CN115160113A - Method for simultaneously synthesizing two citral intermediates - Google Patents
Method for simultaneously synthesizing two citral intermediates Download PDFInfo
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- CN115160113A CN115160113A CN202210785691.5A CN202210785691A CN115160113A CN 115160113 A CN115160113 A CN 115160113A CN 202210785691 A CN202210785691 A CN 202210785691A CN 115160113 A CN115160113 A CN 115160113A
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- Prior art keywords
- methyl
- butene
- isoprenyl
- reaction
- butenyl ether
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 239000000543 intermediate Substances 0.000 title abstract description 14
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 title abstract description 5
- 229940043350 citral Drugs 0.000 title abstract description 5
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 title abstract description 5
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical compound CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims abstract description 44
- DYUAZBUZLHXXLK-UHFFFAOYSA-N 3-methyl-1,1-bis(3-methylbut-3-enoxy)but-2-ene Chemical compound C(CC(=C)C)OC(C=C(C)C)OCCC(=C)C DYUAZBUZLHXXLK-UHFFFAOYSA-N 0.000 claims abstract description 40
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- NSBIHQJWKCGFMZ-UHFFFAOYSA-N CC(C=CC(C=C(C)C)OC(C=C(C)C)C=CC(=C)C)=C Chemical compound CC(C=CC(C=C(C)C)OC(C=C(C)C)C=CC(=C)C)=C NSBIHQJWKCGFMZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000006462 rearrangement reaction Methods 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 229940078552 o-xylene Drugs 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- 235000021357 Behenic acid Nutrition 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- AMNQGHSNHCPOMO-UHFFFAOYSA-N [O-2].[V+5].CC[O-].CC[O-].CC[O-] Chemical compound [O-2].[V+5].CC[O-].CC[O-].CC[O-] AMNQGHSNHCPOMO-UHFFFAOYSA-N 0.000 claims description 2
- ZJQJDTJZDJTKRK-UHFFFAOYSA-N [O-2].[V+5].[O-]C.[O-]C.[O-]C Chemical compound [O-2].[V+5].[O-]C.[O-]C.[O-]C ZJQJDTJZDJTKRK-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229940116226 behenic acid Drugs 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- CZMNFHBVFGQLCG-UHFFFAOYSA-N 2-methylpropan-1-ol;oxovanadium Chemical compound [V]=O.CC(C)CO.CC(C)CO.CC(C)CO CZMNFHBVFGQLCG-UHFFFAOYSA-N 0.000 claims 1
- LVVXRUMQXAHLCK-UHFFFAOYSA-N [O-2].[V+5].CCCC[O-].CCCC[O-].CCCC[O-] Chemical compound [O-2].[V+5].CCCC[O-].CCCC[O-].CCCC[O-] LVVXRUMQXAHLCK-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000007039 two-step reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 10
- -1 triphenylsiloxy vanadium oxide Chemical compound 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000006661 Meyer-Schuster rearrangement reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- KWNDSKBANPEPIP-UHFFFAOYSA-N 3-methyl-1,1-bis(3-methylbuta-1,3-dienoxy)but-2-ene Chemical compound C(=CC(C)=C)OC(C=C(C)C)OC=CC(C)=C KWNDSKBANPEPIP-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
-
- 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
-
- 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
- C07C45/512—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 a free hydroxyl group
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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 method for simultaneously synthesizing two citral intermediates, namely 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether, which specifically comprises the following steps: dissolving 3-methyl-2-butynol in a solvent, carrying out a rearrangement reaction under the catalysis of a combined catalyst to generate 3-methyl-2-butenal, adding 3-methyl-2-butenol into a reaction system, and continuously reacting the 3-methyl-2-butenal and 3-methyl-2-butenol to obtain 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether. The method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and prenyl-3-methyl-2-butenyl ether by using 3-methyl-2-butynol and 3-methyl-2-butenol as raw materials through continuous two-step reaction simplifies reaction steps, remarkably improves reaction efficiency, reduces equipment cost and labor cost and reduces production cost.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, relates to synthesis of organic intermediates, and particularly relates to a method for simultaneously synthesizing two citral intermediates, namely 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and prenyl-3-methyl-2-butenyl ether.
Background
3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether are important intermediates for the synthesis of fragrances and a range of vitamins. For example, the two can be used as raw materials to synthesize citral with high efficiency. With the increasing use amount of the compounds, the synthesis methods thereof are always in wide focus.
At present, the synthesis method of 3-methyl-2-butene-1-aldehyde diisopentenyl acetal is realized by a two-step strategy, and the synthesis method of isoprenyl-3-methyl-2-butenyl ether is realized by a three-step strategy. The most important and most common method is that 3-methyl-2-butynol is taken as a raw material in the first step, and Meyer-Schuster rearrangement is carried out under the action of a metal catalyst to synthesize the intermediate 3-methyl-2-butenal. For example, ti (OR) has been reported in the literature (Tetrahedron Lett.,1988, 29, 6253 and Polyhedron, 2000, 19,1693, respectively) 4 (R = n-Bu ori-Pr), cuCl and p-toluenesulfonic acid are used as combined catalysts to realize Meyer-Schuster rearrangement of 2-methyl-3-butyn-2-ol in o-dichlorobenzene and obtain 3-methyl-2-butenal with yield of 83-98 percent, and the route has simple reaction but uses a solvent o-dichlorobenzene with high toxicity.
The literature (Tetrahedron Letters, 1990,31,7521) adopts a montmorillonite-supported vanadium catalyst to react 2-methyl-3-butyn-2-ol in xylene to obtain 3-methyl-2-butenal, and only 82% of yield is obtained, and meanwhile, the preparation of the vanadium catalyst is difficult and the cost is high.
The patent CN110028392A discloses a method for isomerizing and synthesizing 3-methyl-2-butenal from 3-methyl-2-butynol catalyzed by a palladium and acid combined catalyst, wherein the 3-methyl-2-butenal reacts under normal pressure, the selectivity of the 3-methyl-2-butenal can reach more than 95%, and the yield is more than 85%. Because a palladium catalyst with higher price is used in the reaction, the cost is relatively higher, and the industrial application of the catalyst is not facilitated.
Patent CN109336750a discloses a method for preparing 3-methyl-2-butenal by catalytic rearrangement using metal oxides such as molybdenum, titanium and vanadium as catalysts and 3-methyl-2-butynol as a raw material in the presence of an auxiliary agent. The method has high requirement on the water content of the 3-methyl-2-butynol, the water content is less than 0.1 percent, the reaction temperature is high, the energy consumption is high, and the used metal oxidant is easy to cause heavy metal pollution.
Patent CN110330415A discloses a method for obtaining 3-methyl-2-butenal by Meyer-Schuster rearrangement reaction of 3-methyl-2-butynol under the conditions of resin, catalyst, solvent and acid gas. The resin is not easy to prepare, the reaction steps are complex, the operation requirement is high, and the industrialization is not facilitated.
After separating to obtain an intermediate 3-methyl-2-butenal, performing condensation reaction between the intermediate and 3-methyl-2-butenol to obtain a product 3-methyl-2-butene-1-aldehyde diisopentenyl acetal. The important synthesis method of the step is that the patent US4933500A discloses that the condensation reaction of 3-methyl-2-butenal and 3-methyl-2-butenol is realized under the negative pressure condition of 80 mmHg (10.7 kPa) (absolute pressure) by taking lithium chloride as a catalyst, and the defect that the lithium chloride has strong corrosion to equipment and is not beneficial to industrial production is overcome.
Patents CN102942460a and CN104788295B disclose a method for preparing unsaturated acetal, which uses nitric acid as a catalyst, and designs two types of tower-type reaction and separation integrated devices respectively, so that 3-methyl-2-butene-1-aldehyde diisopentenyl acetal can be synthesized continuously at low cost.
Patent US5177265a discloses that a condensation reaction of 3-methyl-2-butenal and 3-methyl-2-butenol is achieved under negative pressure with phosphoric acid as a catalyst and toluene as a solvent, and the conversion of the isopropenal is 83%. However, the excess acid after the completion needs to be neutralized by adding a base, which increases the reaction cost and the difficulty of post-treatment.
The literature (Chinese Journal of Applied Chemistry, 2012, 29, 270) reports that 0.33 mol% of isopentenoic acid is used as a catalyst, 3-methyl-2-butenal and 3-methyl-2-butenol are used as raw materials, cyclohexane is used as a solvent, and the reaction is carried out under the negative pressure condition of 70-75 ℃ to obtain a condensation product, but the conversion rate of the 3-methyl-2-butenal is only 63.5%.
The third step product, namely, the prenyl-3-methyl-2-butenyl ether, needs to be prepared by using 3-methyl-2-butene-1-aldehyde diisopentenyl acetal, and corresponding patents and literatures also report. Patent CN103787852a discloses a method for preparing prenyl-3-methyl-2-butenyl ether from 3-methyl-2-butene-1-aldehyde diisopentenyl acetal, which is carried out in a membrane cracking reactor with nitrogen stripping, and can continuously obtain cracked product prenyl-3-methyl-2-butenyl ether, which has the disadvantage of higher requirements for equipment.
Patent CN108117484a discloses a method for preparing isoprenyl-3-methyl-2-butenyl ether by cracking 3-methyl-2-butene-1-aldehyde diisopentenyl acetal under supercritical conditions. The method has the advantages of thorough reaction, high reaction rate and high conversion rate, but the supercritical condition has high requirement on equipment and relatively high cost.
Patent CN106977383A discloses a method for preparing isoprenyl-3-methyl-2-butenyl ether using a microreactor and a micro heat exchanger system. Compared with the traditional reactor, the micro-reactor and the micro-heat exchanger have the channel size of micron to millimeter, larger specific surface area and smaller volume. On the premise of ensuring better mixing effect, the larger specific surface area ensures better heat transfer effect, but has higher requirement on equipment and weaker industrialization prospect.
Patent CN112142571A discloses a method for preparing isoprenyl-3-methyl-2-butenyl ether by continuously catalytically cracking acetal. The method is carried out by adopting a cracking mode of continuous feeding and discharging of a fixed bed reactor, 3-methyl-2-butene-1-aldehyde diisoprenyl acetal is catalytically cracked under the synergistic action of an acidic solid catalyst and an auxiliary agent, and the cracked product is rectified and separated under the reduced pressure condition.
In summary, the existing methods respectively use two or three steps to synthesize 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether, and the 3-methyl-2-butenal obtained in the first step has poor stability, is easy to deteriorate, and is not beneficial to industrial application. Meanwhile, the method of two or three steps has high requirements on equipment, needs a larger field and increases corresponding cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and prenyl-3-methyl-2-butenyl ether, the invention adopts 3-methyl-2-butynol and 3-methyl-2-butenol as raw materials, and 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and prenyl-3-methyl-2-butenyl ether are simultaneously synthesized through continuous two-step reaction, so that the reaction efficiency is obviously improved.
The invention is realized by the following technical scheme:
a method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether comprises the following steps: dissolving 3-methyl-2-butynol in a solvent, carrying out a rearrangement reaction under the catalysis of a combined catalyst to generate 3-methyl-2-butenal, adding 3-methyl-2-butenol into a reaction system, and continuously reacting the 3-methyl-2-butenal and 3-methyl-2-butenol to obtain 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether.
The chemical reaction equation is as follows:
the invention further improves the scheme as follows:
the combined catalyst is a combination of a metal catalyst and an organic acid catalyst, and the mass ratio of the metal catalyst to the organic acid catalyst is 30-6.
Further, the metal catalyst is one or a mixture of more than two of vanadium pentoxide, ammonium metavanadate, sodium metavanadate, vanadium acetylacetonate, trimethoxy vanadium oxide, triethoxy vanadium oxide, triisopropoxyl vanadium oxide, tri-n-butoxyl vanadium oxide and triphenyl siloxyl vanadium oxide.
Further, the organic acid catalyst is one or a mixture of more than two of benzoic acid, 3-methyl-2-butenoic acid, crotonic acid, stearic acid, p-toluenesulfonic acid, cinnamic acid, lauric acid, palmitic acid and behenic acid.
Further, the solvent is one or a mixture of more than two of toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, fluorobenzene, o-dichlorobenzene, mesitylene, anisole and phenetole.
Furthermore, the mass ratio of the 3-methyl-2-butynol to the combined catalyst is 5-35, and the mass ratio of the 3-methyl-2-butynol to the 3-methyl-2-butenol is 1:3-15.
Further, the temperature of the rearrangement reaction is 150 to 155 ℃, and the time is 2 to 18h.
Further, the continuous reaction of the 3-methyl-2-butenal and the 3-methyl-2-butenol is carried out at the temperature of 85-90 ℃ for 5-8h.
Furthermore, in the reaction process, a water pump is used for reducing the pressure for reaction, and a water separator is used for carrying out water generated in the reaction.
Further, after the reaction is finished, the 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and the isoprenyl-3-methyl-2-butenyl ether pure products are respectively obtained through reduced pressure rectification, and the combined catalyst obtained through filtering after mother liquor is desolventized can be recycled for more than three times.
The beneficial effects of the invention are as follows:
the method for simultaneously synthesizing the 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and the prenyl-3-methyl-2-butenyl ether by using the 3-methyl-2-butynol and the 3-methyl-2-butenol as the raw materials through the continuous two-step reaction simplifies the reaction steps, obviously improves the reaction efficiency, reduces the equipment cost and the labor cost and reduces the production cost.
The solvent used in the invention is an inert solvent which can be azeotroped with water, and can carry out azeotropic reflux with water to carry out generated water in the reaction process, thereby improving the conversion rate of the reaction.
Detailed Description
Example 1
10 g of 3-methyl-2-butynol, 20 g o-xylene and 3 g triphenylsiloxy vanadium oxide, 200 mg of 3-methyl-2-butenoic acid were charged into a 100 mL reactor, and then reacted at 150 ℃ for about 3 hours, GC showed 21.9% of the 3-methyl-2-butynol remained, and 77.8% of 3-methyl-2-butenal was obtained, and the reaction was stopped. Then the temperature is reduced to 85-90 ℃, 40 g of 3-methyl-2-butenol is added, the reaction is carried out for 5 hours under the reduced pressure of a water pump, and simultaneously, water generated in the reaction is carried out by a water separator. GC showed 69.1% of 3-methyl-2-buten-1-al diisopentenyl acetal, 5.9% of isoprenyl-3-methyl-2-butenyl ether and the remaining 24.3% of 3-methyl-2-butenal. After the temperature is returned to the room temperature, the product 3-methyl-2-butene-1-aldehyde diisopentenyl acetal 5.4 g, isoprenyl-3-methyl-2-butenyl ether 0.4 g and intermediate 3-methyl-2-butenal 1.9 g are obtained by rectification. Finally, the residual catalyst after the solvent is removed can be recycled.
Example 2
10 g of 3-methyl-2-butynol, 20 g o-xylene and 3 g triphenylsiloxy vanadium oxide, 100 mg of 3-methyl-2-butenoic acid were charged into a 100 mL reactor, and then reacted at 150 ℃ for about 4 hours, GC showed 9.5% of the remaining 3-methyl-2-butynol, and 90.1% of 3-methyl-2-butenal was obtained, and the reaction was stopped. Then the temperature is reduced to 85-90 ℃,30 g of 3-methyl-2-butenol is added, the reaction is carried out for 8 hours under the reduced pressure of a water pump, and simultaneously, water generated in the reaction is carried out by a water separator. GC showed 68.1% of 3-methyl-2-butene-1-aldehyde diisopentenyl acetal, 10.0% of isoprenyl-3-methyl-2-butenyl ether, and the remaining 19.8% of 3-methyl-2-butenal. After the temperature is returned to the room temperature, the product of 3-methyl-2-butene-1-aldehyde diisopentenyl acetal 6.1 g, prenyl-3-methyl-2-butenyl ether 0.9 g and the intermediate of 3-methyl-2-butenal 1.8 g are obtained by rectification. Finally, the residual catalyst after the solvent is removed can be recycled.
Example 3
10 g of 3-methyl-2-butynol, 20 g o-xylene and 3 g triphenylsiloxy vanadium oxide, 100 mg of 3-methyl-2-butenoic acid were charged into a 100 mL reactor and then reacted at 150 ℃ for about 3 hours, GC showed 21.0% of 3-methyl-2-butynol remained, and the reaction was stopped to obtain 78.8% of 3-methyl-2-butenal. Then the temperature is reduced to 85-90 ℃, 60 g of 3-methyl-2-butenol is added, the reaction is carried out for 5 hours under the reduced pressure of a water pump, and simultaneously, water generated in the reaction is carried out by a water separator. GC showed 58.4% of 3-methyl-2-butene-1-aldehyde diisopentenyl acetal, 9.3% of isoprenyl-3-methyl-2-butenyl ether and the remaining 30.6% of 3-methyl-2-butenal. After the temperature is returned to the room temperature, the product 3-methyl-2-butene-1-aldehyde diisopentenyl acetal 4.6 g, isoprenyl-3-methyl-2-butenyl ether 0.7 g and intermediate 3-methyl-2-butenal 2.4 g are obtained by rectification. Finally, the residual catalyst after the solvent is removed can be recycled.
Example 4
10 g of 3-methyl-2-butynol, 20 g o-xylene and 3 g triphenylsiloxy vanadium oxide, 500 mg of 3-methyl-2-butenoic acid were charged into a 100 mL reactor, and then reacted at 150 ℃ for about 3 hours, GC showed 13.6% of the remaining 3-methyl-2-butynol, and 85.9% of 3-methyl-2-butenal was obtained, and the reaction was stopped. Then cooling to 85-90 ℃, adding 30 g of 3-methyl-2-butenol, reacting for 5 hours under the reduced pressure of a water pump, and simultaneously taking out the water generated by the reaction by using a water separator. GC showed 52.7% of 3-methyl-2-butene-1-aldehyde diisopentenyl acetal, 11.5% of isoprenyl-3-methyl-2-butenyl ether, and the remaining 33.7% of 3-methyl-2-butenal. After the temperature is returned to the room temperature, the product 3-methyl-2-butene-1-aldehyde diisopentenyl acetal 4.5 g, isoprenyl-3-methyl-2-butenyl ether 0.9 g and intermediate 3-methyl-2-butenal 2.9 g are obtained by rectification. Finally, the residual catalyst after the solvent is removed can be recycled.
Example 5
30 g of 3-methyl-2-butynol, 150 g mesitylene and 1.5 g triphenylsiloxy vanadium oxide, 300 mg of 3-methyl-2-butenoic acid were charged into a 500 mL reaction vessel, and then reacted at 155 ℃ for about 18 hours, GC showed 30.9% of the 3-methyl-2-butynol remained, giving 58.2% of 3-methyl-2-butenal, and the reaction was stopped. Then the temperature is reduced to 85-90 ℃, 390 g of 3-methyl-2-butenol is added, the reaction is carried out for 8 hours under the reduced pressure of a water pump, and simultaneously, water generated by the reaction is carried out by a water separator. GC showed 72.7% of 3-methyl-2-buten-1-al diisopentenyl acetal, 10.2% of isoprenyl-3-methyl-2-butenyl ether and 13.3% of 3-methyl-2-butenal remaining. After the temperature is returned to the room temperature, the product 3-methyl-2-butene-1-aldehyde diisopentenyl acetal 12.7 g, isoprenyl-3-methyl-2-butenyl ether 1.7 g and intermediate 3-methyl-2-butenal 2.3 g are obtained by rectification. Finally, the residual catalyst after the solvent is removed can be recycled.
Claims (10)
1. A method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether is characterized by comprising the following steps: dissolving 3-methyl-2-butynol in a solvent, carrying out rearrangement reaction under the catalysis of a combined catalyst to generate 3-methyl-2-butenal, adding 3-methyl-2-butenol into a reaction system, and continuously reacting the 3-methyl-2-butenal with 3-methyl-2-butenol to obtain 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether.
2. The method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether as claimed in claim 1, wherein: the combined catalyst is a combination of a metal catalyst and an organic acid catalyst, and the mass ratio of the metal catalyst to the organic acid catalyst is 30: 1-6.
3. The method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether as claimed in claim 2, wherein: the metal catalyst is one or the mixture of more than two of vanadium pentoxide, ammonium metavanadate, sodium metavanadate, vanadium acetylacetonate, trimethoxy vanadium oxide, triethoxy vanadium oxide, triisopropoxy vanadium oxide, tri-n-butoxy vanadium oxide and triphenyl silica-oxy vanadium oxide.
4. The method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether as claimed in claim 2, wherein: the organic acid catalyst is one or more of benzoic acid, 3-methyl-2-butenoic acid, crotonic acid, stearic acid, p-toluenesulfonic acid, cinnamic acid, lauric acid, palmitic acid and behenic acid.
5. The method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether as claimed in claim 1, wherein: the solvent is one or more than two of toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, fluorobenzene, o-dichlorobenzene, mesitylene, anisole and phenetole.
6. The method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether as claimed in claim 1, wherein: the mass ratio of the 3-methyl-2-butynol to the combined catalyst is 100-35, and the mass ratio of the 3-methyl-2-butynol to the 3-methyl-2-butenol is 1:3-15.
7. The method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether as claimed in claim 1, wherein: the temperature of the rearrangement reaction is 150 to 155 ℃, and the time is 2 to 18h.
8. The method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether as claimed in claim 1, wherein: the continuous reaction of the 3-methyl-2-butenal and the 3-methyl-2-butenol is carried out at the temperature of 85-90 ℃ for 5-8h.
9. The method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether as claimed in claim 8, wherein: in the reaction process, a water pump is used for reducing pressure for reaction, and a water separator is used for carrying out water generated in the reaction.
10. The method for simultaneously synthesizing 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether as claimed in claim 1, wherein: after the reaction is finished, 3-methyl-2-butene-1-aldehyde diisopentenyl acetal and isoprenyl-3-methyl-2-butenyl ether pure products are respectively obtained through reduced pressure rectification, and the combined catalyst obtained through filtering after mother liquor is desolventized can be recycled for more than three times.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101381290A (en) * | 2008-10-30 | 2009-03-11 | 浙江大学 | Continuous gas phase reaction method of isoprene-3-methyl butan-2-alkenyl ether |
| CN106977383A (en) * | 2017-03-10 | 2017-07-25 | 万华化学集团股份有限公司 | A kind of method for preparing citral |
| CN109336750A (en) * | 2018-11-23 | 2019-02-15 | 山东新和成药业有限公司 | A kind of synthesis technology of isoamyl olefine aldehydr |
| CN112574018A (en) * | 2020-11-30 | 2021-03-30 | 万华化学集团股份有限公司 | Low-color-number citral and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381290A (en) * | 2008-10-30 | 2009-03-11 | 浙江大学 | Continuous gas phase reaction method of isoprene-3-methyl butan-2-alkenyl ether |
| CN106977383A (en) * | 2017-03-10 | 2017-07-25 | 万华化学集团股份有限公司 | A kind of method for preparing citral |
| CN109336750A (en) * | 2018-11-23 | 2019-02-15 | 山东新和成药业有限公司 | A kind of synthesis technology of isoamyl olefine aldehydr |
| CN112574018A (en) * | 2020-11-30 | 2021-03-30 | 万华化学集团股份有限公司 | Low-color-number citral and preparation method thereof |
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