WO2023123126A1 - 一种含氮多孔有机聚合物复合材料及其制备方法与应用 - Google Patents
一种含氮多孔有机聚合物复合材料及其制备方法与应用 Download PDFInfo
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- WO2023123126A1 WO2023123126A1 PCT/CN2021/142699 CN2021142699W WO2023123126A1 WO 2023123126 A1 WO2023123126 A1 WO 2023123126A1 CN 2021142699 W CN2021142699 W CN 2021142699W WO 2023123126 A1 WO2023123126 A1 WO 2023123126A1
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- nitrogen
- organic polymer
- porous organic
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- composite material
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000003333 secondary alcohols Chemical class 0.000 claims abstract description 62
- 150000003138 primary alcohols Chemical class 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 secondary alcohol compound Chemical class 0.000 claims abstract description 17
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 10
- 239000004305 biphenyl Substances 0.000 claims abstract description 9
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 9
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 150000003303 ruthenium Chemical class 0.000 claims description 9
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- JESIHYIJKKUWIS-UHFFFAOYSA-N 1-(4-Methylphenyl)ethanol Chemical compound CC(O)C1=CC=C(C)C=C1 JESIHYIJKKUWIS-UHFFFAOYSA-N 0.000 claims description 4
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- WYLYBQSHRJMURN-UHFFFAOYSA-N (2-methoxyphenyl)methanol Chemical compound COC1=CC=CC=C1CO WYLYBQSHRJMURN-UHFFFAOYSA-N 0.000 claims description 2
- ZSRDNPVYGSFUMD-UHFFFAOYSA-N (3-chlorophenyl)methanol Chemical compound OCC1=CC=CC(Cl)=C1 ZSRDNPVYGSFUMD-UHFFFAOYSA-N 0.000 claims description 2
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 claims description 2
- DDUBOVLGCYUYFX-UHFFFAOYSA-N 1-(2-chlorophenyl)ethanol Chemical compound CC(O)C1=CC=CC=C1Cl DDUBOVLGCYUYFX-UHFFFAOYSA-N 0.000 claims description 2
- SPNHUMWMKXWVIU-UHFFFAOYSA-N 1-(3-methylphenyl)ethanol Chemical compound CC(O)C1=CC=CC(C)=C1 SPNHUMWMKXWVIU-UHFFFAOYSA-N 0.000 claims description 2
- XTDTYSBVMBQIBT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanol Chemical compound CC(O)C1=CC=C(Br)C=C1 XTDTYSBVMBQIBT-UHFFFAOYSA-N 0.000 claims description 2
- MVOSNPUNXINWAD-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanol Chemical compound CC(O)C1=CC=C(Cl)C=C1 MVOSNPUNXINWAD-UHFFFAOYSA-N 0.000 claims description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 claims description 2
- IIGNZLVHOZEOPV-UHFFFAOYSA-N 3-Methoxybenzyl alcohol Chemical compound COC1=CC=CC(CO)=C1 IIGNZLVHOZEOPV-UHFFFAOYSA-N 0.000 claims description 2
- JJCKHVUTVOPLBV-UHFFFAOYSA-N 3-Methylbenzyl alcohol Chemical compound CC1=CC=CC(CO)=C1 JJCKHVUTVOPLBV-UHFFFAOYSA-N 0.000 claims description 2
- MOOUWXDQAUXZRG-UHFFFAOYSA-N 4-(trifluoromethyl)benzyl alcohol Chemical compound OCC1=CC=C(C(F)(F)F)C=C1 MOOUWXDQAUXZRG-UHFFFAOYSA-N 0.000 claims description 2
- IUUULXXWNYKJSL-UHFFFAOYSA-N 4-methoxy-alpha-methylbenzyl alcohol Chemical compound COC1=CC=C(C(C)O)C=C1 IUUULXXWNYKJSL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- FVEINXLJOJPHLH-UHFFFAOYSA-N p-tert-Butylbenzyl alcohol Chemical compound CC(C)(C)C1=CC=C(CO)C=C1 FVEINXLJOJPHLH-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 2
- ZUBPFBWAXNCEOG-UHFFFAOYSA-N 1-(3-methoxyphenyl)ethanol Chemical compound COC1=CC=CC(C(C)O)=C1 ZUBPFBWAXNCEOG-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 64
- 239000002184 metal Substances 0.000 abstract description 64
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 62
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 59
- 229920000642 polymer Polymers 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- BUTGVBZBUDLKCM-UHFFFAOYSA-N 1h-benzimidazole;pyridine Chemical compound C1=CC=NC=C1.C1=CC=C2NC=NC2=C1 BUTGVBZBUDLKCM-UHFFFAOYSA-N 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 120
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 77
- 238000006243 chemical reaction Methods 0.000 description 75
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 61
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 60
- 229910052757 nitrogen Inorganic materials 0.000 description 50
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- 239000012074 organic phase Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 20
- 239000012043 crude product Substances 0.000 description 20
- 239000003480 eluent Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 20
- 239000003208 petroleum Substances 0.000 description 20
- 239000000741 silica gel Substances 0.000 description 20
- 229910002027 silica gel Inorganic materials 0.000 description 20
- 238000010257 thawing Methods 0.000 description 20
- 238000001914 filtration Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002861 polymer material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000002186 photoelectron spectrum Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SDCBYRLJYGORNK-UHFFFAOYSA-N 1-(2-methylphenyl)ethanol Chemical compound CC(O)C1=CC=CC=C1C SDCBYRLJYGORNK-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- YSVZGWAJIHWNQK-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)C(CO)C1C2 YSVZGWAJIHWNQK-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/40—Halogenated unsaturated alcohols
- C07C33/46—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the invention belongs to the technical field of catalytic chemistry, and relates to the preparation of a nitrogen-containing porous organic polymer composite material and its catalyzed cross-coupling reaction of secondary alcohols and primary alcohols to synthesize ⁇ -alkylated secondary alcohol compounds.
- Alcohols are very important in organic synthesis and chemical industry.
- Traditional routes to obtain ⁇ -alkylated alcohols from secondary alcohols usually require a multistep process involving oxidation of secondary alcohols, metallation of alkyl halides, and reduction of ⁇ -alkylated ketones.
- Reaction of an alcohol as an alkylating agent with another alcohol has been considered as a green direct method to obtain ⁇ -alkylated alcohols, H2 and/or H2O are produced as by-products during the transition metal-catalyzed reaction , has high atom utilization efficiency and is environmentally friendly.
- the metal-catalyzed cross-coupling reaction of secondary alcohols and primary alcohols is mainly carried out by dehydrogenation-condensation-hydrogenation steps, selectively obtaining ⁇ , ⁇ -unsaturated ketones, ⁇ -alkylated ketones, ⁇ -alkane Kylated secondary alcohols.
- Various homogeneous catalytic systems using metal complexes such as Ru, Ir, Pd, Cu, Co, and Mn have been developed for the ⁇ -alkylation of secondary alcohols with primary alcohols.
- the prior art still needs to be improved in terms of metal pollution reduction and catalyst recovery performance.
- the object of the present invention is to provide a preparation of nitrogen-containing porous organic polymer composite material and its catalyzed cross-coupling reaction of secondary alcohol and primary alcohol to synthesize ⁇ -alkylated secondary alcohol compounds.
- Nitrogen-containing porous organic polymers were prepared by a simple method using 2,6-bis(benzimidazole)pyridine and biphenyl as polymerization monomers. After the polymer is loaded with metal ruthenium, a composite material is obtained as a catalyst, and in toluene solvent, the cross-coupling reaction involving secondary alcohol and primary alcohol is catalyzed to finally prepare ⁇ -alkylated secondary alcohol.
- the composite material used as a catalyst can be reused more than 4 times, and it is still stable after 4 cycles, and its catalytic activity does not decrease significantly. It is an effective and efficient catalyst.
- a nitrogen-containing porous organic polymer composite material which is prepared from pyridine compounds and benzene compounds to prepare nitrogen-containing porous organic polymers, and then reacts with ruthenium salts to obtain the nitrogen-containing porous organic polymers.
- Polymer composite material preferably, nitrogen-containing porous organic polymer is prepared from pyridine compound and benzene compound under inert gas, and then reacted with ruthenium salt to obtain nitrogen-containing porous organic polymer composite material.
- the pyridine compound is 2,6-bis(benzimidazole)pyridine
- the benzene compound is biphenyl
- the ruthenium salt is ruthenium trichloride.
- the preparation method of the above-mentioned nitrogen-containing porous organic polymer composite material comprises the following steps: under an inert gas, 2,6-bis(benzimidazole)pyridine, biphenyl and aluminum chloride are added to anhydrous chloroform, and then React for 15 to 30 hours, then wash the obtained precipitate with water, dilute hydrochloric acid, and organic solvent to obtain a nitrogen-containing porous organic polymer, and then add RuCl 3 and nitrogen-containing porous organic polymer to absolute ethanol , and then reflux and stir for 8 to 15 hours to obtain a nitrogen-containing polymer-supported metal ruthenium composite material.
- the reaction is carried out at 50-65°C for 15-30 hours, and then the obtained precipitate is washed with water, dilute hydrochloric acid, water, methanol, and ether in sequence, and then vacuum-dried to obtain a nitrogen-containing porous organic polymer; reflux Stirring for 8-15 hours, washing the obtained precipitate with water, dilute hydrochloric acid, water, methanol, and ether in sequence, and then vacuum-drying to obtain a nitrogen-containing porous organic polymer composite material.
- the inert gas is selected from any one of nitrogen and argon, preferably nitrogen; chloroform is used as an organic solvent; aluminum trichloride is used as a catalyst.
- the invention discloses the application of the above-mentioned nitrogen-containing porous organic polymer composite material in the preparation of recyclable catalysts or the above-mentioned nitrogen-containing porous organic polymer composite material in catalyzing the cross-coupling of secondary alcohol and primary alcohol to synthesize ⁇ -alkylation Application of secondary alcohols.
- the secondary alcohol is selected from 1-phenethyl alcohol, 1-(4-chlorophenyl)ethanol, 1-(4-bromophenyl)ethanol, 1-(4-methylphenyl)ethanol, 1-(4 -methoxyphenyl)ethanol, 1-(2-chlorophenyl)ethanol, 1-(2-methoxy)ethanol, 1-(2-methylphenyl)ethanol, 1-(3-methoxy Any one in phenyl alcohol) ethanol, 1-(3-methylphenyl) ethanol;
- the primary alcohol is selected from benzyl alcohol, 4-chlorobenzyl alcohol, 4-trifluoromethyl benzyl alcohol, 4- Methoxybenzyl alcohol, 4-tert-butylbenzyl alcohol, 2-methylbenzyl alcohol, 2-methoxybenzyl alcohol, 3-methoxybenzyl alcohol, 3-methylbenzyl alcohol, 3-chlorobenzyl alcohol any of the
- the invention discloses a method for the synthesis of ⁇ -alkylated secondary alcohol compounds by catalyzing the cross-coupling of the secondary alcohol and the primary alcohol by the above-mentioned nitrogen-containing porous organic polymer composite material, comprising the following steps: mixing the secondary alcohol, the primary alcohol, Alkali, nitrogen-containing porous organic polymer composite material and solvent, under nitrogen, react at 100-140 ° C for 4-12 hours to obtain ⁇ -alkylated secondary alcohol compounds; further, after the reaction is completed, the composite material catalyst is removed by filtration, Water was added, extracted with ethyl acetate, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, and concentrated under reduced pressure, the crude product was purified by silica gel column, using petroleum ether and ethyl acetate as eluents, to obtain ⁇ -Alkylated secondary alcohols.
- the reaction of the secondary alcohol and the primary alcohol to prepare the ⁇ -alkylated secondary alcohol is carried out in the presence of a base in a nitrogen atmosphere; the secondary alcohol, primary alcohol, alkali, nitrogen-containing porous organic polymer composite material Dosage ratio is 1 mmol : (1-1.5) mmol : (0.3-1) mmol : (15-25) mg, preferably 1 mmol : 1.2 mmol : 0.5 mmol : 20 mg.
- the alkali is potassium hydroxide or cesium hydroxide.
- the temperature of the reaction is 100-140°C.
- reaction time is 4 to 12 hours.
- the present invention discloses a preparation method of a nitrogen-containing porous organic polymer for the first time, which uses 2,6-bis(benzimidazole) Pyridine and biphenyl are monomers, chloroform is a solvent, and aluminum trichloride is a catalyst; the polymer has good stability, large specific surface area and uniform pore size distribution.
- the nitrogen-containing porous organic polymer described in the present invention can support metal ruthenium, and the metal ruthenium has the characteristics of uniform distribution and trivalent valence.
- the nitrogen-containing porous organic polymer-supported metal ruthenium composite material described in the present invention can be applied to catalyze the cross-coupling reaction of secondary alcohols and primary alcohols to synthesize ⁇ -alkylated secondary alcohols, with high conversion efficiency, It has the characteristics of wide application range and green and mild reaction conditions.
- the catalyst is centrifuged from the reaction system, washed and dried, and then added to a new reaction system to proceed to the next round of reaction.
- the nitrogen-containing polymer-loaded metal ruthenium composite material can be reused 4 times, and its catalytic activity did not decrease significantly.
- Fig. 1 is a scanning electron microscope image of the nitrogen-containing porous organic polymer material of the present invention.
- Fig. 2 is a solid NMR carbon spectrum of the nitrogen-containing porous organic polymer material of the present invention.
- Fig. 3 is the nitrogen adsorption/desorption isotherm at 77 K of the nitrogen-containing porous organic polymer and the nitrogen-containing porous organic polymer-supported metal ruthenium composite material of the present invention.
- Fig. 4 is nitrogen-containing porous organic polymer of the present invention and nitrogen-containing porous organic polymer loaded metal ruthenium composite material N 1s photoelectron energy spectrum, compares the photoelectron energy spectrum of nitrogen before and after metal loading, and its binding energy increases to some extent, this It is caused by the coordination between nitrogen and ruthenium.
- Fig. 5 is an element distribution diagram of the nitrogen-containing porous organic polymer-supported metal ruthenium composite material of the present invention, illustrating the uniform distribution of C, N, and Ru elements.
- Fig. 6 is the nitrogen-containing porous organic polymer loaded metal ruthenium composite material of the present invention as the efficiency diagram of the reaction recycling of the catalyst embodiment 3, from which it can be seen that the catalyst maintains a higher efficiency in the process of recycling, and no Significantly decreased.
- metal ruthenium is evenly distributed on the nitrogen-containing polymer, and its substrate is a nitrogen-containing polymer, wherein the valence of metal ruthenium is trivalent; preferably, the nitrogen-containing polymer
- the loading amount of ruthenium is 2.5 wt% ⁇ 3.5 wt%, preferably 2.9 wt% to 3.3 wt%, which can be obtained by using the mass percentage between metal ruthenium and nitrogen-containing polymer material.
- Example 2 RuCl 3 (17 mg) and pyrazole polymer (200 mg) were added to a three-neck round bottom flask containing 25 mL of absolute ethanol, and liquid nitrogen freezing-pumping-nitrogen filling-thawing was repeated three times, Then reflux and stir for 12 hours. After the reaction, the solid was separated by centrifugation, washed with water, ethanol and ether in turn, and then vacuum-dried to obtain the corresponding nitrogen-containing polymer-loaded metal ruthenium composite material (the loading capacity of ruthenium is 3.11 wt%) , as the catalyst for the following examples.
- Fig. 1 is the scanning electron microscope figure of above-mentioned nitrogen-containing porous organic polymer material
- Fig. 2 is the solid nuclear magnetic carbon spectrogram of above-mentioned nitrogen-containing porous organic polymer material
- Fig. 3 is above-mentioned nitrogen-containing porous organic polymer and nitrogen-containing porous organic polymer Nitrogen adsorption/desorption isotherms of metal ruthenium composites loaded with metals at 77 K; Fig.
- FIG. 4 shows the N 1s photoelectron spectra of the above nitrogen-containing porous organic polymers and nitrogen-containing porous organic polymers loaded metal ruthenium composites, comparing metal-loaded Before and after the photoelectron spectrum of nitrogen, its binding energy has increased, which is caused by the coordination between nitrogen and ruthenium;
- Figure 5 is the element distribution diagram of the above-mentioned nitrogen-containing porous organic polymer loaded metal ruthenium composite material, illustrating Uniform distribution of C, N, Ru elements.
- the catalyst is separated from the reaction system by centrifugation. After the catalyst is washed and dried with water, methanol and ether, the next round of catalytic reaction will be carried out; the catalyst is recycled according to the above process, and the cycle 4 After several times, it still maintains a high activity, see Figure 6.
- the precursor prepared by the present invention is a nitrogen-containing porous organic polymer, and the metal ruthenium in the prepared composite material is evenly distributed on the polymer substrate, which is useful for catalyzing the cross-coupling of secondary alcohols and primary alcohols to synthesize ⁇ -alkylated secondary Alcohol compounds have high catalytic efficiency.
- the use of the catalyst of the invention can reduce metal pollution to products and has recyclability, and the functionalized nitrogen-containing porous organic polymer is loaded with metal to composite material, which can exhibit excellent catalytic performance in various reactions.
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Abstract
本发明公开了一种含氮多孔有机聚合物复合材料及其制备方法与应用。具体而言，本发明以三氯化铝为催化剂，将2,6-双（苯并咪唑）吡啶和联苯共聚得到多孔有机聚合物，以其作为载体通过配位作用将三氯化钌负载于该聚合物上，得到复合材料。该材料能够高效催化二级醇和一级醇的交叉偶联反应，合成β-烷基化的仲醇类化合物。该催化体系具有宽泛的官能团耐受性，催化剂连续循环使用多次后，仍保持较高催化活性且金属钌没有浸出。
Description
本发明属于催化化学技术领域，涉及一种含氮多孔有机聚合物复合材料的制备及其催化二级醇和一级醇的交叉偶联反应合成β-烷基化的仲醇类化合物。
醇类化合物在有机合成和化学工业中非常重要。从仲醇获得β-烷基化醇的传统路线通常需要多步过程，该过程涉及仲醇的氧化、烷基卤化物的金属化和β-烷基化酮的还原。通过醇作为烷基化试剂与另一种醇反应已被认为是获得β-烷基化醇的绿色直接方法，在过渡金属催化的反应过程中，H
2和/或H
2O作为副产物产生，具有高效的原子利用效率且对环境无害。其中，通过金属催化仲醇和伯醇的交叉偶联反应主要是通过脱氢-缩合-氢化步骤进行的，选择性地得到α,β-不饱和酮，α-烷基化的酮，β-烷基化的仲醇。目前已经开发出使用Ru，Ir，Pd，Cu，Co和Mn等金属络合物的各种均相催化体系，用于仲醇与伯醇的β-烷基化反应。但是现有技术在减少金属污染以及催化剂回收性能方面还需要提高。
针对上述情况，本发明的目的在于提供种含氮多孔有机聚合物复合材料的制备及其催化二级醇和一级醇的交叉偶联反应合成β-烷基化的仲醇类化合物。以2,6-双（苯并咪唑）吡啶和联苯为聚合单体，通过简单的方法制备了含氮多孔有机聚合物。该聚合物负载金属钌之后得到复合材料作为催化剂，在甲苯溶剂中，催化二级醇和一级醇参与的交叉偶联反应，最终制得β-烷基化的仲醇。另外，在上述反应体系中，作为催化剂使用的复合材料可以被重复利用4次以上，循环4次后仍然稳定，并且其催化活性也未出现明显降低，是一种有效且高效的催化剂。
为了实现上述目的，本发明采用如下技术方案：一种含氮多孔有机聚合物复合材料，由吡啶化合物、苯化合物制备含氮多孔有机聚合物，然后与钌盐反应，得到所述含氮多孔有机聚合物复合材料；优选的，惰性气体下，由吡啶化合物、苯化合物制备含氮多孔有机聚合物，然后与钌盐反应，得到含氮多孔有机聚合物复合材料。优选的，吡啶化合物为2,6-双（苯并咪唑）吡啶；苯化合物为联苯；钌盐为三氯化钌。
上述含氮多孔有机聚合物复合材料的制备方法包括如下步骤：惰性气体下，将2,6-双（苯并咪唑）吡啶，联苯和三氯化铝加入到无水三氯甲烷中，而后反应15～30小时，然后将得到的沉淀物用水、稀盐酸、有机溶剂洗涤，得到含氮多孔有机聚合物，然后在惰性气体下，将RuCl
3和含氮多孔有机聚合物加入到无水乙醇中，而后回流搅拌8～15小时，得到含氮聚合物负载金属钌复合材料。
上述技术方案中，反应在50～65℃下进行15～30小时，然后将得到的沉淀物依次用水、稀盐酸、水、甲醇、乙醚洗涤，然后真空干燥，得到含氮多孔有机聚合物；回流搅拌8～15小时，将得到的沉淀物依次用水、稀盐酸、水、甲醇、乙醚洗涤，然后真空干燥，得到含氮多孔有机聚合物复合材料。
上述技术方案中，所述惰性气体选自氮气、氩气中的任意一种，优选氮气；以三氯甲烷为有机溶剂；三氯化铝为催化剂。
本发明公开了上述含氮多孔有机聚合物复合材料在制备可循环催化剂中的应用或者上述含氮多孔有机聚合物复合材料在催化二级醇和一级醇的交叉偶联反合成β-烷基化仲醇类化合物中的应用。所述二级醇选自1-苯乙醇、1-（4-氯苯基）乙醇、1-（4-溴苯基）乙醇、1-（4-甲基苯基）乙醇、1-（4-甲氧基苯基）乙醇、1-（2-氯苯基）乙醇、1-（2-甲氧基）乙醇、1-（2-甲基苯基）乙醇、1-（3-甲氧基苯基）乙醇、1-（3-甲基苯基）乙醇中的任意一种；所述一级醇选自苯甲醇、4-氯苯甲醇、4-三氟甲基苯甲醇、4-甲氧基苯甲醇、4-叔丁基苯甲醇、2-甲基苯甲醇、2-甲氧基苯甲醇、3-甲氧基苯甲醇、3-甲基苯甲醇、3-氯苯甲醇中的任意一种。
本发明公开了上述含氮多孔有机聚合物复合材料催化二级醇和一级醇的交叉偶联反合成β-烷基化仲醇类化合物的方法包括如下步骤：混合二级醇、一级醇、碱、含氮多孔有机聚合物复合材料与溶剂，氮气下，100～140℃反应4～12小时，得到β-烷基化仲醇类化合物；进一步的，反应结束后，过滤除去复合材料催化剂，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩，粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到β-烷基化仲醇类化合物。
上述技术方案中，二级醇和一级醇反应制备β-烷基化仲醇在碱存在下、在氮气氛围中进行；二级醇、一级醇、碱、含氮多孔有机聚合物复合材料的用量比为1
mmol : （1～1.5） mmol : （0.3～1） mmol : （15～25）mg，优选为1 mmol : 1.2
mmol : 0.5 mmol : 20 mg。
上述技术方案中，所述碱为氢氧化钾或者氢氧化铯。
上述技术方案中，所述反应的温度为100～140℃。
上述技术方案中，所述反应的时间为4～12小时。
与现有技术相比，采用上述技术方案的本发明具有下列优点：（1）本发明首次披露了一种含氮多孔有机聚合物的制备方法，其以2,6-双（苯并咪唑）吡啶和联苯为单体，三氯甲烷为溶剂，三氯化铝为催化剂；该聚合物稳定性好，比表面积大，孔径分布均匀。
（2）本发明中记载的含氮多孔有机聚合物可以负载金属钌，且金属钌具有分布均匀、化合价为三价等特点。
（3）本发明中记载的含氮多孔有机聚合物负载金属钌复合材料可以应用于催化二级醇和一级醇的交叉偶联反合成β-烷基化仲醇类化合物，具有转化效率高、适用范围广、反应条件绿色温和等特点。
（4）催化反应结束后，从反应体系中离心出催化剂，将催化剂洗涤干燥后加入到新的反应体系中，即可进行下一轮反应，该含氮聚合物负载金属钌复合材料能够重复使用4次，并且其催化活性也未出现明显降低。
图1为本发明的含氮多孔有机聚合物材料的扫描电镜图。
图2为本发明含氮多孔有机聚合物材料的固体核磁碳谱图。
图3为本发明的含氮多孔有机聚合物和含氮多孔有机聚合物负载金属钌复合材料在77 K下的氮气吸附/解吸等温线。
图4为本发明的含氮多孔有机聚合物和含氮多孔有机聚合物负载金属钌复合材料的N 1s光电子能谱，对比金属负载前后氮的光电子能谱，其结合能有所增大，这是氮钌之间的配位作用造成的。
图5为本发明的含氮多孔有机聚合物负载金属钌复合材料的元素分布图，说明了C、N、Ru元素的均匀分布。
图6为本发明的含氮多孔有机聚合物负载金属钌复合材料作为催化剂催化实施例3反应循环利用的效率图，从中可以看出，在循环使用的过程中催化剂保持较高的效率，没有发生明显下降。
下面将结合附图和具体实施例对本发明做出进一步的描述。除非另有说明，下列实施例中所使用的试剂、材料、仪器等均可通过商业手段获得，具体的制备操作以及测试表征都是常规技术。本发明公开的含氮多孔有机聚合物复合材料中，金属钌均匀分布在含氮聚合物上，其基底为含氮聚合物，其中金属钌呈现的化合价为三价；优选的，含氮聚合物负载金属钌材料中，钌的负载量为2.5
wt%～3.5 wt%，优选2.9
wt%～3.3 wt%，可以利用金属钌与含氮聚合物材料之间的质量百分比获得。
实施例1：在氮气氛围下，将2,6-双（苯并咪唑）吡啶（1mmol），联苯(0.154g,
1 mmol)和三氯化铝(10 mmol, 1.33 g)加入到无水三氯甲烷20 mL中，而后在58 ℃下搅拌反应24小时，反应结束后，将得到的沉淀物依次用水、稀盐酸（HCl-H
2O，v/v = 1 : 1）、水、甲醇、乙醚洗涤，然后真空干燥，得到含氮多孔有机聚合物。
实施例2：将RuCl
3
(17 mg)、吡唑聚合物（200 mg）加入到含有25mL无水乙醇的三颈圆底烧瓶中，液氮冷冻-抽气-充氮气-解冻反复进行三次，而后回流搅拌12小时，反应结束后，离心分离出固体，依次用水、乙醇和乙醚洗涤，然后真空干燥，即得相应的含氮聚合物负载金属钌复合材料（钌的负载量为3.11
wt%），作为以下实施例的催化剂。
上述反应示意如下。
图1为上述含氮多孔有机聚合物材料的扫描电镜图；图2为上述含氮多孔有机聚合物材料的固体核磁碳谱图；图3为上述含氮多孔有机聚合物和含氮多孔有机聚合物负载金属钌复合材料在77 K下的氮气吸附/解吸等温线；图4为上述含氮多孔有机聚合物和含氮多孔有机聚合物负载金属钌复合材料的N 1s光电子能谱，对比金属负载前后氮的光电子能谱，其结合能有所增大，这是氮钌之间的配位作用造成的；图5为上述含氮多孔有机聚合物负载金属钌复合材料的元素分布图，说明了C、N、Ru元素的均匀分布。
实施例3。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩，粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇，HPLC收率93%，分离收率88%。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.34 – 7.26 (m, 4H), 7.26 – 7.20
(m, 3H), 7.15 (t, J = 6.2 Hz, 3H), 4.59 (dd, J = 7.4, 5.7 Hz, 1H), 2.65 (m,
2H), 2.23 (s, 1H), 2.14 – 1.86 (m, 2H).
13C
NMR (100 MHz, CDCl
3, ppm): δ
144.7, 141.9, 128.54, 128.51, 128.45, 127.7, 126.0, 125.9, 73.9, 40.5, 32.1。
上述反应结束后，通过离心的方式，从反应体系中分离出催化剂，催化剂经水、甲醇、乙醚洗涤烘干后，再将进行下一轮催化反应；按照上述过程对催化剂进行循环利用，循环4次后仍保持较高活性，参见图6。
在上述反应过程的基础上，保持底物不变，改变其他条件，得到如表1的结果。
表1 反应条件与产物收率。
表1中，
1a (1
mmol),
2a (1.2 mmol), cat. (20 mg), base (eq.), toluene (2 mL) ，HPLC收率（联苯为内标物）。
实施例4。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩，粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.31 (d,
J
= 8.3 Hz, 2H), 7.28 (t,
J = 7.7 Hz, 4H), 7.18 (t,
J = 8.6 Hz,
3H), 4.69 – 4.62 (m, 1H), 2.77 – 2.61 (m, 2H), 2.09 (m, 1H), 1.98 (m, 1H), 1.81 (s, 1H).
13C
NMR (100 MHz, CDCl
3, ppm): δ
143.2, 141.6, 133.4, 128.8, 128.6, 128.5, 127.4, 126.1, 73.3, 40.6, 32.1。
实施例5。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.47 (d,
J
= 8.3 Hz, 2H), 7.28 (t,
J = 7.5 Hz, 2H), 7.22 (d,
J = 8.3 Hz,
2H), 7.18 (t,
J = 8.3 Hz, 3H), 4.65 (dd,
J = 7.6, 5.5 Hz, 1H),
2.78 – 2.61 (m, 2H), 2.16 – 2.05 (m, 1H), 2.03 – 1.93
(m, 1H), 1.77 (s, 1H).
13C NMR (100 MHz, CDCl
3, ppm): δ 142.7, 140.6, 130.7, 127.7, 127.6, 127.6, 126.8, 125.1,
125.1, 120.5, 72.3, 39.6, 31.0。
实施例6。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.27 – 7.21 (m, 2H), 7.19 (s, 1H), 7.18 – 7.08 (m, 6H), 4.63 – 4.51
(m, 1H), 2.76 – 2.54 (m, 2H), 2.31 (s, 3H), 2.19 (s,
1H), 2.12 – 2.01 (m, 1H), 2.01 – 1.90 (m, 1H).
13C NMR (100 MHz, CDCl
3,
ppm): δ 142.0, 141.7, 137.3, 129.2, 128.5,
128.4, 126.0, 125.9, 73.7, 40.4, 32.1, 21.2。
实施例7。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.29 – 7.21 (m, 3H), 7.20 (d,
J = 1.9 Hz, 1H), 7.15 (dd,
J = 7.1, 5.3 Hz, 3H), 6.90 – 6.77
(m, 2H), 4.61 – 4.50 (m, 1H), 3.74 (s, 3H), 2.80 – 2.50 (m, 2H), 2.29 (s, 1H), 2.14 – 2.02 (m, 1H), 1.95 (m, 1H).
13C NMR (100 MHz,
CDCl
3, ppm): δ 159.1, 141.9,
136.8, 128.5, 128.4, 127.3, 125.9, 113.9, 73.4, 55.3, 40.4, 32.1。
实施例8。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (600 MHz,
CDCl
3) δ 7.57 (dd,
J
= 7.7, 1.6 Hz, 1H), 7.34 – 7.30 (m, 1H),
7.29 – 7.25 (m, 3H), 7.23 – 7.19 (m, 3H), 7.17 (d,
J = 7.3 Hz, 2H), 5.13 (dd,
J = 8.4, 4.1 Hz, 1H), 2.93 – 2.81
(m, 1H), 2.74 (m, 1H), 2.15 – 1.99 (m, 2H),
1.85 (s, 1H).
13C NMR (151 MHz, CDCl
3) δ 142.1, 141.8, 132.0, 129.6, 129.2, 128.6, 128.5, 128.4,
127.3, 127.2, 126.0, 125.4, 70.4, 39.1, 32.3。
实施例9。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.45 (dd,
J
= 7.5, 1.4 Hz, 1H), 7.42 – 7.37 (m, 2H),
7.37 – 7.22 (m, 4H), 7.07 (t,
J = 7.3
Hz, 1H), 6.96 (d,
J = 8.2 Hz, 1H), 5.03 (s, 1H), 3.89 (s, 3H), 3.03 (s,
1H), 3.00 – 2.90 (m, 1H), 2.81 (m, 1H), 2.32 – 2.14 (m, 2H).
13C NMR (100 MHz, CDCl
3,
ppm): δ 156.5, 142.2, 132.4, 128.5, 128.3,
126.9, 125.7, 120.7, 110.5, 70.1, 55.2, 38.8, 32.3。
实施例10。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5 mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.43 (d,
J
= 7.5 Hz, 1H), 7.28 – 7.21 (m, 2H), 7.20 – 7.09 (m, 5H), 7.07 (d,
J = 7.2 Hz, 1H), 4.83 (dd,
J = 8.0, 4.5 Hz, 1H), 2.79 (m, 1H), 2.67 (m, 1H), 2.17 (s, 3H), 2.10 (s,
1H), 2.05 – 1.87 (m, 2H).
13C NMR (100
MHz, CDCl
3, ppm): δ 142.8, 141.9,
134.5, 130.5, 128.5, 128.4, 127.2, 126.3, 125.9, 125.2, 69.9, 39.5, 32.3, 18.9。
实施例11。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.23 (dd,
J
= 14.1, 7.0 Hz, 3H), 7.16 (t,
J = 9.4 Hz, 3H), 6.87 (d,
J = 2.0
Hz, 2H), 6.77 (dd,
J = 8.1, 1.8 Hz, 1H), 4.57 (dd,
J = 7.1, 5.9
Hz, 1H), 3.73 (s, 3H), 2.75 – 2.53 (m, 2H),
2.42 (s, 1H), 2.14 – 1.88 (m, 2H).
13C
NMR (150 MHz, CDCl
3, ppm): δ
159.8, 146.4, 141.9, 129.5, 128.5, 128.4, 125.9, 118.3, 113.0, 111.5, 73.7,
55.2, 40.4, 32.1.
19F NMR (377 MHz, CDCl
3, ppm):
δ-63.3。
实施例12。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.29 – 7.20 (m, 2H), 7.19 (d,
J = 7.5 Hz, 1H), 7.14 (dd,
J = 8.4, 4.0 Hz, 3H), 7.12 – 7.00
(m, 3H), 4.54 (m, 1H), 2.77 – 2.54 (m, 2H),
2.33 (s, 1H), 2.30 (s, 3H), 2.01 (m, 2H).
13C NMR (100 MHz, CDCl
3,
ppm): δ 144.6, 141.9, 138.1, 128.5, 128.4,
128.4, 126.7, 125.9, 123.1, 73.8, 40.4, 32.1, 21.5。
实施例13。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.34 (q,
J
= 6.2 Hz, 4H), 7.25 (dd,
J = 16.2, 9.5 Hz, 3H), 7.11 (d,
J = 8.3
Hz, 2H), 4.65 (t,
J = 4.7 Hz, 1H), 2.82 – 2.54
(m, 2H), 2.19 – 1.88 (m, 3H).
13C NMR (100
MHz, CDCl
3, ppm): δ 144.6, 140.4,
131.7, 130.0, 128.7, 128.6, 127.9, 126.1, 73.9, 40.5, 31.5。
实施例14。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.49 (d,
J
= 8.1 Hz, 2H), 7.31 (s, 1H), 7.28 (dd,
J = 8.6, 2.1 Hz, 3H), 7.23 (t,
J
= 5.8 Hz, 3H), 4.59 (dd,
J = 7.7, 5.5 Hz, 1H), 2.83 – 2.56 (m, 2H), 2.48 (s, 1H), 2.17 – 1.85 (m, 2H).
13C NMR (100 MHz, CDCl
3,
ppm): δ 146.1, 144.4, 128.8, 128.7, 127.9,
126.0, 125.4, 125.4, 125.3, 125.3, 73.7, 40.1, 31.9。
实施例15。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.34 (d,
J
= 2.3 Hz, 4H), 7.31 – 7.25 (m, 1H),
7.10 (dd,
J = 8.1, 3.8 Hz, 2H), 6.83 (dd,
J = 8.1, 5.8 Hz, 2H),
4.74 – 4.61 (m, 1H), 3.78 (s, 3H), 2.78 – 2.54 (m, 2H), 2.23 – 1.83
(m, 3H).
13C NMR (100 MHz, CDCl
3, ppm): δ 157.9, 144.8, 134.0, 129.5, 128.6, 127.7, 126.1, 114.0,
74.0, 55.4, 40.9, 31.3。
实施例16。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.33 – 7.25 (m, 6H), 7.25 – 7.19
(m, 1H), 7.09 (d,
J = 8.3 Hz, 2H), 4.60 (t,
J = 6.5 Hz, 1H), 2.78
– 2.48 (m, 2H), 2.27 (s, 1H), 2.03 (m,
2H), 1.29 (s, 9H).
13C NMR (100 MHz, CDCl
3, ppm): δ 148.7, 144.7, 138.8, 128.5, 128.2, 127.6, 126.1, 125.3,
73.9, 40.5, 34.4, 31.5, 31.5。
实施例17。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.27 (d,
J =
4.4 Hz, 4H), 7.23 – 7.19 (m, 1H),
7.07 (dd,
J = 5.9, 3.2 Hz, 4H), 4.60 (dd,
J = 7.6, 5.5 Hz, 1H),
2.72 – 2.63 (m, 1H), 2.58 – 2.49 (m, 1H), 2.41 (s, 1H), 2.20 (s, 3H), 2.02 – 1.87 (m, 2H).
13C NMR (100 MHz, CDCl
3,
ppm): δ 144.6, 140.1, 136.0, 130.2, 128.8,
128.5, 127.6, 125.99, 125.98, 74.1, 39.2, 29.4, 19.2。
实施例18。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.28 (dd,
J
= 9.1, 5.2 Hz, 4H), 7.22 – 7.08 (m, 3H),
6.89 – 6.77 (m, 2H), 4.56 (dd,
J = 8.3,
5.0 Hz, 1H), 3.74 (s, 3H), 2.70 (m, 2H), 2.65 (s, 1H), 2.07 – 1.91 (m, 2H).
13C NMR (100 MHz, CDCl
3,
ppm): δ 157.4, 144.7, 130.1, 130.1, 128.3,
127.3, 127.2, 126.0, 120.7, 110.4, 73.6, 55.3, 39.3, 26.5。
实施例19。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.38 – 7.19 (m, 5H), 7.20 – 7.12
(m, 1H), 6.72 (dd,
J = 19.4, 7.1 Hz, 3H), 4.65 – 4.52 (m, 1H), 3.72 (s, 3H), 2.78 – 2.50 (m, 2H), 2.35 (s, 1H), 2.16 – 1.89 (m, 2H).
13C NMR (100 MHz, CDCl
3,
ppm): δ 159.7, 144.7, 143.5, 129.4, 128.5,
127.60, 126.0, 120.9, 114.3, 111.2, 73.8, 55.1, 40.4, 32.1。
实施例20。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.28 (s, 4H),
7.24 (d,
J = 5.8 Hz, 1H), 7.13 (t,
J = 7.7 Hz, 1H), 7.02 – 6.87 (m, 3H), 4.71 – 4.45
(m, 1H), 2.72 – 2.51 (m, 2H), 2.29 (s, 4H), 2.00 (m,
2H).
13C NMR (100 MHz, CDCl
3, ppm): δ 144.7, 141.8, 137.9, 129.3, 128.5, 128.3, 127.6, 126.6,
126.0, 125.5, 73.9, 40.5, 32.0, 21.5。
实施例21 。
将二级醇（1 mmol）、一级醇（1.2 mmol）、含氮聚合物负载金属钌复合材料（20 mg）、氢氧化钾（0.5
mmol）加入到装有磁力搅拌子15 mL反应管中，加入2 mL甲苯，液氮冷冻-抽气-充氮气-解冻反复进行三次，在130 ℃油浴锅中反应12小时；反应结束后，过滤除去含氮聚合物负载金属钌复合材料，加入水，用乙酸乙酯进行萃取，合并有机相，有机相经无水硫酸钠干燥，并在减压下浓缩。粗产物通过硅胶柱纯化，使用石油醚和乙酸乙酯作为洗脱剂，得到相应的仲醇。
所得产物的核磁数据如下：
1H NMR (400 MHz,
CDCl
3, ppm): δ 7.33 – 7.30 (m, 1H), 7.29 (s, 1H), 7.26 (dd,
J = 11.3,
4.8 Hz, 2H), 7.17 – 7.10 (m, 3H),
7.00 (dt,
J = 6.5, 1.7 Hz, 1H), 4.57 (t,
J = 6.5 Hz, 1H), 2.60
(m, 2H), 2.41 (s, 1H), 2.10 – 1.86 (m, 2H).
13C
NMR (100 MHz, CDCl
3, ppm): δ
144.4, 144.0, 134.1, 129.7, 128.6, 128.6, 127.8, 126.7, 126.1, 126.0, 73.7,
40.2, 31.7。
上述实施例的产物对应的分离收率见表2。
表2 实施例产物收率：
。
本发明制备的前驱体是含氮多孔有机聚合物，制备的复合材料中金属钌均匀分布在聚合物基底上，其对于催化二级醇和一级醇的交叉偶联反合成β-烷基化仲醇类化合物具有高效的催化效率。本发明催化剂的使用能够减少金属对产品的污染且有可回收利用性，在功能化的含氮多孔有机聚合物上负载金属的到复合材料，可以在各种反应中表现出色的催化性能。
Claims (10)
- 一种含氮多孔有机聚合物复合材料，其特征在于，由吡啶化合物、苯化合物制备含氮多孔有机聚合物，然后与钌盐反应，得到含氮多孔有机聚合物复合材料。
- 根据权利要求1所述含氮多孔有机聚合物复合材料，其特征在于，吡啶化合物为2,6-双（苯并咪唑）吡啶；苯化合物为联苯；钌盐为三氯化钌。
- 权利要求1所述含氮多孔有机聚合物复合材料的制备方法，其特征在于，包括如下步骤：惰性气体下，由吡啶化合物、苯化合物制备含氮多孔有机聚合物，然后与钌盐反应，得到含氮多孔有机聚合物复合材料。
- 根据权利要求3所述含氮多孔有机聚合物复合材料的制备方法，其特征在于，制备含氮多孔有机聚合物在有机溶剂中进行，无机铝盐为催化剂。
- 根据权利要求4所述含氮多孔有机聚合物复合材料的制备方法，其特征在于，将2,6-双（苯并咪唑）吡啶，联苯和无机铝盐在有机溶剂中反应15～30小时，然后将得到的沉淀物用水、稀盐酸、有机溶剂洗涤，得到含氮多孔有机聚合物。
- 根据权利要求3所述含氮多孔有机聚合物复合材料的制备方法，其特征在于，含氮多孔有机聚合物与钌盐在溶剂中回流反应，得到含氮多孔有机聚合物复合材料。
- 含氮多孔有机聚合物在制备权利要求1所述含氮多孔有机聚合物复合材料中的应用，其特征在于，由吡啶化合物、苯化合物制备含氮多孔有机聚合物。
- 权利要求1所述含氮多孔有机聚合物复合材料在制备可循环催化剂中的应用。
- 权利要求1所述含氮多孔有机聚合物复合材料在催化二级醇和一级醇的交叉偶联反合成β-烷基化仲醇类化合物中的应用。
- 根据权利要求9所述的应用，其特征在于，所述二级醇选自1-苯乙醇、1-（4-氯苯基）乙醇、1-（4-溴苯基）乙醇、1-（4-甲基苯基）乙醇、1-（4-甲氧基苯基）乙醇、1-（2-氯苯基）乙醇、1-（2-甲氧基）乙醇、1-（2-甲基苯基）乙醇、1-（3-甲氧基苯基）乙醇、1-（3-甲基苯基）乙醇中的任意一种；所述一级醇选自苯甲醇、4-氯苯甲醇、4-三氟甲基苯甲醇、4-甲氧基苯甲醇、4-叔丁基苯甲醇、2-甲基苯甲醇、2-甲氧基苯甲醇、3-甲氧基苯甲醇、3-甲基苯甲醇、3-氯苯甲醇中的任意一种。
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