CN103193660B - Synthetic method of 4-alkoxy phenylamine compound - Google Patents
Synthetic method of 4-alkoxy phenylamine compound Download PDFInfo
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- CN103193660B CN103193660B CN201310110916.8A CN201310110916A CN103193660B CN 103193660 B CN103193660 B CN 103193660B CN 201310110916 A CN201310110916 A CN 201310110916A CN 103193660 B CN103193660 B CN 103193660B
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 aromatic nitro compound Chemical class 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 150000002500 ions Chemical class 0.000 claims description 24
- 230000002378 acidificating effect Effects 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000002608 ionic liquid Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- ULIJLHUMGZOVKE-UHFFFAOYSA-N S(O)(O)(=O)=O.CN1C=NC=C1.C(CC)S(=O)(=O)O Chemical compound S(O)(O)(=O)=O.CN1C=NC=C1.C(CC)S(=O)(=O)O ULIJLHUMGZOVKE-UHFFFAOYSA-N 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000006665 Bamberger reaction Methods 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 230000008707 rearrangement Effects 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004904 shortening Methods 0.000 description 6
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 5
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- RTRXLVQDWQKTCL-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;propane-1-sulfonate Chemical compound C[NH+]1C=CN=C1.CCCS([O-])(=O)=O RTRXLVQDWQKTCL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- HXLMUUQFILSEMW-UHFFFAOYSA-N C(CC)S(=O)(=O)O.S(=O)(=O)(O)O.N1=CC=CC=C1 Chemical compound C(CC)S(=O)(=O)O.S(=O)(=O)(O)O.N1=CC=CC=C1 HXLMUUQFILSEMW-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- JNXWGWKKXBSQAC-UHFFFAOYSA-N [C].[Ni].[Ru] Chemical compound [C].[Ni].[Ru] JNXWGWKKXBSQAC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- TVEOIQKGZSIMNG-UHFFFAOYSA-N hydron;1-methyl-1h-imidazol-1-ium;sulfate Chemical compound OS([O-])(=O)=O.C[NH+]1C=CN=C1 TVEOIQKGZSIMNG-UHFFFAOYSA-N 0.000 description 1
- JNONJXMVMJSMTC-UHFFFAOYSA-N hydron;triethylazanium;sulfate Chemical compound OS(O)(=O)=O.CCN(CC)CC JNONJXMVMJSMTC-UHFFFAOYSA-N 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- XSUMSESCSPMNPN-UHFFFAOYSA-N propane-1-sulfonate;pyridin-1-ium Chemical compound C1=CC=NC=C1.CCCS(O)(=O)=O XSUMSESCSPMNPN-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a 4-alkoxy phenylamine compound by catalytic hydrogenation rearrangement of an aromatic nitro compound. The preparation method is used for synthesizing the 4-alkoxy phenylamine compound by adopting a one-pot process in low-level fatty alcohol by using the aromatic nitro compound as the starting material, using load platinum catalyst as a hydrogenation catalyst and using acid ion liquid as a Bamberger rearrangement catalyst. The conversion ate of the aromatic nitro compound is 100% and the yield of the 4-alkoxy phenylamine compound is higher than 65%. The synthetic method is environment-friendly in process, simple to operate, capable of repeatedly using the catalyst, low in production cost and remarkable in industrial production advantages.
Description
(1) technical field
The present invention relates to a kind of aromatic nitro compound shortening and the method that Bamberger resets synthesis 4-alkoxy benzene aminated compounds occurs, under acidic ion liquid and loaded platinum catalyst effect, particularly being reset the method for synthesis 4-alkoxy benzene aminated compounds by aromatic nitro compound shortening.
(2) background technology
4-alkoxy benzene aminated compounds is the important dyestuff of a class and medicine intermediate.The traditional synthesis of this compounds needs could be realized by polystep reaction, and complex process, whole productive rate is lower, and environmental pollution is serious.The most elder generation of prior synthesizing method as P-nethoxyaniline (being also called Para-Anisidine) is raw material with parachloronitrobenzene, carry out methoxylation and obtain p-Nitromethoxybenzene, then (Yuan Zhongyi is obtained to nitroreduction, Hu Shuan, Lv Rongwen, Lv Lianhai. backbone ruthenium nickel carbon selectivity shortening prepares Para-Anisidine. fine chemistry industry, 2006, (5): 514-517.).4-alkoxy benzene aminated compounds also can by aromatic nitro compound shortening Bamberger rearrangement reaction one-step synthesis.If Qiu Xiao etc. is raw material with Ortho Nitro Toluene, in methyl alcohol, acetic acid and sulfuric acid mixed solution, under Pt/C catalyst action, there is hydrogenation and Bamberger reset and generate 2-methyl-4-anisidine (Qiu Xiao, the synthesis of Jiang Jiajun, Wang Xingyi, Shen Yongjia .2-methyl-4-p-methoxy-phenyl aniline. organic chemistry, 2005,25 (5): 561-565.) but in reaction process with the vitriol oil and acetic acid for Bamberger rearrangement catalyst, equipment corrosion is serious, and easy contaminate environment.
(3) summary of the invention
Under the object of the present invention is to provide a kind of mild conditions, aromatic nitro compound " one kettle way " shortening Bamberger resets the environment-friendly method synthesizing 4-alkoxy benzene aminated compounds.
For achieving the above object, the technical solution used in the present invention is as follows:
The synthetic method of the 4-alkoxy benzene aminated compounds shown in a kind of formula II, described method for: the aromatic nitro compound shown in formula I is starting raw material, with fatty alcohol roh for solvent, under the effect of loaded platinum catalyst and acidic ion liquid, at 30 ~ 180 DEG C of temperature, logical hydrogen reacts 1 ~ 20 hour under 0.1 ~ 2.0MPa, and reaction terminates rear reaction solution and obtains the 4-alkoxy benzene aminated compounds shown in formula II through aftertreatment:
In formula I or formula II, R
1, R
2, R
3, R
4respective is independently hydrogen, chlorine, methyl or ethyl, and preferred formula I is oil of mirbane or Ortho Nitro Toluene, i.e. preferred R
1, R
2, R
3, R
4be all hydrogen or R
1for methyl, R
2, R
3, R
4for hydrogen.
R in ROH or formula II is methyl or ethyl, and preferred R is methyl;
The acidic ion liquid that described acidic ion liquid is imidazoles, quaternary amines or pyridines positively charged ion and bisulfate ion, dihydrogen phosphate or tosic acid negatively charged ion are formed;
Described loaded platinum catalyst is with gac, aluminum oxide, silicon oxide or titanium oxide for carrier, and load has Pt to be the catalyzer of active ingredient, and wherein the charge capacity of Pt is 0.5 ~ 10.0wt%, preferably 3%.Described carrier is preferably gac, when carrier is gac, is Pt/C catalyzer.Described loaded platinum catalyst is conventional catalyzer, directly can buy on market and obtain.
Further, acidic ion liquid of the present invention is preferably one of following: N-methylimidazolium hydrogen sulphate ionic liquid ([Hmim] HSO4), triethylamine hydrogen sulphate ionic liquid ([(C
2h
5)
3nH] HSO
4), imidazoles propanesulfonic acid hydrogen sulphate ionic liquid ([HSO
3-pHIM] HSO
4), N-Methylimidazole propanesulfonic acid hydrogen sulphate ionic liquid ([HSO
3-pMIM] HSO
4), pyridine propanesulfonic acid hydrogen sulphate ionic liquid ([HSO
3-pPydin] HSO
4), pyridine propanesulfonic acid tosic acid ionic liquid ([HSO
3-pPydin]
+[pTSA]
-), be more preferably N-Methylimidazole propanesulfonic acid hydrogen sulphate ionic liquid or imidazoles propanesulfonic acid hydrogen sulphate ionic liquid.Described acidic ion liquid is published known compound, and those skilled in the art can obtain its preparation method according to existing document.
Aromatic nitro compound shown in formula I of the present invention is 1:0.1 ~ 10 with the ratio of the amount of substance of acidic ion liquid, and preferred 1:0.4 ~ 1.5, are more preferably 1:0.9 ~ 1.3.
The mass ratio of the aromatic nitro compound shown in described formula I and loaded platinum catalyst is 1:0.001 ~ 0.3, preferred 1:0.008 ~ 0.01.
The volumetric usage of described solvent counts 5 ~ 35mL/g with the quality of the aromatic nitro compound shown in formula I, preferred 1:20 ~ 25mL/g.
Described reaction solution post-treating method is: after reaction terminates, by reaction solution suction filtration, the recyclable loaded platinum catalyst of filter cake, filtrate is steamed except desolventizing through revolving, residuum is extracted with ethyl acetate, and ethyl acetate can extraction and recovery acidic ion liquid, layering removing ethyl acetate layer, the liquid phase of residue containing product, through underpressure distillation, obtains 4-alkoxy benzene aminated compounds.
Preferably 2 ~ 12 hours time of reaction of the present invention, more preferably 3 ~ 4 hours.
The temperature of described reaction is preferably 40 ~ 60 DEG C, more preferably 50 DEG C.
The pressure of described reaction is 0.1 ~ 2.0MPa, preferably 0.12 ~ 0.2MPa, more preferably 0.14 ~ 0.2MPa.
The present invention is starting raw material with aromatic nitro compound, is hydrogenation catalyst with load type platinum, is Bamberger rearrangement catalyst with acidic ion liquid, adopts " one kettle way " to synthesize 4-alkoxy benzene aminated compounds in lower aliphatic alcohols.Concrete, described aromatic nitro compound shortening resets the method for 4-alkoxy benzene aminated compounds processed, step is as follows: be 1:0.001 ~ 0.3 according to the mass ratio of aromatic nitro compound and loaded platinum catalyst, aromatic nitro compound is 1:0.1 ~ 10 with the ratio of the amount of substance of acidic ion liquid, the volumetric usage of solvent counts 5 ~ 35mL/g with the quality of the aromatic nitro compound shown in formula I, by aromatic nitro compound, loaded platinum catalyst, acidic ion liquid, solvent adds autoclave, air in logical hydrogen exchange autoclave also keeps hydrogen pressure 0.1 ~ 2.0MPa, intensification remains on 30 ~ 180 DEG C, react 2 ~ 12 hours, after reaction terminates, by reaction solution suction filtration, filtrate is steamed except desolventizing through revolving, residuum is extracted with ethyl acetate, layering removing ethyl acetate layer, the liquid phase of residue containing product is through underpressure distillation, obtain 4-alkoxy benzene aminated compounds.
Further, described method is preferably carried out according to the following steps: be 1:0.008 ~ 0.01 according to the mass ratio of the aromatic nitro compound shown in formula I and Pt/C catalyzer, aromatic nitro compound is 1:0.9 ~ 1.3 with the ratio of the amount of substance of acidic ion liquid, the volumetric usage of solvent counts 20 ~ 25mL/g with the quality of the aromatic nitro compound shown in formula I, by aromatic nitro compound, Pt/C catalyzer, acidic ion liquid, solvent adds autoclave, air in logical hydrogen exchange autoclave also keeps hydrogen pressure 0.14 ~ 0.2MPa, intensification remains on 40 ~ 60 DEG C, react 3 ~ 4 hours, after reaction terminates, by reaction solution suction filtration, filtrate is steamed except desolventizing through revolving, residuum is extracted with ethyl acetate, layering removing ethyl acetate layer, the liquid phase of residue containing product is through underpressure distillation, obtain the 4-alkoxy benzene aminated compounds shown in formula II.
Compared with prior art, its beneficial effect is embodied in the present invention:
1. be starting raw material with aromatic nitro compound, adopt " one kettle way " to synthesize 4-alkoxy benzene aminated compounds under mild conditions, technique is simple, cost is low, operational safety, environmentally friendly.The yield that aromatic nitro compound transformation efficiency can reach 100%, 4-alkoxy benzene aminated compounds is greater than 65%.
2. replace sulfuric acid with acidic ion liquid, environmental pollution and equipment corrosion can be reduced, and all recyclable recycling of catalyzer and acidic ion liquid, can reduce costs, be suitable for suitability for industrialized production.
(4) embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
In the embodiment of the present invention, N-Methylimidazole propanesulfonic acid hydrogen sulphate ionic liquid prepares by the following method: take 12.2g(0.1mol) l, 3-propane sultone, add in 100mL flask after dissolving with 50mL toluene, in ice bath, drip 8mL(0.1mol) N-Methylimidazole, 80 DEG C of reactions 2 hours are slowly warming up to after dripping, be cooled to room temperature, filter, gained white precipitate ethyl acetate washs 4 times, at 100 DEG C, drying 5 hours, obtains intermediate.Intermediate is added in 100mL single port flask, add 50mL water and make it dissolve, then at ambient temperature, drip the vitriol oil of 5.43mL98% (containing H with constant pressure funnel
2sO
4for 0.1mol), be slowly warming up to 90 DEG C of reactions 2 hours after dripping, then underpressure distillation dewaters, and gained sticks thick liquid and is N-Methylimidazole propanesulfonic acid hydrosulfate, and molecular formula is C
7h
14n
2o
7s
2, molecular weight is 302.
Change the N-Methylimidazole in aforesaid method into imidazoles, prepare imidazoles propanesulfonic acid hydrogen sulphate ionic liquid in the same way, molecular formula is C
6h
12n
2o
7s
2, molecular weight is 288.
Embodiment 1:
The synthesis of P-nethoxyaniline: add 2.4g(0.02mol in autoclave) oil of mirbane, 50mL methyl alcohol, 4.53g (0.015mol) N-Methylimidazole propanesulfonic acid hydrogen sulphate ionic liquid and 0.02g Pt charge capacity are the Pt/C catalyzer of 3wt%, temperature of reaction 50 DEG C, pass into hydrogen to pressure 0.12MPa, react 4 hours, the transformation efficiency that vapor-phase chromatography detects oil of mirbane is 100%, and the yield of P-nethoxyaniline is 10%.
Embodiment 2:
The synthesis of 2-methyl-4-anisidine: add 2.4g(0.018mol in 100mL autoclave) Ortho Nitro Toluene, 50mL methyl alcohol, 4.896g (0.017mol) imidazoles propanesulfonic acid hydrogen sulphate ionic liquid and 0.02gPt charge capacity are the Pt/C catalyzer of 3wt%, temperature of reaction 50 DEG C, pass into hydrogen to pressure 0.14MPa, react 3 hours, the transformation efficiency of gas chromatographic analysis Ortho Nitro Toluene is the yield of 92.6%, 2-methyl-4-anisidine is 73.2%.
Embodiment 3:
Other operations are with embodiment 2, and difference is that acidic ion liquid used is N-Methylimidazole propanesulfonic acid hydrosulfate, reacts 3 hours, and the transformation efficiency of gas chromatographic analysis Ortho Nitro Toluene is the yield of 100%, 2-methyl-4-anisidine is 68%.By reaction solution suction filtration removing Pt/C catalyzer, filtrate is steamed except desolventizing through revolving, residuum is extracted with ethyl acetate 3 acidic ion liquids reclaimed in reaction solution, layering removing ethyl acetate layer, rest layers is the liquid containing product, underpressure distillation, obtains 4-alkoxy benzene aminated compounds, and yield is 60%.
Embodiment 4-11:
Other operations, with embodiment 3, change some reaction conditionss, obtain following reaction result (table 1):
Table 1
Claims (4)
1. the synthetic method of the 4-alkoxy benzene aminated compounds shown in a formula II, it is characterized in that described method for: the aromatic nitro compound shown in formula I is starting raw material, with fatty alcohol roh for solvent, under the effect of loaded platinum catalyst and acidic ion liquid, at 30 ~ 180 DEG C of temperature, logical hydrogen reacts 1 ~ 20 hour under the hydrogen pressure of 0.1 ~ 2.0MPa, and reaction terminates rear reaction solution and obtains the 4-alkoxy benzene aminated compounds shown in formula II through aftertreatment:
In formula I or formula II, R
1, R
2, R
3, R
4respective is independently hydrogen, chlorine, methyl or ethyl, and the R in ROH or formula II is methyl or ethyl;
Described acidic ion liquid is N-Methylimidazole propanesulfonic acid hydrogen sulphate ionic liquid or imidazoles propanesulfonic acid hydrogen sulphate ionic liquid;
Described loaded platinum catalyst is with gac, aluminum oxide, silicon oxide or titanium oxide for carrier, and load has Pt to be the catalyzer of active ingredient, and wherein the charge capacity of Pt is 0.5 ~ 10.0wt%;
Aromatic nitro compound shown in described formula I is 1:0.9 ~ 1.3 with the ratio of the amount of substance of acidic ion liquid;
The mass ratio of the aromatic nitro compound shown in described formula I and loaded platinum catalyst is 1:0.008 ~ 0.01.
2. the method for claim 1, is characterized in that the volumetric usage of described solvent counts 5 ~ 35mL/g with the quality of the aromatic nitro compound shown in formula I.
3. the method for claim 1, it is characterized in that described reaction solution post-treating method is: after reaction terminates, reaction solution suction filtration, filtrate is steamed except desolventizing through revolving, residuum is extracted with ethyl acetate, layering removing ethyl acetate layer, the liquid phase of residue containing product, through underpressure distillation, obtains 4-alkoxy benzene aminated compounds.
4. the method for claim 1, it is characterized in that described method is carried out according to the following steps: be 1:0.008 ~ 0.01 according to the mass ratio of the aromatic nitro compound shown in formula I and Pt/C catalyzer, aromatic nitro compound is 1:0.9 ~ 1.3 with the ratio of the amount of substance of acidic ion liquid, the volumetric usage of solvent counts 20 ~ 25mL/g with the quality of the aromatic nitro compound shown in formula I, by aromatic nitro compound, Pt/C catalyzer, acidic ion liquid, solvent adds autoclave, air in logical hydrogen exchange autoclave also keeps hydrogen pressure 0.14 ~ 0.2MPa, intensification remains on 40 ~ 60 DEG C, react 3 ~ 4 hours, after reaction terminates, by reaction solution suction filtration, filtrate is steamed except desolventizing through revolving, residuum is extracted with ethyl acetate, layering removing ethyl acetate layer, the liquid phase of residue containing product is through underpressure distillation, obtain the 4-alkoxy benzene aminated compounds shown in formula II.
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| CN112812027B (en) * | 2021-01-06 | 2022-05-27 | 湘潭大学 | Methoxyaniline compound and synthetic method thereof |
| CN115477589B (en) * | 2022-11-02 | 2023-03-24 | 山东道可化学有限公司 | Method for continuously preparing 2-methyl-4-methoxyaniline |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61109759A (en) * | 1984-11-01 | 1986-05-28 | Mitsui Toatsu Chem Inc | Production of 4-alkoxyaniline |
| US5304680A (en) * | 1990-07-20 | 1994-04-19 | Bayer Aktiengesellschaft | Process for the preparation of aromatic amines which are substituted by C1 -C4 -alkoxy in the p-position |
| CN101182300A (en) * | 2007-12-12 | 2008-05-21 | 河北工业大学 | Quaternary ammonium ionic liquid as well as preparation and application method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3383416A (en) * | 1965-07-08 | 1968-05-14 | Roland G. Benner | Process for preparing aminophenol |
| JPS6033102B2 (en) * | 1977-11-04 | 1985-08-01 | 三井東圧化学株式会社 | Method for producing para-aminophenol and nuclear-substituted para-aminophenol |
| JP2984047B2 (en) * | 1990-10-11 | 1999-11-29 | 郡山化成株式会社 | Method for producing 1-amino-4-alkoxybenzenes |
| CN101735254B (en) * | 2008-11-12 | 2012-05-16 | 宁波大学 | Boric acid ester synthesis method |
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2013
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| JPS61109759A (en) * | 1984-11-01 | 1986-05-28 | Mitsui Toatsu Chem Inc | Production of 4-alkoxyaniline |
| US5304680A (en) * | 1990-07-20 | 1994-04-19 | Bayer Aktiengesellschaft | Process for the preparation of aromatic amines which are substituted by C1 -C4 -alkoxy in the p-position |
| CN101182300A (en) * | 2007-12-12 | 2008-05-21 | 河北工业大学 | Quaternary ammonium ionic liquid as well as preparation and application method thereof |
Non-Patent Citations (1)
| Title |
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| 铂-酸性离子液体双功能催化剂及催化合成对氨基苯酚;崔咏梅;《河北工业大学博士学位论文》;20091215;第41页第3-4-1节 * |
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