CN104387235A - Method for synthesizing prenol employing selective hydrogenation of 3-methylcrotonaldehyde - Google Patents
Method for synthesizing prenol employing selective hydrogenation of 3-methylcrotonaldehyde Download PDFInfo
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- CN104387235A CN104387235A CN201410671165.1A CN201410671165A CN104387235A CN 104387235 A CN104387235 A CN 104387235A CN 201410671165 A CN201410671165 A CN 201410671165A CN 104387235 A CN104387235 A CN 104387235A
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- Prior art keywords
- olefine aldehydr
- water
- prenol
- isoamyl olefine
- selective hydrogenation
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- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 27
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical compound CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 title abstract 8
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Chemical group 0.000 claims abstract description 24
- 239000001257 hydrogen Chemical group 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 55
- 230000009466 transformation Effects 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 10
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 4
- 235000021050 feed intake Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- GWZHWRVINLCSIC-UHFFFAOYSA-N [Ir].[N+](=O)(O)[O-] Chemical compound [Ir].[N+](=O)(O)[O-] GWZHWRVINLCSIC-UHFFFAOYSA-N 0.000 claims description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 239000008346 aqueous phase Substances 0.000 description 11
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000013517 stratification Methods 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000006317 isomerization reaction Methods 0.000 description 5
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VBPSVYDSYVJIPX-UHFFFAOYSA-N methylbutenol Natural products CCC=C(C)O VBPSVYDSYVJIPX-UHFFFAOYSA-N 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- VYFPSYVVFFFYBF-UHFFFAOYSA-N sodium;triphenylphosphane Chemical compound [Na].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VYFPSYVVFFFYBF-UHFFFAOYSA-N 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- -1 chrysanthemumic acid methyl esters Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- 238000010478 Prins reaction Methods 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 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 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing prenol employing selective hydrogenation of 3-methylcrotonaldehyde. The method comprises the following steps: feeding, nitrogen and hydrogen substitution, hydrogenation reaction, and separation. The used raw materials comprise 1 part of 3-methylcrotonaldehyde, 0.1-10 parts of water and 0.02-0.2 part of a catalyst; and the used catalyst is a water-soluble complex which is formed by a water-soluble salt of the group VIII metal and a water-soluble ligand. The 3-methylcrotonaldehyde conversion ratio and the selectivity of prenol of the synthetic reaction are high; a water phase of the catalyst can be applied repeatedly for over 20 times; the unit consumption of the catalyst is low; the production cost is greatly reduced; and the method is suitable for industrial production.
Description
Technical field
The present invention relates to the synthetic method of a kind of medicine, spices and pesticide intermediate prenol, specifically a kind of method of isoamyl olefine aldehydr selective hydrogenation synthesis prenol.
Background technology
Prenol (3-methyl-2 butenol), a kind of important medicine, spices and pesticide intermediate, can be used for producing citral, different vegetable alcohol, DV chrysanthemumic acid methyl esters, vitamin-E, vitamin A, carotenoid intermediate etc., also can be used for other organic syntheses.
The synthetic method of current prenol mainly contains following several:
1, iso-butylene method: patent US4028424 describes with iso-butylene and formaldehyde for raw material obtains prenol through prins reaction, but this reaction preference is poor, and the selectivity of prenol is about 5%, generates the 3-methyl-3-butenol of 80 ~ 90% simultaneously;
Patent WO2008037693 describes with iso-butylene and formaldehyde as raw material obtains 3-methyl-3-butenol through condensation reaction, again the isomerization on heterogeneous noble metal catalyst of 3-methyl-3-butenol is generated 3-methyl-2 butenol, this catalyzer is made up of Pd, Se and Te, and this reaction has the excessive hydrogenation product primary isoamyl alcohol of 2.5% to generate in addition;
Patent US4219683 describes and 3-methyl-3-butenol isomery under palladium catalyst and hydrogen exist is converted into prenol, and transformation efficiency is 39 ~ 54%, selectivity 82 ~ 99%.The shortcoming of this operational path is, iso-butylene and formaldehyde reaction need High Temperature High Pressure, severe reaction conditions, and in addition, the isomerization reaction low conversion rate of 3-methyl-3-butenol, separating difficulty is large.
2, methyl butenol isomerate process: under alkaline condition, acetone and acetylene ethynylation, generate methylbutynol, then obtain methyl butenol with lindlar catalyst hydrogenation, obtain prenol in isomerization.
Describe with 2-methyl-3-butene-2 alcohol (methyl butenol) for raw material in patent US3925485 example, with positive vanadic acid tetrahydrochysene virtue camphor tree ester for catalyzer, 150 DEG C of reaction 7h, obtain the transformation efficiency 25.6% of prenol, yield can to 83%; One or more describing in use rhenium catalyst, tungsten catalyst and vanadium catalyst of patent CN101381283A carry out the isomerization reaction of methyl butenol, temperature 130 ~ 150 DEG C, under pressure 0.2 ~ 0.3MPa, can obtain prenol continuously, yield is 86 ~ 93%.The shortcoming of above-mentioned two patent techniques is isomerization reaction is balanced reaction, low conversion rate, and separating difficulty is large, and the catalyst preparing difficulty used, price is higher.
3, isoamyl olefine aldehydr hydrogenation method: isoamyl olefine aldehydr is carried out selective hydrogenation and obtains prenol.The people such as Tomoo (J Org Chem 1998,63:2378-2381) use α, and beta-unsaturated carbonyl compound has the Rh of high catalytic activity
6(CO)
16be catalyzer with amine substance, with formic acid and Virahol for hydrogen source, carry out hydrogenation reaction to isoamyl olefine aldehydr, transformation efficiency can reach 92%, prenol selectivity 96%, and primary isoamyl alcohol selectivity reaches 4%.Patent US4929776 adopts RuH
2(PPh
3) be catalyzer, isopropyl alcohol and water or toluene make solvent, and isoamyl olefine aldehydr is at 35 ~ 50 DEG C, and hydrogenation under 2 ~ 3MPa, transformation efficiency can reach 100%, and prenol selectivity reaches 90%.
Patent CN1258506C and CN1323059C describes the method using Ru doped F e loaded catalyst and Pt/ZnO to carry out the selective hydrogenation of olefinic beta-unsaturated carbonyl compounds to prepare corresponding unsaturated alcohol, wherein the selectivity of unsaturated alcohol reaches more than 90%, saturated alcohol selectivity 4 ~ 6%, but the example all not describing isoamyl olefine aldehydr hydrogenation.
Isoamyl olefine aldehydr Hydrogenation is to have C=C and C=O key in isoamyl olefine aldehydr molecule for its technological difficulties of prenol simultaneously, because C=O bond energy is greater than C=C bond energy, and the two has conjugation, make reaction will on C=O key hydrogenation and not destroy C=C key more difficult, inevitably there is primary isoamyl alcohol (saturated alcohol) product in hydrogenation process.
Summary of the invention
Technical problem to be solved by this invention is the deficiency overcoming the existence of above-mentioned prior art, there is provided a kind of isoamyl olefine aldehydr in water-organic biphasic, carry out the method for selective hydrogenation synthesis prenol, realize following goal of the invention: the selectivity of isoamyl olefine aldehydr transformation efficiency and prenol is high; Product is easily separated with catalyzer, easy and simple to handle, energy-saving and cost-reducing; Catalyzer aqueous phase can realize the recycled of more than 20 times, and catalyst consumption is low, significantly reduces production cost, is applicable to suitability for industrialized production.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A method for isoamyl olefine aldehydr selective hydrogenation synthesis prenol, comprises the following steps: feed intake; Nitrogen, hydrogen exchange; Hydrogenation reaction; Be separated.
Below the further improvement to technique scheme:
In described material addition step, the raw material of input is: isoamyl olefine aldehydr, water and catalyzer, wherein the water soluble complex that formed of the catalyzer water-soluble salt that is group VIII metal and water soluble ligand.
The water-soluble salt of described group VIII metal is one or more in ruthenium acetate, ruthenium chloride, nitric acid ruthenium, rhodium sulfate, rhodium chloride, rhodium nitrate, acid chloride, Palladous chloride, Palladous nitrate, iridium acetate, iridium chloride, nitric acid iridium.
Described water soluble ligand is water-soluble phosphine ligand and water-soluble imine ligand.
The water-soluble salt of described group VIII metal and the mass ratio of water soluble ligand are 0.001 ~ 0.01:1.
The mass ratio dropping into raw material is: 1 part of isoamyl olefine aldehydr, 0.1 ~ 10 part of water and 0.02 ~ 0.2 part of catalyzer.
In described hydrogenation reaction step, hydrogen pressure 0.5 ~ 15.0MPa, temperature of reaction 30 ~ 150 DEG C.
In described hydrogenation reaction step, under the condition of mixing speed 200 ~ 1000rpm, compressive reaction 3 ~ 30h.
In described hydrogenation reaction step, until isoamyl olefine aldehydr transformation efficiency > 98%, stop this reactions steps.
Adopt the method, transformation efficiency >=98% of isoamyl olefine aldehydr, prenol selectivity >=99%, the selectivity < 1% of excessive hydrogenation product primary isoamyl alcohol.
The present invention compared with prior art, has the following advantages:
1. use water-organic biphasic reaction, react complete two phase stratification, directly can obtain product, be easy to being separated of product and catalyzer, easy and simple to handle, energy-saving and cost-reducing;
2. the water-soluble group VIII metal complex catalysis system used, the selectivity of isoamyl olefine aldehydr transformation efficiency and prenol is higher, and transformation efficiency reaches more than 98%, and prenol selectivity reaches more than 99%, and the selectivity of excessive hydrogenation product primary isoamyl alcohol is less than 1%;
3. catalyzer aqueous phase can realize the recycled of more than 20 times, and catalyst consumption is low, significantly reduces production cost, is applicable to suitability for industrialized production.
Below in conjunction with embodiment, technical scheme of the present invention is described further.
Embodiment
A method for isoamyl olefine aldehydr selective hydrogenation synthesis prenol, comprises the following steps:
A, to feed intake
By 1 part of isoamyl olefine aldehydr, 0.1 ~ 10 part of water, and the water soluble complex catalyzer that the water-soluble salt of 0.02 ~ 0.2 part of group VIII metal and water soluble ligand are formed joins in autoclave.
B, nitrogen, hydrogen exchange
Nitrogen replacement three times, hydrogen exchange three times.
C, hydrogenation reaction
Then at hydrogen pressure 0.5 ~ 15.0MPa, temperature of reaction 30 ~ 150 DEG C, under the condition of mixing speed 200 ~ 1000rpm, compressive reaction 3 ~ 30h, until isoamyl olefine aldehydr transformation efficiency > 98%.
D, separation
After reaction terminates, stratification, the aqueous phase containing catalyzer continues cover and uses lower batch reaction, and organic phase is prenol.
Embodiment 1
6g ruthenium chloride and three-(to phenoxy group-Soxylat A 25-7)-phosphine complex catalyst, 500g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then add 200g isoamyl olefine aldehydr.Ruthenium chloride and three in complex catalyst-(to phenoxy group-Soxylat A 25-7)-phosphine mass ratio is 0.009:1.
With nitrogen replacement three times, rear hydrogen exchange three times.
Be heated to 150 DEG C, pressurized with hydrogen stirs to 3.0MPa, 700rpm, and react 3 hours, sampling analysis isoamyl olefine aldehydr transformation efficiency is greater than 99%.
With water cooling, extrude reaction solution, stratification, the aqueous phase containing catalyzer can continue cover and use lower batch reaction, and organic phase is prenol.
Through gas chromatographic analysis, the transformation efficiency of isoamyl olefine aldehydr is 99.98%, prenol selectivity 99.10%.
Embodiment 2
25g rhodium nitrate and triphenylphosphine sodium sulfonate complex catalyst, 200g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then add 300g isoamyl olefine aldehydr.The mass ratio of complex catalyst rhodium nitrate and triphenylphosphine sodium sulfonate is 0.001:1.
With nitrogen replacement three times, rear hydrogen exchange three times.
Be heated to 30 DEG C, pressurized with hydrogen stirs to 5.0MPa, 700rpm, and react 28 hours, sampling analysis isoamyl olefine aldehydr transformation efficiency is greater than 98%.
With water cooling, extrude reaction solution, stratification, the aqueous phase containing catalyzer can continue cover and use lower batch reaction, and organic phase is prenol.
Through gas chromatographic analysis, the transformation efficiency of isoamyl olefine aldehydr is 98.15%, prenol selectivity 99.20%.
Embodiment 3
25g rhodium nitrate and three-(to phenoxy group-Soxylat A 25-7)-phosphine complex catalyst, 800g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then add 100g isoamyl olefine aldehydr.The mass ratio of rhodium nitrate and three in complex catalyst-(to phenoxy group-Soxylat A 25-7)-phosphine is 0.01:1.
With nitrogen replacement three times, rear hydrogen exchange three times.
Be heated to 100 DEG C, pressurized with hydrogen stirs to 0.5MPa, 500rpm, and react 18.5 hours, sampling analysis isoamyl olefine aldehydr transformation efficiency is greater than 98%.
With water cooling, extrude reaction solution, stratification, the aqueous phase containing catalyzer can continue cover and use lower batch reaction, and organic phase is prenol.
Through gas chromatographic analysis, the transformation efficiency of isoamyl olefine aldehydr is 98.05%, prenol selectivity 99.40%.
Embodiment 4
20g palladous sulfate and three-(4-methoxyl group-3-sodium sulfonate phenyl) phosphine complex catalyst, 1000g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then add 250g isoamyl olefine aldehydr.The mass ratio of Palladous chloride and three in complex catalyst-(4-methoxyl group-3-sodium sulfonate phenyl) phosphine is 0.006:1.
With nitrogen replacement three times, rear hydrogen exchange three times.
Be heated to 130 DEG C, pressurized with hydrogen stirs to 2.0MPa, 1000rpm, and react 20 hours, sampling analysis isoamyl olefine aldehydr transformation efficiency is greater than 99%.
With water cooling, extrude reaction solution, stratification, the aqueous phase containing catalyzer can continue cover and use lower batch reaction, and organic phase is prenol.
Through gas chromatographic analysis, the transformation efficiency of isoamyl olefine aldehydr is 99.05%, prenol selectivity 99.01%.
Embodiment 5
2g rhodium chloride and three-(2-methoxyl group-3-sodium sulfonate phenyl) phosphine, 1000g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then add 100g isoamyl olefine aldehydr.The mass ratio of rhodium sulfate and three in complex catalyst-(2-methoxyl group-3-sodium sulfonate phenyl) phosphine is 0.001:1.
With nitrogen replacement three times, rear hydrogen exchange three times.
Be heated to 130 DEG C, pressurized with hydrogen stirs to 10.0MPa, 1000rpm, reacts 19 hours.Sampling analysis isoamyl olefine aldehydr transformation efficiency is greater than 90%.
With water cooling, extrude reaction solution, stratification, the aqueous phase containing catalyzer can continue cover and use lower batch reaction, and organic phase is prenol.
Through gas chromatographic analysis, the transformation efficiency of isoamyl olefine aldehydr is 98.11%, prenol selectivity 99.37%.
Embodiment 6
20g Palladous chloride and 5-[1-(2,6-di-isopropyl phenyl imido)-ethyl]-2-furane sulfonic acid triethyl ammonium complex catalyst, 600g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then add 300g isoamyl olefine aldehydr.In complex catalyst, the mass ratio of Palladous chloride and 5-[1-(2,6-di-isopropyl phenyl imido)-ethyl]-2-furane sulfonic acid triethyl ammonium is 0.008:1.
With nitrogen replacement three times, rear hydrogen exchange three times.
Be heated to 100 DEG C, pressurized with hydrogen stirs to 2.0MPa, 1000rpm, reacts 9 hours.Sampling analysis isoamyl olefine aldehydr transformation efficiency is greater than 98%,
With water cooling, extrude reaction solution, stratification, the aqueous phase containing catalyzer can continue cover and use lower batch reaction, and organic phase is prenol.
Through gas chromatographic analysis, the transformation efficiency of isoamyl olefine aldehydr is 98.35%, prenol selectivity 99.01%.
Embodiment 7
10g iridium chloride and triphenylphosphine sodium sulfonate complex catalyst, 600g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then add 300g isoamyl olefine aldehydr.In complex catalyst, the mass ratio of iridium chloride and triphenylphosphine sodium sulfonate is 0.004:1.
With nitrogen replacement three times, rear hydrogen exchange three times.
Be heated to 70 DEG C, pressurized with hydrogen stirs to 2.5MPa, 1000rpm, reacts 10 hours.Sampling analysis isoamyl olefine aldehydr transformation efficiency is greater than 98%.
With water cooling, extrude reaction solution, stratification, the aqueous phase containing catalyzer can continue cover and use lower batch reaction, and organic phase is prenol.
Through gas chromatographic analysis, the transformation efficiency of isoamyl olefine aldehydr is 99.93%, prenol selectivity 99.22%.
Applied mechanically by aqueous phase containing catalyzer in embodiment 7, its experimental result is as following table:
As seen from the above table, catalyst recovery apply mechanically 18 post-reacted selectivity and transformation efficiency still higher.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.
Claims (10)
1. a method for isoamyl olefine aldehydr selective hydrogenation synthesis prenol, is characterized in that: comprise the following steps: feed intake; Nitrogen, hydrogen exchange; Hydrogenation reaction; Be separated.
2. the method for a kind of isoamyl olefine aldehydr selective hydrogenation synthesis prenol as claimed in claim 1, it is characterized in that: in described material addition step, the raw material dropped into is: isoamyl olefine aldehydr, water and catalyzer, wherein the water soluble complex that formed of the catalyzer water-soluble salt that is group VIII metal and water soluble ligand.
3. the method for a kind of isoamyl olefine aldehydr selective hydrogenation synthesis prenol as claimed in claim 2, is characterized in that: the water-soluble salt of described group VIII metal is one or more in ruthenium acetate, ruthenium chloride, nitric acid ruthenium, rhodium sulfate, rhodium chloride, rhodium nitrate, acid chloride, Palladous chloride, Palladous nitrate, iridium acetate, iridium chloride, nitric acid iridium.
4. the method for a kind of isoamyl olefine aldehydr selective hydrogenation synthesis prenol as claimed in claim 2, is characterized in that: described water soluble ligand is water-soluble phosphine ligand and water-soluble imine ligand.
5. the method for a kind of isoamyl olefine aldehydr selective hydrogenation synthesis prenol as claimed in claim 2, is characterized in that: the water-soluble salt of described group VIII metal and the mass ratio of water soluble ligand are 0.001 ~ 0.01:1.
6. the method for a kind of isoamyl olefine aldehydr selective hydrogenation synthesis prenol as claimed in claim 2, is characterized in that: the mass ratio dropping into raw material is: 1 part of isoamyl olefine aldehydr, 0.1 ~ 10 part of water and 0.02 ~ 0.2 part of catalyzer.
7. the method for a kind of isoamyl olefine aldehydr selective hydrogenation synthesis prenol as claimed in claim 1, is characterized in that: in described hydrogenation reaction step, hydrogen pressure 0.5 ~ 15.0MPa, temperature of reaction 30 ~ 150 DEG C.
8. the method for a kind of isoamyl olefine aldehydr selective hydrogenation synthesis prenol as claimed in claim 1, is characterized in that: in described hydrogenation reaction step, under the condition of mixing speed 200 ~ 1000rpm, compressive reaction 3 ~ 30h.
9. the method for a kind of isoamyl olefine aldehydr selective hydrogenation synthesis prenol as claimed in claim 1, is characterized in that: in described hydrogenation reaction step, until isoamyl olefine aldehydr transformation efficiency > 98%, stops this reactions steps.
10. the method for a kind of isoamyl olefine aldehydr selective hydrogenation synthesis prenol as claimed in claim 1, it is characterized in that: adopt the method, transformation efficiency >=98% of isoamyl olefine aldehydr, prenol selectivity >=99%, the selectivity < 1% of excessive hydrogenation product primary isoamyl alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107089900A (en) * | 2017-04-28 | 2017-08-25 | 山东新和成药业有限公司 | A kind of preparation method of β benzyl carbinols |
| CN110643556A (en) * | 2019-08-23 | 2020-01-03 | 浙江工业大学 | A recombinant genetically engineered bacterium co-expressing alkenaldehyde reductase and glucose dehydrogenase and its application |
| CN114262257A (en) * | 2020-09-16 | 2022-04-01 | 万华化学集团股份有限公司 | Method for recovering isoamyl alcohol through hydrogenation of citral process waste liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4219677A (en) * | 1976-07-27 | 1980-08-26 | Rhone-Poulenc Industries | Telomerization process |
| US4925990A (en) * | 1987-12-01 | 1990-05-15 | Rhone-Poulenc Sante | Process for the preparation of unsaturated alcohols |
| US4929776A (en) * | 1987-12-01 | 1990-05-29 | Rhone-Poulenc Sante | Process for the preparation of unsaturated alcohols |
| CN101031531A (en) * | 2004-09-29 | 2007-09-05 | 巴斯福股份公司 | Proess for producing an optically active 2-methyl-alkane-1-ols from the corresponding 2-methylalk-2-en-1-als, comprising a step of enantioselective acylation to enrich one enantiomer |
-
2014
- 2014-11-21 CN CN201410671165.1A patent/CN104387235B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4219677A (en) * | 1976-07-27 | 1980-08-26 | Rhone-Poulenc Industries | Telomerization process |
| US4925990A (en) * | 1987-12-01 | 1990-05-15 | Rhone-Poulenc Sante | Process for the preparation of unsaturated alcohols |
| US4929776A (en) * | 1987-12-01 | 1990-05-29 | Rhone-Poulenc Sante | Process for the preparation of unsaturated alcohols |
| CN101031531A (en) * | 2004-09-29 | 2007-09-05 | 巴斯福股份公司 | Proess for producing an optically active 2-methyl-alkane-1-ols from the corresponding 2-methylalk-2-en-1-als, comprising a step of enantioselective acylation to enrich one enantiomer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107089900A (en) * | 2017-04-28 | 2017-08-25 | 山东新和成药业有限公司 | A kind of preparation method of β benzyl carbinols |
| CN107089900B (en) * | 2017-04-28 | 2020-06-26 | 山东新和成药业有限公司 | Preparation method of β -phenethyl alcohol |
| CN110643556A (en) * | 2019-08-23 | 2020-01-03 | 浙江工业大学 | A recombinant genetically engineered bacterium co-expressing alkenaldehyde reductase and glucose dehydrogenase and its application |
| CN114262257A (en) * | 2020-09-16 | 2022-04-01 | 万华化学集团股份有限公司 | Method for recovering isoamyl alcohol through hydrogenation of citral process waste liquid |
| CN114262257B (en) * | 2020-09-16 | 2023-07-14 | 万华化学集团股份有限公司 | A method for recovering isoamyl alcohol by hydrogenation of citral process waste liquid |
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