CN114249661B - Method for preparing amine ether compound by utilizing N-alkylation reaction of aromatic amine and alcohol ether substance - Google Patents
Method for preparing amine ether compound by utilizing N-alkylation reaction of aromatic amine and alcohol ether substance Download PDFInfo
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 31
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 28
- -1 amine ether compound Chemical class 0.000 title claims abstract description 25
- 238000007126 N-alkylation reaction Methods 0.000 title claims abstract description 24
- 239000000126 substance Substances 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims abstract description 31
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims abstract description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000009471 action Effects 0.000 claims abstract description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 28
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- DTEGEQGTAYAXBC-UHFFFAOYSA-N 2,6-diethyl-n-(2-propoxyethyl)aniline Chemical compound CCCOCCNC1=C(CC)C=CC=C1CC DTEGEQGTAYAXBC-UHFFFAOYSA-N 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 7
- 239000002168 alkylating agent Substances 0.000 description 6
- 229940100198 alkylating agent Drugs 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 230000002152 alkylating effect Effects 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- WXCIATVPPDUURB-UHFFFAOYSA-N 2-(2,6-diethylanilino)propan-1-ol Chemical compound CC(CO)NC1=C(C=CC=C1CC)CC WXCIATVPPDUURB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BHDSGQOSIWVMJW-UHFFFAOYSA-N 1-(2-chloroethoxy)propane Chemical compound CCCOCCCl BHDSGQOSIWVMJW-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000005824 Ullmann-Goldberg substitution reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical class ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention discloses a method for preparing an amine ether compound by utilizing N-alkylation reaction of aromatic amine and alcohol ether substances shown in a formula I, which comprises the steps of taking the aromatic amine and the alcohol ether substances as reactants, and preparing the amine ether compound by one-step N-alkylation reaction under the action of an amphoteric oxide catalyst in inert atmosphere; the amphoteric oxide carrier is Al 2 O 3 、ZrO 2 Or CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The alcohol ether material is ethylene glycol mono-n-propyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether or ethylene glycol monobutyl ether. The invention has the characteristics of environment protection, simplicity, reliability and high yield.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a method for preparing an amine ether compound by utilizing N-alkylation reaction of aromatic amine and alcohol ether substances.
Background
N-alkylation reaction is an important organic synthesis reaction, and the synthesized product relates to important technological fields including chemical industry, medical treatment, medicine, national defense and the like. With the development of chemical technology in recent years, such reactions have become one of the important research points of organic chemistry. The alkylation reaction of nitrogen is mostly to take substances such as halohydrocarbon, aldehyde, amine and the like as alkylating agents from nitrogen-containing compounds, and obtain alkylated amine through condensation, oxidation, reduction, coupling and other reactions under certain conditions. N-alkylation of aromatic amines is classified into 3 types according to the type of reaction and alkylating agent used: (1) substituted alkylation: alkylation is carried out by taking alcohol, alkyl halide (particularly alkyl iodide, alkyl bromide and alkyl chloride) and ester of strong acid as alkylating agent; (2) addition alkylation: the aromatic amine, the acrylic acid derivative and the epoxy compound are used as alkylating agents for addition, but the product is provided with hydroxyl groups, and the hydroxyl groups on the product need to be further treated; (3) reductive alkylation: aromatic amines are condensed with alkylating agents such as aldehydes and ketones. With respect to this study of C-N bond construction, early days there were well known Ullmann reactions and Goldberg reactions. Because of the limited conditions at that time, these processes often suffer from a number of disadvantages (1) the use of organic halides in the reaction, by-products of hydrogen halides and large amounts of acidic wastewater, which are harmful to the environment; (2) Without a better catalytic system, the reaction often needs a high temperature of 200 ℃ or above; (3) A lot of strong alkali needs to be added as an acid binding agent to generate a large amount of inorganic solid waste; (4) low atom utilization rate and poor product selectivity.
At present, in the production process of generating amine ether compounds, most of the amine ether compounds are usually obtained by using aniline compounds and chloroether compounds through N-alkylation reaction. In the process of N-alkylation reaction, an auxiliary agent or an acid binding agent is usually required to be added to ensure that the target product has better selectivity and yield. In the invention patent with application publication number of CN111100019A, du Xiaohua et al take raw material 2, 6-diethyl aniline and chloroethyl propyl ether to carry out N-alkylation reaction, add N, N-di-N-propyl-2-propoxyethylamine as auxiliary agent to inhibit secondary nitrogen alkylation reaction, and add NaOH to adjust pH value of reaction liquid to improve selectivity of target product. In the invention patent with the application publication number of CN102229542A, two steps are needed to generate an amine ether compound, 2, 6-ethylaniline and ethylene oxide are used as starting materials, N- (1-methyl-2-hydroxyethyl) -2, 6-diethylaniline is prepared under the conditions of a solvent and a catalyst, then the N- (1-methyl-2-hydroxyethyl) -2, 6-diethylaniline and N-chloropropane are used as starting materials to react, and in the reaction process, strong alkali is added as an acid-binding agent to react to generate amine ether. Then during the reaction there is a potential for corrosion of the experimental equipment and other byproducts.
Through research and development for many years, alcohol has been proved to have the same properties as halogenated alkane and halogenated aromatic hydrocarbon in the reaction process, and becomes a new generation of alkylating reagent, and alcohol is used as the alkylating reagent to react with aromatic amine to synthesize substituted aromatic amine, so that the alcohol has the advantages of low-cost and easily obtained raw materials, high atom utilization rate, only water as a byproduct and the like. Therefore, a green organic synthesis method using alcohol as an alkylating agent is becoming more and more popular to researchers. Nickel-based loading on theta-Al in the reaction of amines with alcohol N-alkylation, such as Ken-ichi Shimizu (ACS catalyst.2013, 3,5,998-1005) in Japan 2 O 3 The research finds that the acid-base bifunctional carrier has higher activity than the alkaline or acid carrier, which indicates that acid-base sites on the carrier are necessary.
However, in the N-alkylation reaction of catalytic aromatic amine and alcohol ether substances, the alcohol ether substances containing ether bonds react more complex under relative conditions, the ether bonds can be broken in the reaction process to generate small molecules such as aldehyde or alcohol, and the substances after the breaking of the bonds can be used as alkylating reagents to generate a series of byproducts, so that the reaction selectivity is reduced. The choice of a suitable catalyst support and its modification of the metal is of great significance for the N-alkylation reaction.
From the viewpoint of sustainable chemistry, the preparation of a series of catalysts capable of minimizing by-products and three wastes is one of the most important targets in the industrial development.
Disclosure of Invention
The invention aims to provide a method for preparing an amine ether compound by utilizing N-alkylation reaction of aromatic amine and alcohol ether substances, which has the characteristics of environment friendliness, simplicity, reliability and high yield.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for preparing amine ether compound by N-alkylation reaction of aromatic amine and alcohol ether substance shown in formula I, wherein the method is to prepare amine ether compound by one-step N-alkylation reaction of aromatic amine and alcohol ether substance in inert atmosphere under the action of amphoteric oxide catalyst; the amphoteric oxide carrier is Al 2 O 3 、ZrO 2 Or CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The alcohol ether material is ethylene glycol mono-n-propyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether isopropyl ether, diethylene glycol monobutyl ether or ethylene glycol monobutyl ether;
wherein R is H or C 1 -C 10 An alkyl group; r is R 1 、R 2 、R 3 、R 4 、R 5 Each independently is H or C 1 -C 10 An alkyl group.
The N-alkylation reaction refers to the reaction of amino in aromatic amine and hydroxyl in alcohol ether substances, and dehydration is carried out to generate amine ether compounds.
The amphoteric oxide catalyst used in the present invention may be prepared by commercially available products or by conventional methods. In general, the larger the specific surface area of the catalyst, the more active sites, so increasing the specific surface area of the catalyst is advantageous for improving the catalytic activity thereof. The specific surface area of the amphoteric oxide catalyst is controlled to be 15m 2 And/g.
Preferably, the amphoteric oxide carrier is nano-scale zirconia. Particularly preferablyThe nanoscale zirconia is prepared by the following method: polyether F127 is dissolved in ethanol under the condition of room temperature, and the solution I is recorded; zrOCl is then stirred vigorously 2 ·8H 2 Adding O into the solution I, stirring for 5-12h, drying, aging at 30-80deg.C (preferably 40deg.C) for 1-5 days (preferably 2 days) to obtain gel, drying the gel at 80-130deg.C for 12-36h, and calcining at 350-550deg.C (preferably 400deg.C) in air for 2-6h (preferably 4 h) to obtain nanometer zirconia; wherein polyether F127, ethanol and ZrOCl 2 ·8H 2 The feed ratio of O is 1.0g:8-20mL:1-3g.
Preferably, the method for preparing the amine ether compound is carried out according to the following steps: adding aromatic amine, alcohol ether and amphoteric oxide catalyst into a high-pressure reaction kettle, introducing inert gas to replace air in the reaction kettle, controlling the pressure of the inert gas to be normal pressure-4.0 MPa, and controlling the reaction temperature to be 100-300 ℃ for N-alkylation reaction to generate amine ether compound. In the reaction process, sampling is carried out at fixed time for detection until the reactant is not converted continuously, and the product reaches equilibrium, namely the reaction end point. Further preferably, the inert gas pressure is 1.0 to 1.5MPa. The further reaction temperature is 200-250 ℃.
Preferably, the molar ratio of the aromatic amine to the alcohol ether is 1-10, preferably 2-4:1, and most preferably 3:1.
Preferably, the feeding mass of the amphoteric oxide catalyst is 0.01% -10.0% of the total mass of the aromatic amine and the alcohol ether substances, and more preferably 1.0% -5.0%.
Preferably, the inert gas is nitrogen or argon.
Compared with the prior art, the invention has the following remarkable effects:
(1) The invention adopts arylamine derivatives and alcohol derivatives containing ether bonds as raw materials to directly catalyze N-alkylation reaction to prepare amine ether compounds, the existing multi-step reaction of halogenating first and then N-alkylation is changed into one-step reaction, the reaction path is simpler, alcohol ether is used as an alkylating reagent of amine, and water is the only byproduct, so that high-acid corrosion equipment is avoided in the halogenation reaction process, and the invention has the characteristics of environmental protection, simplicity and reliability.
(2) The amphoteric oxide catalyst used in the invention has excellent catalytic activity in N-alkylation reaction of arylamine derivatives and alcohol derivatives containing ether bonds, can inhibit breakage of the ether bonds, greatly reduces the generation of byproducts, simultaneously reduces secondary nitrogen alkylation of the products, and has excellent product selectivity. Has excellent stability.
(3) The catalyst is simple and easy to manufacture and can be recycled;
(4) The one-pot reaction of the invention does not need to add strong alkali as an acid binding agent after adding the catalyst.
Drawings
FIG. 1 is a GC analysis chart of the product obtained in example 4.
FIG. 2 shows ZrO as obtained in example 3 2 X-ray diffraction (XRD) patterns of (a).
FIG. 3 is an X-ray diffraction (XRD) pattern of 1.0N-ZSM-5 obtained in example 10.
Detailed Description
The following describes the technical scheme of the present invention by specific examples, but the scope of the present invention is not limited thereto:
the conversion and selectivity in the following examples were calculated from the analysis results of gas chromatography.
Example 1:
al used in this example 2 O 3 The preparation process of the catalyst is as follows:
1.0g of polyether P123 is weighed and placed on a constant temperature heating magnetic stirrer, 20mL of absolute ethyl alcohol is slowly added dropwise, stirring is started to fully dissolve the polyether P123, and the solution is marked as solution I. Slowly adding 1.25mL of 35wt% hydrochloric acid, 0.5g of citric acid and 2.0425g of aluminum isopropoxide into the solution I under intense stirring, stirring for 5h, drying at 110 ℃ for 48 h, and roasting at 450 ℃ for 4h under air atmosphere to obtain P-Al 2 O 3 。
2, 6-diethylaniline and ethylene glycol mono-n-propyl ether were charged in a 250ml autoclave, wherein n 2, 6-diethylaniline :n Alcohol ethers =3:1, 5.0wt% p-Al was added 2 O 3 Catalyst (5.0 wt% means P-Al) 2 O 3 The mass of the catalyst is 5.0wt% of the total mass of 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether, other examples are understood as such, and the following description is omitted), nitrogen is introduced to replace air in the reaction kettle, the pressure of the nitrogen is controlled to be 1.0MPa, the temperature is controlled to be 250 ℃ for 30 hours, and the reaction mixture is filtered to recover P-Al 2 O 3 The selectivity of the 2, 6-diethyl anilino ethyl propyl ether obtained by GC detection of the catalyst and the conversion rate of the ethylene glycol mono-n-propyl ether are 86.6 percent and 93.12 percent.
Example 2:
the example used was commercially available gamma-Al 2 O 3 Purchased from Shandong aluminum technologies, inc.
2, 6-diethylaniline and ethylene glycol mono-n-propyl ether were charged in a 250ml autoclave, wherein n 2, 6-diethylaniline :n Alcohol ethers =3:1, 5.0wt% γ -Al was added 2 O 3 The catalyst is introduced into nitrogen to replace air in the reaction kettle, the pressure of the nitrogen is controlled to be 1.0MPa, the temperature is controlled to be 250 ℃ for reaction for 30 hours, and the reaction mixture is filtered to recycle commercial Al 2 O 3 The selectivity of the 2, 6-diethyl anilino ethyl propyl ether obtained by GC detection of the filtrate is 85.6%, and the conversion rate of the ethylene glycol mono-n-propyl ether is 86.30%.
Example 3:
the example used was commercial nanoscale zirconium dioxide, purchased from microphone, with an average particle size of 50nm.
2, 6-diethylaniline and ethylene glycol mono-n-propyl ether were charged in a 250ml autoclave, wherein n 2, 6-diethylaniline :n Alcohol ethers =3:1, 5.0wt% zro is added 2 The catalyst is introduced into nitrogen to replace air in the reaction kettle, the pressure of the nitrogen is controlled to be 1.0MPa, the temperature is controlled to be 200 ℃ for reaction for 30 hours, and the reaction mixture is filtered to recover ZrO 2 The selectivity of the 2, 6-diethyl anilino ethyl propyl ether obtained by GC detection of the catalyst and the conversion rate of the ethylene glycol mono-n-propyl ether are 93.03 percent and 93.10 percent.
Example 4:
1.0g F127 was dissolved in 10mL of ethanol at room temperature, solution I was noted. Then 1.61g ZrOCl was stirred vigorously 2 ·8H 2 And adding O into the solution I, stirring for 2 hours, and drying. And after aging at 40 ℃ for 2 days, the gel product was dried in another oven at 100 ℃ for 24 hours. And calcining at 400deg.C in air for 4 hr to obtain nanometer zirconia F-ZrO 2 。
2, 6-diethylaniline and ethylene glycol mono-n-propyl ether were charged in a 250ml autoclave, wherein n 2, 6-diethylaniline :n Alcohol ethers =3:1, 5.0wt% f-ZrO is added 2 The catalyst is introduced into nitrogen to replace air in the reaction kettle, the pressure of the nitrogen is controlled to be 1.0MPa, the temperature is controlled to be 200 ℃ for reaction for 30 hours, and the reaction mixture is filtered to recover F-ZrO 2 The selectivity of the 2, 6-diethyl anilino ethyl propyl ether obtained by GC detection of the catalyst and the conversion rate of the ethylene glycol mono-n-propyl ether are 92.73 percent and 99.10 percent.
Example 5:
CeO used in this example 2 The catalyst is purchased from the microphone.
2, 6-diethylaniline and ethylene glycol mono-n-propyl ether were charged in a 250ml autoclave, wherein n 2, 6-diethylaniline :n Ethylene glycol mono-n-propyl ether =3:1, 5.0wt% ceo was added 2 The catalyst is introduced into nitrogen to replace air in the reaction kettle, the pressure of the nitrogen is controlled to be 1.0MPa, the temperature is controlled to be 200 ℃ for reaction for 30 hours, and CeO is recovered by filtering the reaction mixture 2 The selectivity of the 2, 6-diethyl anilino ethyl propyl ether obtained by GC detection of the catalyst and the conversion rate of the ethylene glycol mono-n-propyl ether are 80.63 percent and 60.53 percent.
Example 6:
y used in this example 2 O 3 The catalyst is purchased from the microphone.
2, 6-diethylaniline and ethylene glycol mono-n-propyl ether were charged in a 250ml autoclave, wherein n 2, 6-diethylaniline :n Ethylene glycol mono-n-propyl ether =3:1, 5.0wt% y was added 2 O 3 Catalyst, introducing nitrogen to replace air in the reaction kettle and controlling the pressure of the nitrogen to be1.0MPa, controlling the temperature to be at 200 ℃ for 30h, filtering the reaction mixture to recover Y 2 O 3 The selectivity of the 2, 6-diethyl anilino ethyl propyl ether obtained by GC detection of the catalyst and the conversion rate of the ethylene glycol mono-n-propyl ether are 75.32 percent and 55.34 percent.
Example 7:
the catalyst ZnO support of this example was purchased from Michelia. Weighing 2g of ZnO carrier, pouring the ZnO carrier into 2mL of impregnating solution (0.05 g/mL Pd solution) and adding a little deionized water to enable the ZnO carrier to be flatly paved in the impregnating solution; placing the mixture in a room for 12 hours, and then placing the mixture in a blast drying oven at 110 ℃ for drying for 12 hours; taking out the dried catalyst, putting the catalyst into a muffle furnace, and roasting the catalyst in an air atmosphere at 400 ℃ for 4 hours; and (3) placing the roasted sample in a tube furnace, reducing for 100min in 30ml/min of hydrogen, reducing at 250 ℃, and cooling to room temperature to obtain the Pd/ZnO catalyst.
2, 6-diethylaniline and ethylene glycol mono-n-propyl ether were charged in a 250ml autoclave, wherein n 2, 6-diethylaniline :n Ethylene glycol mono-n-propyl ether =3:1, adding 1.0wt% Pd/ZnO catalyst, introducing nitrogen to replace air in the reaction kettle, controlling the pressure of the nitrogen to be 1.0MPa, controlling the temperature to react at 200 ℃ for 35 hours, filtering the reaction mixture to recover Pd/ZnO catalyst, detecting filtrate by GC to obtain the selectivity of 2, 6-diethyl anilinoethyl propyl ether of 70.63%, and the conversion rate of ethylene glycol mono-n-propyl ether of 54.33%.
Example 8:
the example catalyst SiO 2 The carrier was purchased from Qingdao Degussa chemical Co. Weigh 2g SiO 2 The carrier was poured into 2mL of impregnating solution (0.05 g/mL Pd solution) and a small amount of deionized water was added to make SiO 2 Spreading the carrier in the impregnating solution; placing the mixture in a room for 12 hours, and then placing the mixture in a blast drying oven at 110 ℃ for drying for 12 hours; taking out the dried catalyst, putting the catalyst into a muffle furnace, and roasting the catalyst in air at 400 ℃ for 4 hours; placing the roasted sample in a tube furnace, reducing in 30ml/min hydrogen for 100min at 200deg.C, and cooling to room temperature to obtain Pd/SiO 2 A catalyst.
2, 6-diethylaniline and ethyl were charged into a 250ml autoclaveGlycol mono-n-propyl ether, wherein n 2, 6-diethylaniline :n Ethylene glycol mono-n-propyl ether =3:1, 1.0wt% pd/SiO was added 2 The catalyst is introduced into nitrogen to replace air in the reaction kettle, the pressure of the nitrogen is controlled to be 1.0MPa, the temperature is controlled to be 200 ℃ for reaction for 35 hours, and the reaction mixture is filtered to recover Pd/SiO 2 The selectivity of the 2, 6-diethyl anilino ethyl propyl ether obtained by GC detection of the catalyst and the conversion rate of the ethylene glycol mono-n-propyl ether are 23.75 percent and 4.59 percent.
Example 9:
the catalyst used in this example was SiO after the acid treatment 2 And then used. The treatment method is as follows:
(1) The carrier is treated: weigh 10g SiO 2 The carrier (purchased from Qingdao De solid Seikovia Co., ltd.) is stirred with 25mL of 1mol/L dilute nitric acid for 1h, and then left to stand for 30min, and after repeating the operation for 3 times, the carrier is washed with deionized water and then neutral; drying at 110 deg.c for 12 hr; roasting in air at 600 deg.c for 12 hr to obtain acid treated carrier SiO 2 -N；
(2) Preparing a palladium solution with the concentration of 0.05g/mL as an impregnating solution;
(3) Weighing 2g of the treated carrier, pouring the carrier into 2mL of impregnating solution, and adding a small amount of deionized water to ensure that SiO 2 -the N carrier is tiled in the impregnation fluid; placing the mixture in a room for 12 hours, and then placing the mixture in a blast drying oven at 110 ℃ for drying for 12 hours; taking out the dried catalyst, putting the catalyst into a muffle furnace, and roasting the catalyst for 4 hours at 550 ℃; placing the roasted sample in a tube furnace, reducing in 30ml/min hydrogen for 2h at 400 ℃, and cooling to room temperature to obtain Pd/SiO 2 -an N catalyst.
2, 6-diethylaniline and ethylene glycol mono-n-propyl ether were added to a 250mL autoclave, where n 2, 6-diethylaniline :n Ethylene glycol mono-n-propyl ether =3:1, 1.0wt% pd/SiO was added 2 N catalyst, introducing nitrogen to replace air in the reaction kettle, controlling the pressure of the nitrogen to be 1.0MPa, controlling the temperature to be 200 ℃ for reaction for 8 hours, and filtering the reaction mixture to recover Pd/SiO 2 N catalyst, the selectivity of the filtrate obtained by GC detection to 2, 6-diethyl anilino ethyl propyl ether is56.69% and the conversion of ethylene glycol mono-n-propyl ether was 22.56%.
Example 10:
the catalyst used in this example was purchased from ZSM-5, tianjin southbound catalyst Co. Wherein the silicon-aluminum ratio is 25.
The catalyst used in this example was passed through a nitrided ZSM-5 molecular sieve and then used. The treatment method is as follows: weighing 3g of ZSM-5 sample, placing the sample in a quartz boat, and transferring the quartz boat into a tube furnace; purging the tube furnace with nitrogen to remove air, and then raising the temperature from room temperature to 800 ℃ at a heating rate of 10 ℃/min; nitrogen was switched to 10vol% nh 3 The mixed gas of Ar and the flow rate is 100mL/min, the tubular furnace is kept at 800 ℃ for 1 hour and then cooled to room temperature, and a nitrided sample is obtained and is recorded as 1.0N-ZSM-5.
2, 6-diethylaniline and ethylene glycol mono-n-propyl ether were added to a 250mL autoclave, where n 2, 6-diethylaniline :n Ethylene glycol mono-n-propyl ether =3:1, 5.0wt% of 1.0N-ZSM-5 catalyst was added, nitrogen was introduced to replace air in the reaction vessel and the nitrogen pressure was controlled to be 1.0MPa, the temperature was controlled to be 200 ℃ for reaction for 8 hours, the reaction mixture was filtered to recover 1.0N-ZSM-5 catalyst, the filtrate was detected by GC to obtain a selectivity of 60.78% for 2, 6-diethylaminoethyl propyl ether, and a conversion of 70.43% for ethylene glycol mono-N-propyl ether.
Example 11:
the catalyst used in this example was identical to that used in example 4.
2, 6-diethylaniline and ethylene glycol mono-n-propyl ether were added to a 250mL autoclave, where n 2, 6-diethylaniline :n Alcohol ethers =3:1, 5.0wt% zro is added 2 The catalyst is introduced into nitrogen to replace air in the reaction kettle, the pressure of the nitrogen is controlled to be 1.0MPa, the temperature is controlled to be 200 ℃ for reaction for 30 hours, and the reaction mixture is filtered to recover ZrO 2 The catalyst is recovered and used continuously, after recycling for 5 times, the filtrate is detected by GC to obtain the selectivity of the 2, 6-diethyl anilino ethyl propyl ether of 91.03 percent, and the conversion rate of the ethylene glycol mono-n-propyl ether of 94.10 percent.
The above examples 1,2,3,4,5,7,8,9,10 were carried out with an amphoteric carrier, an acidic carrier, an acid-treated carrier and a nitrided carrier, respectively, as catalysts. It can be seen that the acid-base bifunctional support has higher activity than the alkaline or acidic support, indicating that acid-base sites on the support are necessary.
The above example 11 is a life test of example 2, and the recycling result shows that the catalyst has good stability.
Claims (11)
1. A method for preparing amine ether compound by N-alkylation reaction of aromatic amine and alcohol ether substance shown in formula I, wherein the method is to prepare amine ether compound by one-step N-alkylation reaction of aromatic amine and alcohol ether substance in inert atmosphere under the action of amphoteric oxide catalyst; the amphoteric oxide catalyst is nano-scale zirconia; the alcohol ether material is ethylene glycol mono-n-propyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether or ethylene glycol monobutyl ether;
wherein R is H or C 1 -C 10 An alkyl group; r is R 1 、R 2 、R 3 、R 4 、R 5 Each independently is H or C 1 -C 10 An alkyl group.
2. The method of claim 1, wherein: the nanoscale zirconia is prepared by the following method: polyether F127 is dissolved in ethanol under the condition of room temperature, and the solution I is recorded; zrOCl is then stirred vigorously 2 ·8H 2 Adding O into the solution I, stirring for 5-12h, drying, aging at 30-80 ℃ for 1-5 days to obtain gel, drying the gel at 80-130 ℃ for 12-36h, and calcining at 350-550 ℃ in air for 2-6h to obtain nanoscale zirconia; wherein polyether F127, ethanol and ZrOCl 2 ·8H 2 The feed ratio of O is 1.0g:8-20mL:1-3g.
3. A method according to claim 1 or 2, characterized in that: the method comprises the following steps: adding aromatic amine, alcohol ether and amphoteric oxide catalyst into a high-pressure reaction kettle, introducing inert gas to replace air in the reaction kettle, controlling the pressure of the inert gas to be normal pressure-4.0 MPa, and controlling the reaction temperature to be 100-300 ℃ for N-alkylation reaction to generate amine ether compound.
4. A method as claimed in claim 3, wherein: the inert gas pressure is 1.0-1.5MPa.
5. A method as claimed in claim 3, wherein: the reaction temperature is 200-250 ℃.
6. A method according to claim 1 or 2, characterized in that: the molar ratio of the aromatic amine to the alcohol ether substance is 1-10.
7. The method of claim 6, wherein: the molar ratio of the aromatic amine to the alcohol ether substance is 2-4:1.
8. The method of claim 7, wherein: the molar ratio of the aromatic amine to the alcohol ether substance is 3:1.
9. A method according to claim 1 or 2, characterized in that: the feeding mass of the amphoteric oxide catalyst is 0.01% -10.0% of the total mass of the aromatic amine and the alcohol ether substances.
10. The method of claim 9, wherein: the feeding mass of the amphoteric oxide catalyst is 1.0-5.0% of the total mass of the aromatic amine and the alcohol ether substances.
11. A method according to claim 1 or 2, characterized in that: the inert gas is nitrogen or argon.
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