CN116947608A - Preparation method and application of 1, 4-tetramethoxy-2-butene - Google Patents
Preparation method and application of 1, 4-tetramethoxy-2-butene Download PDFInfo
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- CN116947608A CN116947608A CN202310733107.6A CN202310733107A CN116947608A CN 116947608 A CN116947608 A CN 116947608A CN 202310733107 A CN202310733107 A CN 202310733107A CN 116947608 A CN116947608 A CN 116947608A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 acetaldehyde dimethyl acetal phosphine salt Chemical compound 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- CRZJPEIBPQWDGJ-UHFFFAOYSA-N 2-chloro-1,1-dimethoxyethane Chemical compound COC(CCl)OC CRZJPEIBPQWDGJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940015043 glyoxal Drugs 0.000 claims abstract description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- AYODHZHFDRRQEZ-UHFFFAOYSA-N 2,7-dimethylocta-2,4,6-trienedial Chemical compound O=CC(C)=CC=CC=C(C)C=O AYODHZHFDRRQEZ-UHFFFAOYSA-N 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract 1
- 239000012074 organic phase Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000010992 reflux Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QHMVQKOXILNZQR-UHFFFAOYSA-N 1-methoxyprop-1-ene Chemical compound COC=CC QHMVQKOXILNZQR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000021466 carotenoid Nutrition 0.000 description 2
- 150000001747 carotenoids Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000576 food coloring agent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- 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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double 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
- C07C45/513—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 etherified hydroxyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5352—Phosphoranes containing the structure P=C-
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- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method and application of 1, 4-tetramethoxy-2-butene, and belongs to the field of organic chemical synthesis. The method comprises the following steps: reacting chloroacetaldehyde dimethyl acetal with triphenylphosphine to generate acetaldehyde dimethyl acetal phosphine salt; the acetaldehyde dimethanol phosphine acetal reacts with glyoxal monoacetal to produce 1, 4-tetramethoxy-2-butene. The method is efficient and environment-friendly, and is simple to operate and environment-friendly.
Description
Technical Field
The invention discloses a preparation method and application of 1, 4-tetramethoxy-2-butene, and belongs to the field of organic chemical synthesis.
Background
Carotenoids have a wide range of applications in the fields of food coloring, antioxidation, etc. 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde (called as decadialdehyde for short) is a key intermediate for synthesizing carotenoid, and 1, 4-tetramethoxy-2-butene is a key raw material for synthesizing decadialdehyde. Patent CN114214648B uses furan as raw material and adopts electrochemical method to synthesize 1, 4-tetramethoxy-2-butene. The method needs to bromize furan, and has the advantages of large environmental pollution, complex process and low yield.
Disclosure of Invention
According to the defects of the prior art, the invention discloses a preparation method and application of 1, 4-tetramethoxy-2-butene, wherein the method is simple to operate and environment-friendly, and the yield of 1, 4-tetramethoxy-2-butene is higher. Specifically, the invention can be realized by the following technical scheme:
a preparation method of 1, 4-tetramethoxy-2-butene comprises the following steps:
adding chloroacetaldehyde dimethyl acetal, triphenylphosphine and alkali into an organic solvent, and drying to obtain acetaldehyde dimethyl acetal phosphine salt;
the acetaldehyde dimethyl acetal phosphine salt and glyoxal monoacetal are mixed to obtain a mixed solution containing triphenylphosphine oxide and 1, 4-tetramethoxy-2-butene;
adding a polar solvent into the mixed solution, and distilling to obtain 1, 4-tetramethoxy-2-butene.
Further, the organic solvent includes a mixture of any one or more of toluene, methylene chloride, tetrahydrofuran, n-hexane, n-heptane, and dioxane.
Preferably, the organic solvent is dichloromethane.
Further, the molar ratio of the chloroacetaldehyde dimethyl acetal to the triphenylphosphine is 1:1 to 1.5.
Preferably, the molar ratio of the chloroacetaldehyde dimethyl acetal to triphenylphosphine is 1:1 to 1.2.
Further, the temperature of the mixed reaction of the chloroacetaldehyde dimethyl acetal, the triphenylphosphine and the alkali is 0-100 ℃.
Preferably, the temperature of the mixed reaction of the chloroacetaldehyde dimethyl acetal, the triphenylphosphine and the alkali is 20-60 ℃.
Further, the base includes sodium methoxide or potassium hydroxide.
Preferably, the base is potassium hydroxide.
Further, the molar ratio of the acetaldehyde dimethyl acetal phosphine salt to glyoxal monoacetal is 1:1 to 1.5.
Preferably, the molar ratio of the glyoxylate to the glyoxal monoacetal is 1:1 to 1.2.
Further, the organic solvent for the mixed reaction of the glyoxylate and the glyoxal monoacetal comprises any one or a mixture of more of toluene, methylene dichloride, tetrahydrofuran, normal hexane, normal heptane, methyl tertiary butyl ether and dioxane.
Preferably, the organic solvent for the mixed reaction of the glyoxylate and the glyoxal monoacetal is toluene.
Further, the polar solvent includes a mixture of any one or more of n-hexane, n-heptane and petroleum ether.
Preferably, the polar solvent is n-heptane.
Further, the conditions of the distillation include a heating temperature of 130 to 150 ℃, a vacuum pump pressure of 500 to 600Pa and a separation temperature of 110 to 112 ℃.
The invention has the beneficial effects that:
(1) The preparation method is simple to operate and is environment-friendly.
(2) The purity and recovery rate of the 1, 4-tetramethoxy-2-butene prepared by the method are high.
Drawings
FIG. 1 is a schematic illustration of the preparation route of the present invention.
FIG. 2 is a high performance liquid chromatogram of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde prepared in examples 6 and 7.
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 innovative effort, are intended to be within the scope of the invention.
Example 1:
the preparation method of the 1, 4-tetramethoxy-2-butene specifically comprises the following steps:
(1) Preparation of glyoxylate dimelhylphosphine salt
400ml of dichloromethane and 60.3g of chloroacetaldehyde dimethyl acetal are put into a reaction bottle, stirring is started, 150g of triphenylphosphine is weighed, water bath is heated, micro positive pressure is controlled, the temperature in the reactor is controlled to be 40-45 ℃, and reflux reaction is carried out for 5 hours at constant temperature. Continuously heating to 60-64 ℃, and carrying out constant-temperature reflux reaction for 1h. Cooling to room temperature, dropwise adding 108g of 30% potassium hydroxide aqueous solution, continuously stirring for 30min after the completion of dropwise adding, standing for layering, recovering an organic phase, separating a product, and vacuum drying to obtain 164.8g of acetaldehyde dimethyl acetal phosphine salt.
(2) Preparation of 1, 4-tetramethoxy-2-butene
400ml of toluene is added into a reaction bottle, 164.8g of acetaldehyde dimethyl acetal phosphine salt is added, the temperature is reduced to 0-5 ℃, 166.2g of 30% glyoxal monoacetal aqueous solution is slowly added into the reaction bottle, after the dripping is finished, the temperature is increased to 25-30 ℃, and the reaction is carried out for 4 hours at constant temperature. After the reaction is finished, standing and layering are carried out at normal temperature for 1h. And (3) distilling the organic phase under reduced pressure to recover toluene, adding 600ml of n-heptane completely after the toluene is recovered, stirring and dissolving for 30min, removing by-product triphenylphosphine oxide by suction filtration, recovering n-heptane from filtrate, and distilling under reduced pressure with the external temperature controlled between 130 and 150 ℃ and the vacuum pump pressure controlled between 500 and 600Pa to collect 110-112 ℃ fractions to obtain 82.6g of 1, 4-tetramethoxy-2-butene. The content of 1, 4-tetramethoxy-2-butene was 99.56% by gas chromatography, and the yield was 96.84%.
Example 2:
the preparation method of the 1, 4-tetramethoxy-2-butene specifically comprises the following steps:
(1) Preparation of glyoxylate dimelhylphosphine salt
550ml of n-hexane and 80.4g of chloroacetaldehyde dimethyl acetal are put into a reaction bottle, stirring is started, 200g of triphenylphosphine is weighed, the temperature is raised in a water bath, the temperature in the reactor is controlled to be 35-40 ℃, and the reflux reaction is carried out for 5 hours at constant temperature. Continuously heating to 60-64 ℃, and carrying out constant-temperature reflux reaction for 1h. Cooling to room temperature, dropwise adding 103.2g of 30% sodium hydroxide aqueous solution, continuously stirring for 30min after the completion of dropwise adding, standing for layering, recovering an organic phase, separating a product, and vacuum drying to obtain 219.73g of acetaldehyde dimethyl acetal phosphine salt.
(2) Preparation of 1, 4-tetramethoxy-2-butene
550ml of methyl tertiary butyl ether is added into a reaction bottle, 219.73g of acetaldehyde dimethyl acetal phosphine salt is added, the temperature is reduced to 0-5 ℃, 221.6g of 30% glyoxal monoacetal aqueous solution is slowly added into the reaction bottle in a dropwise manner, the temperature is increased to 25-30 ℃ after the dropwise addition, and the reaction is carried out for 4 hours at constant temperature. After the reaction is finished, standing and layering are carried out at normal temperature for 1h. The organic phase is distilled under reduced pressure to recover methyl tertiary butyl ether, 800ml of n-heptane is added after the recovery of methyl tertiary butyl ether is completed, the mixture is stirred and dissolved for 30min, and the byproduct triphenylphosphine oxide is removed by suction filtration. Recovering n-heptane from the filtrate, and distilling under reduced pressure at 130-150deg.C and 500-600Pa to collect 110-112 deg.C fraction to obtain 107.6g of 1, 4-tetramethoxy-2-butene with content of 99.13% and yield of 94.61% by gas chromatography analysis.
Example 3:
the preparation method of the 1, 4-tetramethoxy-2-butene specifically comprises the following steps:
(1) Preparation of glyoxylate dimelhylphosphine salt
550ml dioxane and 80.4g chloroacetaldehyde dimethyl acetal are put into a reaction bottle, stirring is started, 200g triphenylphosphine is weighed, water bath is heated, the temperature in the reactor is controlled to be 35-40 ℃, and reflux reaction is carried out for 5 hours at constant temperature. Continuously heating to 60-64 ℃, and carrying out constant-temperature reflux reaction for 1h. Cooling to room temperature, dropwise adding 140g of 30% sodium methoxide methanol solution, continuously stirring for 30min after the completion of dropwise adding 200g of water, standing for layering, recovering an organic phase, separating a product, and vacuum drying to obtain 217.89g of acetaldehyde dimethyl acetal phosphine salt.
(2) Preparation of 1, 4-tetramethoxy-2-butene
550ml of toluene is added into a reaction bottle, 217.89g of acetaldehyde dimethyl acetal phosphine salt is added, the temperature is reduced to 0-5 ℃, 221.6g of 30% glyoxal monoacetal aqueous solution is slowly added into the reaction bottle, after the dripping is finished, the temperature is increased to 35-40 ℃, and the reaction is carried out for 2 hours at constant temperature. After the reaction is finished, standing and layering are carried out at normal temperature for 1h. The organic phase is distilled under reduced pressure to recycle toluene, 800ml of n-heptane is added to be stirred and dissolved for 30min after the toluene is recycled, and the byproduct triphenylphosphine oxide is removed by suction filtration. Recovering n-heptane from the filtrate, and distilling under reduced pressure at 130-150deg.C and 500-600Pa to collect 110-112 deg.C fraction to obtain 105.3g of 1, 4-tetramethoxy-2-butene. The content of 1, 4-tetramethoxy-2-butene was 99.27% by gas chromatography, and the yield was 92.59%.
Example 4:
the preparation method of the 1, 4-tetramethoxy-2-butene specifically comprises the following steps:
(1) Preparation of glyoxylate dimelhylphosphine salt
550ml of dichloromethane and 80.4g of chloroacetaldehyde dimethyl acetal are put into a reaction bottle, stirring is started, 200g of triphenylphosphine is weighed, water bath is heated, micro positive pressure is controlled, the temperature in the reactor is controlled to be 40-45 ℃, and reflux reaction is carried out for 5 hours at constant temperature. Continuously heating to 60-64 ℃, and carrying out constant-temperature reflux reaction for 1h. Cooling to room temperature, dropwise adding 140g of 30% sodium methoxide methanol solution, continuously stirring for 30min after the completion of dropwise adding 200g of water, standing for layering, recovering an organic phase, separating a product, and vacuum drying to obtain 219.8g of acetaldehyde dimethanol phosphonate.
(2) Preparation of 1, 4-tetramethoxy-2-butene
550ml of toluene is added into a reaction bottle, 219.8g of acetaldehyde dimethyl acetal phosphine salt is added, the temperature is reduced to 0-5 ℃, 221.6g of 30% glyoxal monoacetal aqueous solution is slowly added into the reaction bottle, after the dripping is finished, the temperature is increased to 35-40 ℃, and the reaction is carried out for 2 hours at constant temperature. After the reaction is finished, standing and layering are carried out at normal temperature for 1h. The organic phase is distilled under reduced pressure to recycle toluene, 800ml of n-heptane is added to be stirred and dissolved for 30min after the toluene is recycled, and the byproduct triphenylphosphine oxide is removed by suction filtration. Recovering n-heptane from the filtrate, and distilling under reduced pressure at 130-150deg.C and 500-600Pa to collect 110-112 deg.C fraction to obtain 111.2g of 1, 4-tetramethoxy-2-butene. The content of 1, 4-tetramethoxy-2-butene was 99.56% by gas chromatography, and the yield was 97.78%.
Example 5:
the preparation method of the 1, 4-tetramethoxy-2-butene specifically comprises the following steps:
(1) Preparation of glyoxylate dimelhylphosphine salt
550ml dioxane and 80.4g chloroacetaldehyde dimethyl acetal are put into a reaction bottle, stirring is started, 200g triphenylphosphine is weighed, water bath is heated, the temperature in the reactor is controlled to be 35-40 ℃, and reflux reaction is carried out for 5 hours at constant temperature. Continuously heating to 60-64 ℃, and carrying out constant-temperature reflux reaction for 1h. Cooling to room temperature, dropwise adding 144g of 30% potassium hydroxide aqueous solution, continuously stirring for 30min after the dropwise addition, standing for layering, recovering an organic phase, separating a product, and vacuum drying to obtain 217.89g of acetaldehyde dimethyl acetal phosphonate.
(2) Preparation of 1, 4-tetramethoxy-2-butene
550ml of tetrahydrofuran is added into a reaction bottle, 217.89g of acetaldehyde dimethyl acetal phosphine salt is added, the temperature is reduced to 0-5 ℃, 221.6g of 30% glyoxal monoacetal aqueous solution is slowly added into the reaction bottle, after the dripping is finished, the temperature is increased to 35-40 ℃, and the reaction is carried out for 3 hours at constant temperature. After the reaction is finished, standing and layering are carried out at normal temperature for 1h. The organic phase is distilled under reduced pressure to recycle tetrahydrofuran, 800ml of n-heptane is added to be stirred and dissolved for 30min after the tetrahydrofuran is recycled, and the byproduct triphenylphosphine oxide is filtered out by suction to be used as a byproduct. Recovering n-heptane from the filtrate, and distilling under reduced pressure at 130-150deg.C and 500-600Pa to collect 110-112 deg.C fraction to obtain 103.6g of 1, 4-tetramethoxy-2-butene. The content of 1, 4-tetramethoxy-2-butene was 98.22% by gas chromatography, and the yield was 91.09%.
Example 6:
the application of the 1, 4-tetramethoxy-2-butene specifically comprises the following steps:
(1) Adding 30g of 1, 4-tetramethoxy-2-butene obtained in example 1, adding 200ml of toluene and 3g of ferric trichloride, stirring, dropwise adding propenyl methyl ether at 0-5 ℃, controlling the dropwise adding time to be completed, preserving heat for 2 hours, adding water to quench reaction, standing for layering, and standing an organic phase for later use.
(2) Adding 200ml of 1% sulfuric acid into the organic phase obtained in the step (1), stirring and heating to 80 ℃, preserving heat and reacting for 7 hours, thermally layering, removing a water layer, adding 100ml of 0.5% sodium carbonate solution into the organic phase, controlling the reaction temperature to 70-80 ℃ and reacting for 5 hours, cooling to 5 ℃, carrying out suction filtration, and carrying out vacuum drying at 55 ℃ to obtain 24g of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde, wherein the liquid chromatography analysis content is 99.57%, and the yield is 85.85%.
Example 7:
the application of the 1, 4-tetramethoxy-2-butene specifically comprises the following steps:
(1) Adding 30g of 1, 4-tetramethoxy-2-butene obtained in example 2, adding 200ml of toluene and 2g of ferric trichloride, stirring, dropwise adding propenyl methyl ether at 0-5 ℃, controlling the dropwise adding time to be completed, preserving heat for 2 hours, adding water to quench reaction, standing for layering, and standing an organic phase for later use.
(2) Adding 200ml of 1% oxalic acid into the organic phase obtained in the step (1), stirring and heating to 90 ℃, preserving heat and reacting for 6 hours, thermally layering, removing a water layer, adding 100ml of 0.5% sodium carbonate solution into the organic phase, controlling the reaction temperature to 70-80 ℃ and reacting for 5 hours, cooling to 5 ℃, carrying out suction filtration, and carrying out vacuum drying at 55 ℃ to obtain 23.67g of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde, wherein the analysis content of the liquid chromatography is 99.41%, and the yield is 84.67%.
From the experimental results, it can be seen that:
(1) The content of 1, 4-tetramethoxy-2-butene prepared by the method disclosed by the invention is more than 98 percent, the recovery yields of the 1, 4-tetramethoxy-2-butene are all more than 90%, which indicates that the 1, 4-tetramethoxy-2-butene prepared by the invention has high purity and high recovery rate;
(2) The by-product triphenylphosphine oxide generated by the experiment can be effectively filtered, and has no pollution to the environment.
The foregoing embodiments have described the technical solutions and advantageous effects of the present invention in detail, and it should be understood that the foregoing embodiments are merely specific examples of the present invention, and are not intended to limit the present invention. Any modifications, additions, and equivalent substitutions made within the principle of the invention should be included in the protection scope of the invention.
Claims (10)
1. A process for the preparation of 1, 4-tetramethoxy-2-butene, characterized in that it comprises the steps of:
adding chloroacetaldehyde dimethyl acetal, triphenylphosphine and alkali into an organic solvent, and drying to obtain acetaldehyde dimethyl acetal phosphine salt;
the acetaldehyde dimethyl acetal phosphine salt and glyoxal monoacetal are mixed to obtain a mixed solution containing triphenylphosphine oxide and 1, 4-tetramethoxy-2-butene;
adding a polar solvent into the mixed solution, and distilling to obtain 1, 4-tetramethoxy-2-butene.
2. The method of claim 1, wherein the organic solvent comprises a mixture of any one or more of toluene, methylene chloride, tetrahydrofuran, n-hexane, n-heptane, and dioxane.
3. The method according to claim 1, wherein the molar ratio of chloroacetaldehyde dimethyl acetal to triphenylphosphine is 1:1 to 1.5.
4. The process of claim 1 wherein the temperature of the mixing reaction of chloroacetaldehyde dimethyl acetal, triphenylphosphine and base is from 0 to 100 ℃.
5. The method of claim 1, wherein the base comprises sodium methoxide or potassium hydroxide.
6. The method according to claim 1, wherein the molar ratio of acetaldehyde dimethanol phosphonate to glyoxal monoacetal is 1:1 to 1.5.
7. The method of claim 1, wherein the organic solvent for the mixed reaction of glyoxylate and glyoxal monoacetal comprises a mixture of any one or more of toluene, methylene chloride, tetrahydrofuran, n-hexane, n-heptane, methyl t-butyl ether, and dioxane.
8. The method of claim 1, wherein the polar solvent comprises a mixture of any one or more of n-hexane, n-heptane, and petroleum ether.
9. The method according to claim 1, wherein the conditions of distillation include a heating temperature of 130 to 150 ℃, a vacuum pump pressure of 500 to 600Pa and a separation temperature of 110 to 112 ℃.
10. Use of 1, 4-tetramethoxy-2-butene obtained by the process according to any of claims 1 to 9 for the preparation of 2, 7-dimethyl-2, 4, 6-octatriene-1, 8-dialdehyde.
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