intermediate 2.
Step three: synthesis of 4-acetoxy-2-methyl-2-butene-1-aldehyde.
Further, the synthesis of intermediate 1 comprises the following steps:
step one: respectively preparing haloacetaldehyde dimethyl acetal and propenyl diethyl ether according to the weight ratio for standby.
Step two: respectively pumping raw materials of haloacetaldehyde dimethyl acetal and propenyl diethyl ether into two reaction kettles by using a pneumatic diaphragm pump, wherein the haloacetaldehyde dimethyl acetal is prepared by the following steps: propenyl diethyl ether was 1:1.05 to 1.15 (molar ratio), the molar yield is 73 to 89.6 percent, toluene reaction solvent with the weight ratio of 0.8 to 2:1 is added, nitrogen is filled up to be vacuum, stirring is started, and chilled brine is started for cooling.
Step three: and (3) when the temperature is reduced to-15 ℃, adding boron trifluoride serving as a catalyst, wherein the dosage of the catalyst is 0.5-2.5% of the mass of propenyl diethyl ether, and continuously stirring for 20 minutes.
Step four: opening a bottom valve of a propenyl diethyl ether toluene solution reaction kettle, controlling the flow through a rotameter, slowly dripping propenyl diethyl ether toluene solution, reacting, and controlling the dripping time to be 6 hours.
Step five: maintaining the temperature in the kettle at-15 ℃, stirring and reacting for 60-100 minutes, and standing for 30-60 minutes.
Step six: and (3) pressing the reacted material nitrogen into another reaction kettle, adding 1000 kg of water for washing, separating the lower water phase, keeping the organic phase in the reaction kettle, adding water for washing once, and continuing the water separation operation.
Step seven: recovering toluene as solvent under reduced pressure, starting a secondary vacuum pump to continue to decompress for 30-60 minutes after the solvent recovery is basically finished, and obtaining the residue in the kettle as an intermediate 1, wherein the structural formula is shown as follows:
Further, the synthesis of intermediate 2 comprises the following steps:
Step 1: adding the intermediate 1, trifluoroacetic acid serving as a catalyst and water into a reaction kettle, wherein the dosage (mass fraction) of the catalyst is 0.1-3% of that of the intermediate 1, the dosage of the water is 2-5 times of that of the intermediate 1, adding toluene solvent with the weight ratio of 0.8-2:1, starting stirring, starting hot water with the molar yield of 88-96.6%, heating to 70 ℃, and preserving heat for 100 minutes.
Step 2: and (3) pressing the reacted material nitrogen into another reaction kettle to separate out the water phase, adding 1000 kg of water for washing, separating out the lower water phase, and keeping the organic phase in the reaction kettle.
Step 3: recovering solvent toluene under reduced pressure, starting a secondary vacuum pump to continue to decompress for 30-60 minutes after the solvent recovery is basically finished, and obtaining residue in the kettle as an intermediate 2, wherein the structural formula is shown as follows:
further, the synthesis of 4-acetoxy-2-methyl-2-butene-1-aldehyde comprises the following steps:
step one: transferring the intermediate 2 into a synthesis reaction kettle through a transfer pump, and adding an ethanol solvent with the weight ratio of 0.8-2:1 and the mole ratio of 1:1.2 to 1.5 molar yield of sodium acetate is 85 to 92.1 percent, stirring is started, hot water is started to heat up to 70 ℃, and the temperature is kept for reaction for 120 minutes.
Step two: after the heat preservation is finished, the hot water valve is closed to switch the circulating water for cooling to 30 ℃, and the kettle bottom valve is opened to transfer materials to the desolventizing kettle through the filter.
Step three: recovering ethanol under reduced pressure, starting a secondary vacuum pump for continuously decompressing for 30-60 minutes after the solvent recovery is basically finished, adding toluene for dissolving, washing salt substances with water, separating water phase, recovering toluene under reduced pressure, transferring residues in a kettle into a film tower for rectification, and distilling out materials to obtain a final product, namely 4-acetoxyl-2-methyl-2-butene-1-aldehyde, wherein the structural formula is shown as follows:
Further, the synthesis reaction temperature of the intermediate 1 is between 0 ℃ and minus 25 ℃, the synthesis reaction temperature of the intermediate 2 is between 35 ℃ and 85 ℃, and the synthesis reaction temperature of the 4-acetoxy-2-methyl-2-butene-1-aldehyde is between 45 ℃ and 85 ℃.
Further, the catalyst is trifluoroacetic acid or boron trifluoride.
The invention has the beneficial effects that:
1. the reaction in the synthesis method reduces a large amount of three wastes, and is more environment-friendly;
2. the synthetic method of the invention reduces the reaction risk.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to those skilled in the art that other drawings can be obtained according to these drawings without inventive effort.
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a vapor phase diagram of a pure penta-carbaldehyde product of the present invention;
FIG. 2 is a graph showing the results of analysis of five-carbon aldehydes according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be understood that the terms "open," "upper," "lower," "thickness," "top," "middle," "length," "inner," "peripheral," and the like indicate orientation or positional relationships, merely for convenience in describing the present invention and to simplify the description, and do not indicate or imply that the components or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention.
Referring to FIGS. 1-2, a method for synthesizing an aldehyde comprises the steps of:
step one: respectively preparing haloacetaldehyde dimethyl acetal and propenyl diethyl ether according to the weight ratio for standby.
Step two: respectively pumping raw materials of haloacetaldehyde dimethyl acetal and propenyl diethyl ether into two reaction kettles by using a pneumatic diaphragm pump, wherein the haloacetaldehyde dimethyl acetal is prepared by the following steps: propenyl diethyl ether was 1:1.05 to 1.15 (molar ratio), the molar yield is 73 to 89.6 percent, toluene reaction solvent with the weight ratio of 0.8 to 2:1 is added, the reaction temperature is between 0 ℃ and 25 ℃ below zero, nitrogen is filled up and vacuum is carried out, stirring is started, and chilled brine is started for cooling.
Step three: and (3) when the temperature is reduced to-15 ℃, adding boron trifluoride serving as a catalyst, wherein the dosage of the catalyst is 0.5-2.5% of the mass of propenyl diethyl ether, and continuously stirring for 20 minutes.
Step four: opening a bottom valve of a propenyl diethyl ether toluene solution reaction kettle, controlling the flow through a rotameter, slowly dripping propenyl diethyl ether toluene solution, reacting, and controlling the dripping time to be 6 hours.
Step five: maintaining the temperature in the kettle at-15 ℃, stirring and reacting for 60-100 minutes, and standing for 30-60 minutes.
Step six: and (3) pressing the reacted material nitrogen into another reaction kettle, adding 1000 kg of water for washing, separating the lower water phase, keeping the organic phase in the reaction kettle, adding water for washing once, and continuing the water separation operation.
Step seven: recovering toluene as solvent under reduced pressure, starting a secondary vacuum pump to continue to decompress for 30-60 minutes after the solvent recovery is basically finished, and obtaining the residue in the kettle as an intermediate 1, wherein the structural formula is shown as follows:
Step eight: adding the intermediate 1, the catalyst trifluoroacetic acid and water into a reaction kettle, wherein the dosage (mass fraction) of the catalyst is 0.1-3% of that of the intermediate 1, the dosage of the water is 2-5 times of that of the intermediate 1, adding toluene solvent with the weight ratio of 0.8-2:1, starting stirring, reacting at 35-85 ℃, the molar yield is 88-96.6%, starting hot water, heating to 70 ℃, and reacting for 100 minutes while maintaining the temperature.
Step nine: and (3) pressing the reacted material nitrogen into another reaction kettle to separate out the water phase, adding 1000 kg of water for washing, separating out the lower water phase, and keeping the organic phase in the reaction kettle.
Step ten: recovering solvent toluene under reduced pressure, starting a secondary vacuum pump to continue to decompress for 30-60 minutes after the solvent recovery is basically finished, and obtaining residue in the kettle as an intermediate 2, wherein the structural formula is shown as follows:
Step eleven: transferring the intermediate 2 into a synthesis reaction kettle through a transfer pump, wherein the reaction temperature is 45-85 ℃, and adding an ethanol solvent with the weight ratio of 0.8-2:1 and the mole ratio of 1:1.2 to 1.5 molar yield of sodium acetate is 85 to 92.1 percent, stirring is started, hot water is started to heat up to 70 ℃, and the temperature is kept for reaction for 120 minutes.
Step twelve: after the heat preservation is finished, the hot water valve is closed to switch the circulating water for cooling to 30 ℃, and the kettle bottom valve is opened to transfer materials to the desolventizing kettle through the filter.
Step thirteen: recovering ethanol under reduced pressure, starting a secondary vacuum pump for continuously decompressing for 30-60 minutes after the solvent recovery is basically finished, adding toluene for dissolving, washing salt substances with water, separating water phase, recovering toluene under reduced pressure, transferring residues in a kettle into a film tower for rectification, and distilling out materials to obtain a final product, namely 4-acetoxyl-2-methyl-2-butene-1-aldehyde, wherein the structural formula is shown as follows:
The ratio of the synthesized 4-acetoxy-2-methyl-2-butene-1-aldehyde (five-carbon aldehyde) was used for the test:
Test one:
① Preparing a five-carbon aldehyde toluene solution: mixing 125 kg of pentacarbon aldehyde with 97.88% content and 435 kg of toluene, and stirring uniformly for later use;
② Preparing alkali liquor: 870 kg of toluene, 125 kg of sodium tert-butoxide and 330 kg of DMF are mixed and stirred uniformly for standby;
③ Preparing pentadecyl phosphate toluene solution: 250 kg of pentadecyl phosphate and 870 kg of toluene are mixed and stirred uniformly, the temperature is reduced to minus 50 ℃, and ① and ② are added dropwise into ③.
After the addition of the vitamin A oil and the heat preservation for 30 minutes, the kettle is turned, and the vitamin A oil with the content of 230.23 ten thousand units is obtained through washing, extraction, concentration and 96.8 percent of yield.
And (2) testing II:
① Preparing a five-carbon aldehyde toluene solution: mixing 125 kg 97.08% of pentacarbon aldehyde and 435 kg of toluene, and stirring uniformly for later use;
② Preparing alkali liquor: 870 kg of toluene, 125 kg of sodium tert-butoxide and 330 kg of DMF kg are mixed and stirred uniformly for standby;
③ Preparing pentadecyl phosphate toluene solution: mixing and stirring 250 kg of pentadecyl phosphate and 870 kg of toluene uniformly, cooling to 50 ℃ below zero, and simultaneously adding ① and ② drops of ③;
After the addition of the vitamin A oil and the heat preservation for 30 minutes, the mixture is transferred to a kettle, and the mixture is washed, extracted, concentrated and finally the 243 kg vitamin A oil with the content of 231.03 ten thousand units is obtained, and the yield is 97.2%.
And (3) test III:
① Preparing a five-carbon aldehyde toluene solution: 125 kg of pentacarbon aldehyde with 96.28% content and 435 kg of toluene are mixed and stirred uniformly for standby;
② Preparing alkali liquor: 870 kg of toluene, 125 kg of sodium tert-butoxide and 330 kg of DMF kg are mixed and stirred uniformly for standby;
③ Preparing pentadecyl phosphate toluene solution: mixing and stirring 250 kg of pentadecyl phosphate and 870 kg of toluene uniformly, cooling to 50 ℃ below zero, and simultaneously adding ① and ② drops of ③;
after the addition of the vitamin A oil and the heat preservation for 30 minutes, the mixture is transferred to a kettle, and is washed, extracted, concentrated and the vitamin A oil with the content of 230.58 ten thousand units percent is obtained, wherein the yield is 96.4 percent.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (1)
1. A method for synthesizing an aldehyde, comprising the steps of:
Step one: synthesizing an intermediate 1;
Step two: synthesizing an intermediate 2;
step three: synthesis of 4-acetoxy-2-methyl-2-butene-1-aldehyde;
The synthesis of intermediate 1 comprises the following steps:
step one: respectively preparing haloacetaldehyde dimethyl acetal and propenyl diethyl ether according to the weight ratio for standby;
Step two: respectively pumping raw materials of haloacetaldehyde dimethyl acetal and propenyl diethyl ether into two reaction kettles by using a pneumatic diaphragm pump, wherein the haloacetaldehyde dimethyl acetal is prepared by the following steps: the molar ratio of propenyl diethyl ether is 1:1.05 to 1.15, the molar yield is 73 to 89.6 percent, toluene reaction solvent with the weight ratio of 0.8 to 2:1 is added, nitrogen is filled up for vacuum, stirring is started, and chilled brine is started for cooling;
Step three: when the temperature is reduced to-15 ℃, adding boron trifluoride serving as a catalyst, wherein the dosage of the catalyst is 0.5-2.5% of the mass of propenyl diethyl ether, and continuously stirring for 20 minutes;
step four: opening a bottom valve of a propenyl diethyl ether toluene solution reaction kettle, controlling the flow through a rotameter, slowly dripping propenyl diethyl ether toluene solution, reacting, and controlling the dripping time to be 6 hours;
step five: maintaining the temperature in the kettle at-15 ℃, stirring and reacting for 60-100 minutes, and standing for 30-60 minutes;
Step six: pressing the reacted material nitrogen into another reaction kettle, adding 1000 kg of water for washing, separating the lower water phase, keeping the organic phase in the reaction kettle, adding water for washing once, and continuing the water separation operation;
Step seven: recovering toluene as solvent under reduced pressure, starting a secondary vacuum pump to continue to decompress for 30-60 minutes after the solvent recovery is basically finished, and obtaining the residue in the kettle as an intermediate 1, wherein the structural formula is shown as follows:
The synthesis of intermediate 2 comprises the following steps:
Step 1: adding the intermediate 1, the catalyst trifluoroacetic acid and water into a reaction kettle, wherein the mass fraction of the catalyst is 0.1-3% of that of the intermediate 1, the water consumption is 2-5 times of that of the intermediate 1, adding toluene solvent with the weight ratio of 0.8-2:1, starting stirring, the molar yield is 88-96.6%, starting hot water, heating to 70 ℃, and preserving heat for 100 minutes;
Step 2: pressing the reacted material nitrogen into another reaction kettle to separate out water phase, adding 1000 kg of water for washing, separating out lower water phase, and keeping organic phase in the reaction kettle;
step 3: recovering solvent toluene under reduced pressure, starting a secondary vacuum pump to continue to decompress for 30-60 minutes after the solvent recovery is basically finished, and obtaining residue in the kettle as an intermediate 2, wherein the structural formula is shown as follows:
the synthesis of the 4-acetoxy-2-methyl-2-butene-1-aldehyde comprises the following steps:
Step one: transferring the intermediate 2 from the desolventizing kettle to a synthesis reaction kettle through a transfer pump, and adding an ethanol solvent with the weight ratio of 0.8-2:1 and the mole ratio of 1:1.2 to 1.5 molar yield of sodium acetate is 85 to 92.1 percent, starting stirring, starting hot water to raise the temperature to 70 ℃, and preserving heat for reaction for 120 minutes;
Step two: after the heat preservation is finished, a hot water valve is closed to switch circulating water for cooling to 30 ℃, and a kettle bottom valve is opened to transfer materials to a desolventizing kettle through a filter;
Step three: recovering ethanol under reduced pressure, starting a secondary vacuum pump for continuously decompressing for 30-60 minutes after the solvent recovery is basically finished, adding toluene for dissolving, washing salt substances with water, separating water phase, recovering toluene under reduced pressure, transferring residues in a kettle into a film tower for rectification, and distilling out materials to obtain a final product, namely 4-acetoxyl-2-methyl-2-butene-1-aldehyde, wherein the structural formula is shown as follows:
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