CN109293472B - Method for preparing enol from alkynol through partial hydrogenation - Google Patents
Method for preparing enol from alkynol through partial hydrogenation Download PDFInfo
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- CN109293472B CN109293472B CN201811334142.6A CN201811334142A CN109293472B CN 109293472 B CN109293472 B CN 109293472B CN 201811334142 A CN201811334142 A CN 201811334142A CN 109293472 B CN109293472 B CN 109293472B
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- alkynol
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- acetal
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000002085 enols Chemical class 0.000 title claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 150000001241 acetals Chemical class 0.000 claims description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- MULUCORRSAVKOA-UHFFFAOYSA-N 3,7,11,15-tetramethylhexadec-1-yn-3-ol Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)C#C MULUCORRSAVKOA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 239000011981 lindlar catalyst Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- ZNVPGYAGXVEAFP-SDNWHVSQSA-N (6e)-3,7,11-trimethyldodeca-6,10-dien-1-yn-3-ol Chemical compound CC(C)=CCC\C(C)=C\CCC(C)(O)C#C ZNVPGYAGXVEAFP-SDNWHVSQSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- ACOTYZCHRLPBKW-UHFFFAOYSA-N ethane-1,2-diol;propan-2-one Chemical compound CC(C)=O.OCCO ACOTYZCHRLPBKW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229940074076 glycerol formal Drugs 0.000 claims description 2
- CQBPOPVKDNHISM-UHFFFAOYSA-N propane-1,2,3-triol;propan-2-one Chemical compound CC(C)=O.OCC(O)CO CQBPOPVKDNHISM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000001345 alkine derivatives Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 150000005673 monoalkenes Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 208000005374 Poisoning Diseases 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XLOPRKKSAJMMEW-SFYZADRCSA-N Chrysanthemic acid Natural products CC(C)=C[C@@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-N 0.000 description 2
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 2
- ABSPRNADVQNDOU-UHFFFAOYSA-N Menaquinone 1 Natural products C1=CC=C2C(=O)C(CC=C(C)C)=C(C)C(=O)C2=C1 ABSPRNADVQNDOU-UHFFFAOYSA-N 0.000 description 2
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 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 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000021466 carotenoid Nutrition 0.000 description 2
- 150000001747 carotenoids Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 description 2
- SHUZOJHMOBOZST-UHFFFAOYSA-N phylloquinone Natural products CC(C)CCCCC(C)CCC(C)CCCC(=CCC1=C(C)C(=O)c2ccccc2C1=O)C SHUZOJHMOBOZST-UHFFFAOYSA-N 0.000 description 2
- MBWXNTAXLNYFJB-NKFFZRIASA-N phylloquinone Chemical compound C1=CC=C2C(=O)C(C/C=C(C)/CCC[C@H](C)CCC[C@H](C)CCCC(C)C)=C(C)C(=O)C2=C1 MBWXNTAXLNYFJB-NKFFZRIASA-N 0.000 description 2
- 235000019175 phylloquinone Nutrition 0.000 description 2
- 239000011772 phylloquinone Substances 0.000 description 2
- 229960001898 phytomenadione Drugs 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 235000019155 vitamin A Nutrition 0.000 description 2
- 239000011719 vitamin A Substances 0.000 description 2
- 229940045997 vitamin a Drugs 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JRTBBCBDKSRRCY-UHFFFAOYSA-N 3,7-dimethyloct-6-en-3-ol Chemical compound CCC(C)(O)CCC=C(C)C JRTBBCBDKSRRCY-UHFFFAOYSA-N 0.000 description 1
- XYJQBHCHAZPWHA-UHFFFAOYSA-N CC(C)C([CH2-])=O Chemical compound CC(C)C([CH2-])=O XYJQBHCHAZPWHA-UHFFFAOYSA-N 0.000 description 1
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing enol by partially hydrogenating alkynol. By adding acetal and/or ketal substances, the efficient conversion of alkynol can be realized, the product selectivity is high, the catalyst system is easy to separate, and the operation is simple.
Description
Technical Field
The invention relates to a method for producing VE main intermediate, DV chrysanthemic acid (pyrethroid intermediate), and synthesizing vitamin A, vitamin K1, carotenoid intermediate and perfume. In particular to a method for preparing enol by selective hydrogenation of alkynol.
Background
Enol is a method for preparing intermediates and chemical products thereof in fine chemical engineering, and is mainly used for producing VE main intermediates, DV chrysanthemic acid (pyrethroid intermediates), vitamin A, vitamin K1, carotenoid intermediates, rubber monomers and spices.
The general reaction formula is as follows:
wherein R is1、R2Is hydrogen or a hydrocarbyl group.
The catalyst widely used commercially for the selective hydrogenation of alkynols is the Lindlar catalyst. The catalyst is prepared by precipitating metal palladium on a carrier such as barium sulfate or calcium carbonate, and then poisoning the carrier with lead acetate or quinoline to reduce the catalytic activity of palladium and make the hydrogenation reaction of alkynol stay in the enol stage. However, early researchers found that the catalyst was susceptible to deactivation by poisoning, and that selective hydrogenation was difficult to control.
In order to improve the hydrogenation selectivity, the content of excessive hydrogenation products needs to be controlled, the basic principle is to reduce the activity of the catalyst, and in patent CN201380032718, the particle size of a calcium carbonate carrier is controlled to be more than 10 μm, and the specific surface area is reduced to achieve the purpose. The more general principle is that the activity of the catalyst is reduced by adding sulfur-containing and nitrogen-containing compounds, and the common compounds are quinoline, pyridine, mercaptan and the like. The selection principle is as follows: alkynes have a stronger coordination ability than monoolefins, and if an electron-donating agent having a stronger coordination ability than monoolefins is added in the catalytic hydrogenation reaction, the hydrogenation reaction of monoolefins can be partially or completely inhibited. The inhibiting effect of the electron donor reagent on the hydrogenation of the mono-olefin is related to the electron donor reagent and the substrate, the same electron donor reagent has different inhibiting effects on the selective hydrogenation of different alkynes on the same catalyst, and different electron donor reagents have different inhibiting effects on the selective hydrogenation of the same alkyne on the same catalyst. In patent CN00131057, 10-2000ppm of carbon monoxide gas is added into hydrogen gas, and carbon monoxide is used to modify the surface of the catalyst.
The prior art has the following defects:
1. the conversion rate of alkynol is not high, and the selectivity and yield of enol are low because excessive hydrogenation products are difficult to control.
2. In the prior art, an immobilized catalytic system is adopted, lead acetate or quinoline is used for poisoning treatment, lead ions have toxicity, the smell of quinoline is stimulated, and the content of the quinoline is strictly controlled in a product. Quinoline is usually separated from the product by rectification, which is difficult to separate and increases equipment investment.
Disclosure of Invention
The invention aims to solve the technical problems and provides a method for preparing enol by selective hydrogenation of alkynol, so as to realize the following purposes:
1. the conversion rate of alkynol is more than or equal to 98.0 percent, the selectivity of enol is more than or equal to 99.0 percent, and the selectivity of over-hydrogenated products is less than 1.0 percent.
2. The catalyst is stable, the product is easily separated from the catalytic system, and the operation is simple.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for preparing enol by partial hydrogenation of alkynol takes alkynol with a structural general formula I as a substrate, acetal and/or ketal substances are added into the substrate, and the enol with a structural general formula II is formed by partial hydrogenation of alkynol intramolecular acetylene bonds in the presence of a catalyst:
wherein R is1、R2Is hydrogen or a hydrocarbyl group, especially a branched or straight chain C6-20 alkyl or alkenyl group, more preferably R1Or R2One of which is hydrogen and the other is a branched or straight chain C6-20 alkyl or alkenyl group.
Typical compounds of the alkynols are: dehydronerolidol, dihydrodehydronerolidol, tetrahydrodehydronerolidol, dihydrodehydrolinalool, or dehydroisophytol.
The structure is as follows:
the corresponding partial hydrogenation products are: nerolidol, dihydronerolidol, tetrahydronerolidol, dihydrolinalool, and isophytol.
The structure is as follows:
further, the catalyst for partial hydrogenation is a Lindlar catalyst, preferably the supported metal is palladium, and the carrier is calcium carbonate.
In the present invention, 10 to 2000ppm of carbon monoxide gas is added to the hydrogen gas used for hydrogenation. After carbon monoxide and hydrogen are premixed, partial hydrogenation is carried out after the content of the carbon monoxide and the hydrogen meets the requirement through detection. The purity of hydrogen and carbon monoxide is above 99.99%, and the volume content of oxygen is below 1 ppm. The amount of hydrogen to be introduced for hydrogenation may be such that the pressure in the system is 0.05 to 0.3MPa, preferably 0.1 to 0.15 MPa.
Preferably, acetal and/or ketal substances are added into the substrate, and the addition amount of the acetal and/or ketal substances is 0.01-5% of the molar weight of the substrate. The acetal and/or ketal substances include one or more of glycerol formal, acetone glycerol, acetone methyl glycol, acetone dimethyl acetal, and acetone ethylene glycol. The addition of acetal and/or ketal substances as electron donor agents has an inhibiting effect on the hydrogenation of monoolefine. The principle is that the surface layer or even the subsurface layer of the catalyst support has an important influence on the catalytic activity. The adsorption strength of different bonds on the metal active center is an important factor influencing the reaction selectivity. The selectivity can be improved by introducing a modifier, and a proper electron-donating reagent is selected, so that the adsorption of the electron-donating reagent in the catalyst is weaker than that of alkyne but stronger than that of alkene, thereby not only realizing the rapid adsorption reaction of alkyne, but also preventing the adsorption of alkene, and being beneficial to separating alkene from the catalyst in a certain sense.
In the present invention, the method may further comprise: after the reaction is completed, water (a small amount of water, for example, the amount of water added may be 0.001 vol% to 1 vol%, further 0.01 to 0.5 vol%) is added to the system, and then the acetal and/or ketal substances added are separated from the product by distillation under reduced pressure. Because the added acetal and/or ketal substances can be decomposed into small molecular substances when meeting water, the boiling path difference with the product is obvious. So that it can be separated from the product by simple distillation.
Further, the substrate is diluted with a solvent, which may be one or more of inert aliphatic alkanes, aromatic hydrocarbons, ethers, halogenated alkanes, etc., which do not react with the raw materials, such as one or more of n-heptane, toluene, 1, 2-dichloroethane, 1, 4-dioxane, etc., or may be diluted without using a solvent. The selection principle of the solvent is as follows: 1. does not react with the raw materials and the products; 2. the solvent is to be capable of being separated from the product by simple separation means; 3. the solvent may form an azeotrope with water. The amount of the diluting solvent may be 0.5 to 3 times, preferably 0.8 to 1.5 times, the mass of the alkynol substrate.
In the invention, the absolute reaction pressure is 0.01-2.0MPa, the reaction temperature is 0-90 ℃, and the reaction time is 0.5-24 h.
The invention has the positive effects that: firstly, acetal and/or ketal substances are added into a system to effectively regulate and control the selectivity of Lindlar catalyst active agents, so that the hydrogenation reaction is controlled at an enol stage, the enol selectivity is more than or equal to 99.0 percent, and the selectivity of over-hydrogenated products is less than 1.0 percent. Secondly, the added acetal and/or ketal substances can be separated from the system by using a conventional separation method after simple treatment, the residual amount of the product is almost ignored, and the quality and the smell of the final product are not influenced.
Detailed Description
The process of the present invention will be further illustrated by the following examples, but the present invention is not limited to the examples listed, but also includes any other known variations within the scope of the claims of the present invention.
The analysis method comprises the following steps:
gas chromatograph: agilent7820A, column HP-5(30 m.times.320. mu.m.times.0.25 μm), injection port temperature: 150 ℃; the split ratio is 50: 1; carrier gas flow: 1.5 ml/min; temperature rising procedure: keeping at 40 deg.C for 1min, heating to 90 deg.C at 10 deg.C/min for 0min, heating to 160 deg.C at 5 deg.C/min for 0min, heating to 280 deg.C at 30 deg.C/min for 6 min. Detector temperature: 280 ℃.
Example 1
Firstly, 224.4g of tetrahydrodehydronerolidol, 2g of palladium-calcium carbonate catalyst, 1.0g of dimethyl acetonide and 250g of heptane are added into an autoclave, the autoclave is sealed, after 3 times of replacement by nitrogen, the nitrogen is pressed to 3.0MPa to confirm that the autoclave has good sealing property, the nitrogen is evacuated, the replacement is performed for 6 times by hydrogen containing 500ppm of carbon monoxide, a stirring paddle is started, the hydrogen pressure is kept at 0.1MPa, and the internal temperature of the autoclave is kept at 30 ℃ for reaction for 3 hours. Stopping stirring, emptying gas, and then carrying out GC analysis on the reaction solution, wherein the reaction solution comprises the following components: nerolidol 97.8%, tetrahydrodehydronerolidol 1.4%, dihydronerolidol 0.6%, and others 0.2%. Filtering the reaction liquid, adding 0.5g of pure water, distilling at 90 ℃ to remove the solvents of heptane and ketal, heating to 160 ℃, and distilling at 1KPa to obtain 224.3g of product liquid.
Example 2
First, 294.5g of dehydroisophytol, 1.5g of a palladium-calcium carbonate catalyst, 2.0g of acetonide and 250g of heptane were charged into an autoclave, the autoclave was sealed, and after 3 times of replacement with nitrogen, the autoclave was purged with nitrogen to 3.0MPa to confirm good sealing of the autoclave, the autoclave was evacuated of nitrogen, replaced with hydrogen containing 1000ppm of carbon monoxide for 6 times, and the stirring paddle was turned on to maintain a hydrogen pressure of 0.15MPa, thereby maintaining the internal temperature of the autoclave at 30 ℃ for reaction for 3 hours. Stopping stirring, emptying gas, and then carrying out GC analysis on the reaction solution, wherein the reaction solution comprises the following components: 97.2 percent of isophytol, 1.6 percent of dehydroisophytol, 0.5 percent of dihydroisophytol and 0.7 percent of the rest. Filtering the reaction liquid, adding 0.5g of pure water, distilling at 110 ℃ to remove the solvents of heptane and ketal, heating to 160 ℃, and distilling at 500Pa to obtain 293.8g of product liquid.
From the results of the above examples, it can be seen that by adding acetal and/or ketal materials to the system, the enol selectivity can be more than or equal to 99.0%, and the over-hydrogenated product selectivity can be less than 1.0%. Secondly, the added acetal and/or ketal substances can be separated from the system by using a conventional separation method after simple treatment, the residual amount of the product is almost ignored, and the quality and the smell of the final product are not influenced.
Claims (15)
1. A process for the partial hydrogenation of alkynols to give alkenols, which process comprises: taking alkynol with a general structural formula I as a substrate, adding acetal and/or ketal substances into the substrate, and partially hydrogenating an alkyne bond in an alkynol molecule in the presence of a catalyst to form an enol with a general structural formula II:
wherein R is1、R2Is hydrogen or hydrocarbyl, wherein the partially hydrogenated catalyst is a Lindlar catalyst; adding 10-2000ppm of carbon monoxide gas into hydrogen gas for hydrogenation.
2. The method of claim 1, wherein the hydrocarbyl group is a branched or straight chain C6-C20 alkyl or alkenyl group.
3. The method of claim 1, wherein R is1Or R2One of which is hydrogen and the other is a branched or straight chain C6-C20 alkyl or alkenyl group.
4. The method according to claim 1, wherein the alkynol is selected from the group consisting of dehydronerolidol, dihydrodehydronerolidol, tetrahydrodehydronerolidol, dihydrodehydrolinalool, and dehydroisophytol.
5. A process according to any one of claims 1 to 4, characterised in that in the partially hydrogenated catalyst the supported metal is palladium and the support is calcium carbonate.
6. The method according to any one of claims 1 to 4, wherein an acetal and/or ketal species is added to the substrate in an amount of 0.01 to 5% by mole based on the substrate.
7. The method according to claim 6, wherein the acetal and/or ketal species added is selected from one or more of acetone glycerol, acetone dimethyl acetal, acetone ethylene glycol, glycerol formal.
8. The method according to any one of claims 1 to 4, wherein the acetal and/or ketal species added is separated from the product by distillation under reduced pressure after addition of water to the system after the reaction is completed.
9. The process according to any one of claims 1 to 4, wherein the substrate is diluted with a solvent selected from one or more inert aliphatic alkanes, aromatic hydrocarbons, ethers, halogenated alkanes which do not react with the feedstock.
10. The process according to claim 9, wherein the solvent is selected from one or more of n-heptane, toluene, 1, 2-dichloroethane, 1, 4-dioxane.
11. The method according to claim 9, wherein the amount of the diluting solvent is 0.5 to 3 times the mass of the alkynol substrate.
12. The method according to claim 9, wherein the amount of the diluting solvent is 0.8 to 1.5 times the mass of the alkynol substrate.
13. The process according to any one of claims 1 to 4, wherein the absolute pressure of the hydrogenation reaction is 0.01 to 2.0MPa, the reaction temperature is 0 to 90 ℃ and the reaction time is 0.5 to 24 hours.
14. The method according to any one of claims 1 to 4, wherein the hydrogen for hydrogenation is introduced in an amount such that the absolute pressure in the system is 0.05 to 0.3 MPa.
15. The method according to claim 13, wherein the hydrogen gas for hydrogenation is introduced in an amount such that the absolute pressure in the system is 0.1 to 0.15 MPa.
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| CN101869845A (en) * | 2010-06-21 | 2010-10-27 | 浙江新和成股份有限公司 | Catalyst for selective hydrogenation of dehydroisophytol for synthesizing isophytol |
| CN104854073A (en) * | 2012-12-18 | 2015-08-19 | 帝斯曼知识产权资产管理有限公司 | (6r,10r)-6,10,14-trimetylpentadecan-2-one prepared from 3,7-dimetyloct-2-enal or 3,7-dimetylocta-2,6-dienal |
| CN105283435A (en) * | 2013-06-10 | 2016-01-27 | 奇华顿股份有限公司 | Improvements in or relating to organic compounds |
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| CN101869845A (en) * | 2010-06-21 | 2010-10-27 | 浙江新和成股份有限公司 | Catalyst for selective hydrogenation of dehydroisophytol for synthesizing isophytol |
| CN104854073A (en) * | 2012-12-18 | 2015-08-19 | 帝斯曼知识产权资产管理有限公司 | (6r,10r)-6,10,14-trimetylpentadecan-2-one prepared from 3,7-dimetyloct-2-enal or 3,7-dimetylocta-2,6-dienal |
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