CN114249661A - Method for preparing amine ether compound by N-alkylation reaction of arylamine and alcohol ether substance - Google Patents
Method for preparing amine ether compound by N-alkylation reaction of arylamine and alcohol ether substance Download PDFInfo
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- CN114249661A CN114249661A CN202111597522.0A CN202111597522A CN114249661A CN 114249661 A CN114249661 A CN 114249661A CN 202111597522 A CN202111597522 A CN 202111597522A CN 114249661 A CN114249661 A CN 114249661A
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 30
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 25
- 239000000126 substance Substances 0.000 title claims abstract description 25
- 238000007126 N-alkylation reaction Methods 0.000 title claims abstract description 22
- -1 amine ether compound Chemical class 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims abstract description 32
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 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
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 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
- 238000006243 chemical reaction Methods 0.000 claims description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 55
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 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
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 3
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000000047 product Substances 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
- 239000002253 acid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 230000002152 alkylating effect Effects 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000002168 alkylating agent Substances 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 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
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003892 spreading Methods 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
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-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
- 238000006639 Goldberg reaction Methods 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
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion 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
- 230000007547 defect Effects 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
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010926 purge 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
- 238000002791 soaking Methods 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
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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- 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 amine ether compounds by N-alkylation reaction of arylamine and alcohol ether substances shown in formula I, wherein the method takes arylamine and alcohol ether substances as reactants and prepares the amine ether compounds by one-step N-alkylation reaction under the action of an amphoteric oxide catalyst in an inert atmosphere; the amphoteric oxide carrier is Al2O3、ZrO2Or CeO2(ii) a The alcohol ether substances are ethylene glycol mono-n-propyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether or ethylene glycol monobutyl ether. The method has the characteristics of environmental protection, simplicity, reliability and high yield.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a method for preparing amine ether compounds by utilizing N-alkylation reaction of arylamine and alcohol ether substances.
Background
The N-alkylation reaction is an important organic synthesis reaction, and the synthetic product relates to important scientific and technological fields including chemical industry, medical treatment, medicine, national defense and the like. In recent years, with the development of chemical technology, such reactions have become one of the important research points of organic chemistry. The alkylation reaction of nitrogen is mostly carried out from nitrogen-containing compounds, and the alkylated amine is obtained by taking halohydrocarbon, aldehyde, amine and other substances as an alkylating reagent and carrying out condensation, oxidation, reduction, coupling and other reactions under certain conditions. Depending on the type of reaction and alkylating reagent used, the N-alkylation of aromatic amines is divided into 3 types: (1) substituted alkylation: alkylating with alkylating agents which are esters of alcohols, alkyl halides (in particular alkyl iodides, alkyl bromides and alkyl chlorides) and strong acids; (2) addition alkylation: arylamine, acrylic acid derivative and epoxy compound are used as alkylating agents to be added, but the product is provided with hydroxyl, and the hydroxyl on the product needs to be further processed; (3) reductive alkylation: aromatic amines are condensed with alkylating agents such as aldehydes and ketones. Early studies on the construction of this C-N bond were the well-known Ullmann and Goldberg reactions. Because of the limited conditions, the methods have a plurality of defects that (1) organic halide is used in the reaction, and hydrogen halide which is harmful to the environment and a large amount of acid waste water are generated as by-products; (2) no better catalytic system is provided, and the reaction usually needs high temperature of 200 ℃ and above; (3) a lot of strong base is needed to be added as an acid-binding agent, so that a large amount of inorganic solid waste is generated; (4) low atom utilization rate and poor product selectivity.
In the production process of generating amine ether compounds, aniline compounds and chlorine ether compounds are mostly obtained through an N-alkylation reaction. In the process of the N-alkylation reaction, an auxiliary agent or an acid-binding agent is usually required to be added to enable the target product to have better selectivity and yield. In the invention patent with application publication No. CN111100019A, Dudawa et al, performed N-alkylation reaction of 2, 6-diethylaniline and chloroethyl propyl ether, added N, N-di-N-propyl-2-propoxyethylamine as an auxiliary agent to inhibit secondary nitrogen alkylation reaction, and added NaOH to adjust the pH value of the reaction solution to improve the selectivity of the target product. In the invention patent with application publication number of CN102229542A, two steps are needed to generate amine ether compounds, 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 reacts with N-chloropropane as the starting material, and strong base is added as an acid-binding agent to react to generate the amine ether in the same reaction process. Then there is the potential for corrosion of the experimental equipment and other by-products during the reaction.
Through years of research and development, alcohol is proved to have the same properties as halogenated alkane and halogenated aromatic hydrocarbon in the reaction process, becomes a new generation of alkylating reagent, and is used as the alkylating reagent to react with arylamine to synthesize substituted arylamine, so that the method has the advantages of cheap 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 gaining increasing interest. Such as Ken-ichi Shimizu (ACS Catal.2013,3,5, 998-2O3The research finds that the acid-base bifunctional carrier has higher activity than the alkaline or acid carrier, and indicates that the acid-base sites on the carrier are necessary.
However, in the N-alkylation reaction of catalyzing arylamine and alcohol ether substances, the alcohol ether substances containing ether bonds react more complexly under relative conditions, so that the ether bonds are broken in the reaction process to generate aldehyde or alcohol and other small molecules, and the substances after the bond breaking can be used as an alkylating reagent to generate a series of byproducts, so that the reaction selectivity is reduced. The selection of a suitable catalyst support and its modification of the metal is of great significance for the N-alkylation reaction.
From the sustainable chemistry perspective, the preparation of a series of catalysts that minimize the production of byproducts and three wastes is one of the most important goals in the industrial development.
Disclosure of Invention
The invention aims to provide a method for preparing amine ether compounds by N-alkylation reaction of arylamine and alcohol ether substances, which has the characteristics of environmental protection, simplicity, reliability and high yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing amine ether compounds by N-alkylation reaction of arylamine and alcohol ether substances shown in formula I is characterized in that arylamine and alcohol ether substances are used as reactants, and the amine ether compounds are prepared by one-step N-alkylation reaction under the action of an amphoteric oxide catalyst in an inert atmosphere; the amphoteric oxide carrier is Al2O3、ZrO2Or CeO2(ii) a The alcohol ether substances are ethylene glycol mono-n-propyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether isopropyl ether, diethylene glycol monobutyl ether or ethylene glycol monobutyl ether;
wherein R is H or C1-C10An alkyl group; r1、R2、R3、R4、R5Each independently is H or C1-C10An alkyl group.
The N-alkylation reaction refers to the reaction of amine in arylamine and hydroxyl in alcohol ether substance, and the amine ether compound is generated by dehydration.
The amphoteric oxide catalyst used in the present invention can be prepared by commercially available methods or by conventional methods. Generally, the larger the specific surface area of the catalyst, the more active sites are, so that the increase of the specific surface area of the catalyst is beneficial to the improvement of the catalytic activity of the catalyst. The specific surface area of the amphoteric oxide catalyst is controlled to be 15m2More than g.
Preferably, the amphoteric oxide support is nanoscale zirconia. Particularly preferably, the nanoscale zirconia is prepared by the following method: dissolving polyether F127 in ethanol at room temperature to obtain a solution I; then ZrOCl is stirred vigorously2·8H2Adding O into the solution I, stirring for 5-12h, drying, aging for 1-5 days (preferably 2 days) at 30-80 ℃ (preferably 40 ℃) to obtain gel, drying the gel at 80-130 ℃ for 12-36h, and calcining in air at 350-550 ℃ (preferably 400 ℃) for 2-6h (preferably 4h) to obtain nanoscale zirconia; wherein polyether F127, ethanol and ZrOCl2·8H2The feeding ratio of O is 1.0 g: 8-20 mL: 1-3 g.
Preferably, the method for preparing the amine ether compound is carried out according to the following steps: adding arylamine, alcohol ether substances 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 ℃ to carry out N-alkylation reaction to generate amine ether compounds. And in the reaction process, sampling at regular time for detection until the reactants do not continuously convert and the product reaches the equilibrium, namely the reaction end point. Further preferably, the inert gas pressure is 1.0 to 1.5 MPa. The further reaction temperature was 200 ℃ and 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 arylamine 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 method adopts the arylamine derivatives and the ether bond-containing alcohol derivatives as raw materials, directly catalyzes N-alkylation reaction to prepare the amine ether compounds, changes the prior multi-step reaction of firstly halogenating and then N-alkylating into one-step reaction, has simpler reaction path, takes the alcohol ether as the alkylating reagent of the amine, uses water as the only byproduct, avoids generating high strong acid to corrode equipment in the halogenation reaction process, and has the characteristics of environmental protection, simplicity and reliability.
(2) The amphoteric oxide catalyst used in the invention has excellent catalytic activity in the N-alkylation reaction of aromatic amine derivatives and alcohol derivatives containing ether bonds, can inhibit the breakage of ether bonds, greatly reduces the generation of byproducts, simultaneously reduces the secondary nitrogen alkylation of products, and has excellent product selectivity. Has excellent stability.
(3) The catalyst is simple and easy to prepare and can be recycled;
(4) according to the one-pot reaction, after the catalyst is added, strong alkali is not required to be added as an acid-binding agent.
Drawings
FIG. 1 is a GC analysis of the product obtained in example 4.
FIG. 2 shows ZrO obtained in example 32X-ray diffraction (XRD) pattern of (a).
FIG. 3 is an X-ray diffraction (XRD) pattern of 1.0N-ZSM-5 obtained in example 10.
Detailed Description
The technical solution of the present invention is further illustrated by the following 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 results of gas chromatography analysis.
Example 1:
al used in this example2O3The preparation process of the catalyst is as follows:
1.0g of polyether P123 is weighed, placed on a constant-temperature heating magnetic stirrer, 20mL of absolute ethyl alcohol is slowly dripped, stirring is started to fully dissolve P123, and the solution is marked as solution I. Slowly adding 1.25mL of 35 wt% hydrochloric acid, 0.5g of citric acid and 2.0425g of aluminum isopropoxide into the solution I under the condition of vigorous stirring, stirring for 5h, drying at 110 ℃ for 48 h, and roasting at 450 ℃ for 4h under an air atmosphere to obtain P-Al2O3。
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250ml high-pressure reaction kettle2, 6-diethylaniline:nAlcohol ethersAdding 5.0 wt% of P-Al (3: 1)2O3Catalyst (5.0 wt% means P-Al2O3The mass of the catalyst is 5.0 wt% of the total mass of the 2, 6-diethylaniline and the ethylene glycol mono-n-propyl ether, other embodiments are understood as the same, and are not described in detail below), introducing nitrogen to replace the air in the reaction kettle, controlling the nitrogen pressure to be 1.0MPa, controlling the temperature to react at 250 ℃ for 30h, filtering the reaction mixture to recover P-Al2O3The catalyst and the filtrate are detected by GC to obtain the 2, 6-diethyl anilinoethyl propyl ether with the selectivity of 86.6 percent and the conversion rate of ethylene glycol mono-n-propyl ether of 93.12 percent.
Example 2:
the commercially available gamma-Al is used for this example2O3Purchased from Shandong aluminum industries, Inc.
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250ml high-pressure reaction kettle2, 6-diethylaniline:nAlcohol ethersTo the mixture was added 5.0 wt% of γ -Al (3: 1)2O3Introducing nitrogen to replace air in the reaction kettle, controlling the pressure of the nitrogen to be 1.0MPa and the temperature to be 250 ℃ for reaction for 30 hours, filtering the reaction mixture and recovering commercial Al2O3The catalyst and the filtrate are detected by GC to obtain 2, 6-diethyl anilinoethyl propyl ether with the selectivity of 85.6 percent and the conversion rate of ethylene glycol mono-n-propyl ether of 86.30 percent.
Example 3:
the nanoscale zirconium dioxide used in this example is commercially available as Michelin and has an average particle diameter of 50 nm.
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250ml high-pressure reaction kettle2, 6-diethylaniline:nAlcohol ethers3:1, 5.0 wt% ZrO was added2Introducing nitrogen to replace air in the reaction kettle, controlling the pressure of the nitrogen to be 1.0MPa and the temperature to be 200 ℃ for reaction for 30 hours, filtering the reaction mixture and recovering ZrO2The catalyst and the filtrate are detected by GC to obtain the 2, 6-diethylanilinoethyl propyl ether with the selectivity of 93.03 percent and the conversion rate of the ethylene glycol mono-n-propyl ether of 93.10 percent.
Example 4:
1.0g of F127 was dissolved in 10mL of ethanol at room temperature to obtain solution I. Then, 1.61g of ZrOCl was added under vigorous stirring2·8H2And adding O into the solution I, stirring for 2h, and drying. And after aging for 2 days at 40 ℃, the gel product was dried in another oven at 100 ℃ for 24 h. And keeping the mixture in the air for 4 hours at the temperature of 400 ℃ for calcination to obtain the nano zirconia F-ZrO2。
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250ml high-pressure reaction kettle2, 6-diethylaniline:nAlcohol ethersAdding 5.0 wt% of F-ZrO 2 at a ratio of 3:12Introducing nitrogen to replace air in the reaction kettle, controlling the pressure of the nitrogen to be 1.0MPa and the temperature to be 200 ℃ for reaction for 30 hours, filtering the reaction mixture and recovering F-ZrO2The catalyst and the filtrate are detected by GC to obtain the 2, 6-diethylanilinoethyl propyl ether with the selectivity of 92.73 percent and the conversion rate of the ethylene glycol mono-n-propyl ether of 99.10 percent.
Example 5:
CeO used in this example2Catalyst, purchased from michelin.
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250ml high-pressure reaction kettle2, 6-diethylaniline:nEthylene glycol mono-n-propyl ether(iii) 5.0 wt% CeO was added to the solution 3:12Introducing nitrogen to replace air in the reaction kettle, controlling the pressure of the nitrogen to be 1.0MPa and the temperature to be 200 ℃ for reaction for 30 hours, filtering the reaction mixture and recovering CeO2Catalyst and process for preparing sameAnd the filtrate is detected by GC to obtain 80.63% of 2, 6-diethylanilinoethyl propyl ether and 60.53% of ethylene glycol mono-n-propyl ether.
Example 6:
y used in this example2O3Catalyst, purchased from michelin.
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250ml high-pressure reaction kettle2, 6-diethylaniline:nEthylene glycol mono-n-propyl etherTo 3:1, add 5.0 wt% Y2O3Introducing nitrogen to replace air in the reaction kettle, controlling the pressure of the nitrogen to be 1.0MPa and the temperature to be 200 ℃ for reaction for 30h, filtering the reaction mixture and recovering Y2O3The catalyst and the filtrate are detected by GC to obtain the 2, 6-diethylanilinoethyl propyl ether with the selectivity of 75.32 percent and the conversion rate of the ethylene glycol mono-n-propyl ether of 55.34 percent.
Example 7:
the example catalyst ZnO support, available from Mecline. Weighing 2g of ZnO carrier, pouring the ZnO carrier into 2mL of impregnation liquid (0.05g/mL of Pd solution), and adding a little deionized water to ensure that the ZnO carrier is flatly paved in the impregnation liquid; placing the mixture indoors for 12 hours, and then drying the mixture in a forced air drying oven at 110 ℃ for 12 hours; taking out the dried catalyst, putting the dried catalyst into a muffle furnace, and roasting for 4 hours at 400 ℃ in an air atmosphere; and (3) placing the roasted sample in a tubular furnace, reducing for 100min in 30ml/min hydrogen at the reduction temperature of 250 ℃, and cooling to room temperature to obtain the Pd/ZnO catalyst.
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250ml high-pressure reaction kettle2, 6-diethylaniline:nEthylene glycol mono-n-propyl etherAdding 1.0 wt% of Pd/ZnO catalyst, introducing nitrogen to replace air in a reaction kettle, controlling the nitrogen pressure to be 1.0MPa and the temperature to be 200 ℃ for reaction for 35 hours, filtering the reaction mixture to recover the Pd/ZnO catalyst, and detecting the filtrate by GC to obtain 70.63% of 2, 6-diethylanilinoethylpropyl ether and 54.33% of conversion rate of ethylene glycol mono-n-propyl ether.
Example 8:
catalyst SiO of this example2Vehicle, available from degussa chemical co. Weighing 2gSiO2The carrier was poured into 2mL of the impregnation solution (0.05g/mL Pd solution) and a little deionized water was added to make SiO2Spreading the carrier in the soaking liquid; placing the mixture indoors for 12 hours, and then drying the mixture in a forced air drying oven at 110 ℃ for 12 hours; taking out the dried catalyst, putting the dried catalyst into a muffle furnace, and roasting the catalyst for 4 hours at the temperature of 400 ℃ in the air; placing the roasted sample in a tubular furnace, reducing for 100min in 30ml/min hydrogen at 200 ℃, and cooling to room temperature to obtain Pd/SiO2A catalyst.
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250ml high-pressure reaction kettle2, 6-diethylaniline:nEthylene glycol mono-n-propyl ether1.0 wt% Pd/SiO was added to the solution 3:12Introducing nitrogen to replace air in the reaction kettle, controlling the pressure of the nitrogen to be 1.0MPa and the temperature to be 200 ℃ for reacting for 35 hours, filtering the reaction mixture and recovering Pd/SiO2The catalyst and the filtrate are detected by GC to obtain 2, 6-diethyl anilinoethyl propyl ether with the selectivity of 23.75 percent and the conversion rate of ethylene glycol mono-n-propyl ether of 4.59 percent.
Example 9:
the catalyst used in this example was SiO after acidic treatment2Then used. The treatment method is as follows:
(1) treating the carrier: weighing 10g of SiO2Stirring a carrier (purchased from Qingdao Degussa chemical Co., Ltd.) and 25mL of 1mol/L dilute nitric acid for 1h, standing for 30min, repeating the operation for 3 times, and washing with deionized water to be neutral; drying at 110 deg.C for 12 h; roasting in air at constant temperature of 600 ℃ for 12h to obtain acid-treated carrier SiO2-N；
(2) Preparing 0.05g/mL palladium solution as impregnation liquid;
(3) 2g of the treated carrier is weighed and poured into 2mL of the impregnation solution, and a little deionized water is added to make SiO2-spreading the N support in an impregnation solution; placing the mixture indoors for 12 hours, and then drying the mixture in a forced air drying oven at 110 ℃ for 12 hours; taking out the dried catalyst, putting the dried catalyst into a muffle furnace, and roasting for 4 hours at 550 ℃; placing the roasted sample inReducing in 30ml/min hydrogen for 2h in a tubular furnace at 400 deg.C, and cooling to room temperature to obtain Pd/SiO2-N catalyst.
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250mL high-pressure reaction kettle, wherein n is2, 6-diethylaniline:nEthylene glycol mono-n-propyl ether1.0 wt% Pd/SiO was added to the solution 3:12Introducing nitrogen to replace air in the reaction kettle, controlling the nitrogen pressure to be 1.0MPa and the temperature to be 200 ℃ for reacting for 8h, filtering the reaction mixture and recovering Pd/SiO2And (4) detecting the filtrate by GC to obtain the 2, 6-diethylanilinoethyl propyl ether with the selectivity of 56.69 percent and the conversion rate of the ethylene glycol mono-N-propyl ether of 22.56 percent.
Example 10:
the catalyst used in this example was purchased from ZSM-5 of Tianjin Minn Kanza, Inc. Wherein, the silicon-aluminum ratio is 25.
The catalyst used in this example was applied after nitriding the ZSM-5 molecular sieve. The treatment method is as follows: weighing 3g of ZSM-5 sample, placing the ZSM-5 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 temperature rise rate of 10 ℃/min; nitrogen gas was switched to 10 vol% NH3And maintaining the flow rate of the mixed gas/Ar at 100mL/min for 1 hour at 800 ℃ in a tubular furnace, and cooling to room temperature to obtain a nitrided sample which is recorded as 1.0N-ZSM-5.
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250mL high-pressure reaction kettle, wherein n is2, 6-diethylaniline:nEthylene glycol mono-n-propyl etherAdding 5.0 wt% of 1.0N-ZSM-5 catalyst, introducing nitrogen to replace air in a reaction kettle, controlling the nitrogen pressure to be 1.0MPa and the temperature to be 200 ℃ for reaction for 8 hours, filtering a reaction mixture and recovering the 1.0N-ZSM-5 catalyst, and detecting the filtrate by GC to obtain the 2, 6-diethylanilinoethyl propyl ether with the selectivity of 60.78% and the conversion rate of ethylene glycol mono-N-propyl ether of 70.43%.
Example 11:
the catalyst used in this example was identical to that used in example 4.
Adding 2, 6-diethylaniline and ethylene glycol mono-n-propyl ether into a 250mL high-pressure reaction kettle, wherein n is2, 6-diethylaniline:nAlcohol ethers3:1, 5.0 wt% ZrO was added2Introducing nitrogen to replace air in the reaction kettle, controlling the pressure of the nitrogen to be 1.0MPa and the temperature to be 200 ℃ for reaction for 30 hours, filtering the reaction mixture and recovering ZrO2The catalyst is recycled for continuous use, and after the catalyst is recycled for 5 times, the selectivity of 2, 6-diethylanilinoethyl propyl ether obtained by GC detection of the filtrate is 91.03%, and the conversion rate of ethylene glycol mono-n-propyl ether is 94.10%.
Examples 1,2,3,4,5,7,8,9,10 above are catalysts with an amphoteric support, an acidic support, an acid treated support, and a nitrogenated support, respectively. It can be seen that the acid-base bifunctional support has a higher activity than the basic 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 cycle results show that the catalyst has good stability.
Claims (9)
1. A method for preparing amine ether compounds by N-alkylation reaction of arylamine and alcohol ether substances shown in formula I is characterized in that arylamine and alcohol ether substances are used as reactants, and the amine ether compounds are prepared by one-step N-alkylation reaction under the action of an amphoteric oxide catalyst in an inert atmosphere; the amphoteric oxide carrier is Al2O3、ZrO2Or CeO2(ii) a The alcohol ether substances are 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 C1-C10An alkyl group; r1、R2、R3、R4、R5Each independently is H or C1-C10An alkyl group.
2. The method of claim 1, wherein: the amphoteric oxide carrier is nano-grade zirconia.
3. The method of claim 1, wherein: the nanoscale zirconia is prepared by the following method: dissolving polyether F127 in ethanol at room temperature to obtain a solution I; then ZrOCl is stirred vigorously2·8H2Adding 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 in air at 350-550 ℃ for 2-6h to obtain nano-grade zirconium oxide; wherein polyether F127, ethanol and ZrOCl2·8H2The feeding ratio of O is 1.0 g: 8-20 mL: 1-3 g.
4. A method according to any one of claims 1 to 3, wherein: the method comprises the following steps: adding arylamine, alcohol ether substances 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 ℃ to carry out N-alkylation reaction to generate amine ether compounds.
5. The method of claim 4, wherein: the pressure of the inert gas is 1.0-1.5 MPa.
6. The method of claim 4, wherein: the reaction temperature is 200-250 ℃.
7. A method according to any one of claims 1 to 3, wherein: the molar ratio of the arylamine to the alcohol ether substances is 1-10, preferably 2-4:1, and most preferably 3: 1.
8. A method according to any one of claims 1 to 3, wherein: the feeding mass of the amphoteric oxide catalyst is 0.01-10.0% of the total mass of the arylamine and the alcohol ether substances, and more preferably 1.0-5.0%.
9. A method according to any one of claims 1 to 3, wherein: the inert gas is nitrogen or argon.
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