CN108047065B - A kind of preparation method for the adjacent amino phenylate reducing by-product - Google Patents
A kind of preparation method for the adjacent amino phenylate reducing by-product Download PDFInfo
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- CN108047065B CN108047065B CN201711303926.8A CN201711303926A CN108047065B CN 108047065 B CN108047065 B CN 108047065B CN 201711303926 A CN201711303926 A CN 201711303926A CN 108047065 B CN108047065 B CN 108047065B
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- phenylate
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- adjacent amino
- etherification
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 22
- 239000006227 byproduct Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006266 etherification reaction Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 22
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000008346 aqueous phase Substances 0.000 claims abstract description 10
- 238000005191 phase separation Methods 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012074 organic phase Substances 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 25
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 20
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical group COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000003987 high-resolution gas chromatography Methods 0.000 claims description 17
- 229960000228 cetalkonium chloride Drugs 0.000 claims description 13
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 10
- 238000005292 vacuum distillation Methods 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- CFBYEGUGFPZCNF-UHFFFAOYSA-N 2-nitroanisole Chemical group COC1=CC=CC=C1[N+]([O-])=O CFBYEGUGFPZCNF-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- ULHFFAFDSSHFDA-UHFFFAOYSA-N 1-amino-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1N ULHFFAFDSSHFDA-UHFFFAOYSA-N 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- XGLGESCVNJSAQY-UHFFFAOYSA-N 1-ethoxy-2-nitrobenzene Chemical compound CCOC1=CC=CC=C1[N+]([O-])=O XGLGESCVNJSAQY-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QDYLMAYUEZBUFO-UHFFFAOYSA-N cetalkonium chloride Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 QDYLMAYUEZBUFO-UHFFFAOYSA-N 0.000 claims 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910000564 Raney nickel Inorganic materials 0.000 claims 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 235000012255 calcium oxide Nutrition 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 235000001055 magnesium Nutrition 0.000 claims 1
- 235000012245 magnesium oxide Nutrition 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 16
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 11
- 230000006837 decompression Effects 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- OKUSWAGOKUGEDX-UHFFFAOYSA-N C(CCC)Br(CCCC)(CCCC)CCCC Chemical compound C(CCC)Br(CCCC)(CCCC)CCCC OKUSWAGOKUGEDX-UHFFFAOYSA-N 0.000 description 5
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- -1 hexadecyldimethyl benzyl ammonium Benzylmagnesium chloride Ammonium Chemical compound 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 2
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- JYQWNNQZIKBRJK-UHFFFAOYSA-N C(C1=CC=CC=C1)Cl.C(CCCCCCCCCCCCCCC)[N+](CC1=CC=CC=C1)(C)C Chemical compound C(C1=CC=CC=C1)Cl.C(CCCCCCCCCCCCCCC)[N+](CC1=CC=CC=C1)(C)C JYQWNNQZIKBRJK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical compound C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229940032912 zephiran Drugs 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to the preparation method of adjacent amino phenylate, in particular to a kind of preparation method for the adjacent amino phenylate that can reduce by-product.This method by etherification reaction, etherification product oil aqueous phase separation, catalytic hydrogenation reaction, filtering, rectifying and etc. prepare adjacent amino phenylate.The preparation method of the adjacent amino phenylate provided by the invention for reducing by-product, clean and environmental protection, easy to operate, low energy consumption, no pollution to the environment, and the adjacent amino phenylate yield prepared using this method is high, with high purity.In the preparation method of the adjacent amino phenylate provided by the invention for reducing by-product, phase transfer catalyst dosage is few, and the by-product generated in reaction process is few.
Description
For a large amount of technique waste waters can be generated in pretreatment process, the loss of serious environmental pollution and material is caused
Technical problem, present invention process is simple, high conversion rate；Technical process cleaning, it is environmentally protective；Three-waste pollution is few.
Summary of the invention
The purpose of the present invention is to provide the preparation method that one kind can reduce the adjacent amino phenylate of by-product, this method cleanings
It is environmentally friendly, easy to operate, low energy consumption, no pollution to the environment, the adjacent amino phenylate yield for using this method to prepare is high, purity is high, secondary
Product is few.
The object of the present invention is to provide the preparation method that one kind can reduce the adjacent amino phenylate of by-product, this method includes such as
Lower step:
1) etherification reaction: in etherifying agent, o-nitrochlorobenzene and quaternary ammonium salt catalyst is added, opens and stirs and be heated to
55-65 DEG C, a certain amount of acid binding agent solution and hydrogen peroxide are then added dropwise into reaction, is detected and is reacted with high resolution gas chromatography instrument,
Finally obtain etherification product adjacent nitro phenylate；
2) etherification product in step 1) is cooled to room temperature, makes oily aqueous phase separation, divided and organic phase is gone to be washed with water, washed
Organic phase vacuum distillation afterwards, must be etherified oil；
3) etherificate oil, catalyst thunder Buddhist nun obtained in organic solvent, step 2) catalytic hydrogenation reaction: are added in autoclave
Nickel, distilled water, heating stirring after replacing hydrogen are detected with high resolution gas chromatography instrument and are reacted, until reaction terminates；
4) the catalytic hydrogenation reaction system in step 3) being cooled to room temperature, filtered, the catalyst circulation filtered out uses,
Filtrate decompression distills to obtain the crude product of adjacent amino phenylate；
5) crude product obtained in step 4) is obtained into adjacent amino phenylate by rectifying.
Further, quaternary ammonium salt catalyst described in step 1) is tetrabutylammonium bromide and hexadecyldimethyl benzyl ammonium benzyl chloride
Change the composition of ammonium.
Further, the mass ratio of the tetrabutylammonium bromide and cetalkonium chloride is 1-3:1.
Further, the adjacent amino phenylate is o-aminoanisole, o-phenetidine；The adjacent nitro phenylate is
Ortho-nitroanisole, o-nitrophenetole.
Further, etherifying agent described in step 1) is methanol, or ethyl alcohol.
Further, acid binding agent described in step 1) be sodium hydroxide, sodium carbonate, magnesium carbonate, ammonium carbonate, sodium bicarbonate,
One of magnesia, calcium oxide are a variety of, preferably sodium hydroxide.
Further, quaternary ammonium salt catalyst described in step 1) is tetrabutylammonium bromide, benzyl triethyl ammonium bromide, 16
One of zephiran.
Further, quaternary ammonium salt catalyst described in step 1) is preferably cetalkonium chloride.
Further, in step 1) quaternary ammonium salt catalyst and o-nitrochlorobenzene mass ratio 0.001-0.015:1.
Further, the mass ratio of o-nitrochlorobenzene and hydrogen peroxide is 1:0.0001-0.001 in step 1).
Further, hydrogen peroxide is hydrogen peroxide solution that mass fraction is 35% in step 1).
Further, acid binding agent solution is that acid binding agent and distilled water are formulated according to mass ratio 1:1 in step 1).
Further, the mass ratio of o-nitrochlorobenzene and etherifying agent is 1:1-1.5 in step 1).
Further, dividing in step 2) goes obtained aqueous solution after organic phase to add acid binding agent solution, and carries out recycled.
Further, heating temperature described in step 3) is 80-100 DEG C.
Further, organic solvent described in step 3) is one or more of methanol, ethyl alcohol, toluene.
Further, used catalyst can also be palladium-carbon catalyst or platinum carbon catalyst in step 3).
Further, such as there is emulsion after being cooled to room temperature in catalytic hydrogenation reaction system in step 4), then this is anti-
It answers system to be heated to reflux, filters while hot, the catalyst circulation filtered out uses, and filtrate decompression distills to obtain the thick of adjacent amino phenylate
Product.
Rectifying means in step 4) of the present invention are ordinary skill in the art means.
In the present invention, in order to reduce the generation of tar, during the reaction, a small amount of water, which is added, can inhibit the life of tar
At.
In the present invention, the preparation of adjacent nitro phenylate uses phase transfer catalysis process.Phase-transfer-catalyzed reactions are to utilize catalysis
It is existing in the molecular structure of agent to dissolve in water phase, and have the group for dissolving in organic phase.For nucleophilic substitution, exist in water
When, catalyst can make the original nucleopilic reagent insoluble in organic phase first with the nucleopilic reagent reacting forming ion pair in water phase
Relatively easily enter organic phase and participate in reaction, if quaternary ammonium salt is a kind of common phase transfer catalyst.Contain hydrophobic in molecule
The Long carbon chain of property, structure such as tetrabutylammonium bromide can use general formula QTenXOneIt indicates.Due to catalyst cation partial volume compared with
Greatly, ion exchange is carried out with salt in water phase, is easy to form ion pair Q with the nucleopilic reagent in water phase+YOneAnd enter organic
Phase, the nucleopilic reagent in water phase are transferred to organic phase, in two alternate formation balances, catalyst QTenVolume it is larger, it is such from
Distance between sub- centering negative ions is big, and with regard to very little, nucleophilic tries Liu Y for mutual effectOneIt is just considered as exposed.It enters
After organic phase, reactivity is very strong, generates product, leaving group and Q after reaction with the reaction substrate effect in organic phase immediately+
Form Q+X-Ion pair, takes back water phase, and the circulating repetition above process is achieved that two alternate transfers.
In the present invention, phase transfer catalyst selects quaternary ammonium salt catalyst, can use tetrabutylammonium bromide, or
Benzyl triethyl ammonium bromide, cetalkonium chloride.Wherein, it is preferred to use hexadecyldimethyl benzyl ammonium Benzylmagnesium chloride
Ammonium is as phase transfer catalyst of the invention.In the present invention, phase transfer catalyst can also use tetrabutylammonium bromide and ten
The composition of six zephirans.The present invention is reduced under the conditions of optimum proportioning using the combination catalyst
The dosage of catalyst, also obtains extraordinary catalytic effect.
In the catalytic hydrogenation of adjacent nitro phenylate, dechlorination side reaction easily occurs.The main original of dechlorination side reaction occurs
Because being nitro while adsorbing on the activated centre of catalyst surface, work is also had occurred in the chlorine with lone pair electrons and unoccupied orbital
Property absorption, they with absorption hydrogen in conjunction with dechlorinations generation aniline.Dechlorination side reaction hydrogen chloride generated makes the activity of catalyst
And service life reduction, therefore dechlorination reaction must be inhibited.The present invention provides matching for a kind of preferably o-nitrochlorobenzene and etherifying agent
Than making o-nitrochlorobenzene be converted into adjacent nitro phenylate to the greatest extent during etherification reaction, reducing o-nitrochlorobenzene
Residual.
In the etherification reaction of o-nitrochlorobenzene, due to the alkalinity of reaction system, the hydrolysis of part o-nitrochlorobenzene is had, it is raw
At o-nitrophenol, on the other hand due to the reproducibility of carbinol base, aryl compound and nitroso compound can be generated, they
Occur to be similar to aldol reaction under alkaline condition, then slough the water generation azoxybenzene compound of a molecule, to neighbour
The quality and yield output of nitro phenylate adversely affect.Hydrogen peroxide, which is added, in the present invention can effectively inhibit azoxybenzene by-product
The generation of object.
The present invention has the beneficial effect that compared with prior art
1, the preparation method of the adjacent amino phenylate provided by the invention for reducing by-product, clean and environmental protection, easy to operate, energy
Low, no pollution to the environment is consumed, the adjacent amino phenylate yield prepared using this method is high, with high purity.
2, in the preparation method of the adjacent amino phenylate provided by the invention for reducing by-product, phase transfer catalyst dosage
Few, the by-product generated in reaction process is few.
Specific embodiment
Embodiment 1
1) etherification reaction: being added 500kg methanol in a kettle, and 500kg o-nitrochlorobenzene and 0.5kg cetyl is added
Dimethyl benzyl ammonium chloride catalyst is opened and stirs and be heated to 55 DEG C, and the sodium hydroxide that 100kg is then added dropwise into reaction is molten
Liquid and 0.05kg hydrogen peroxide are detected with high resolution gas chromatography instrument and are reacted, finally obtain etherification product ortho-nitroanisole；
2) etherification product in step 1) is cooled to room temperature, makes oily aqueous phase separation, divided and organic phase is gone to be washed with water, washed
Organic phase vacuum distillation afterwards, must be etherified oil；
3) etherificate oil, 10kg thunder Buddhist nun obtained in 500kg methanol, step 2) catalytic hydrogenation reaction: are added in autoclave
Nickel, 10kg distilled water, heating stirring after replacing hydrogen, heating temperature are 80 DEG C, are detected and are reacted with high resolution gas chromatography instrument, until
Reaction terminates；
4) the catalytic hydrogenation reaction system in step 3) being cooled to room temperature, filtered, the catalyst circulation filtered out uses,
Filtrate decompression distills to obtain the crude product of o-aminoanisole；
5) crude product obtained in step 4) is obtained into o-aminoanisole, the yield of o-aminoanisole by rectifying
It is 94.5%, purity 99.2%, the yield of by-product aniline is 1.5%.
Embodiment 2
1) etherification reaction: being added 750kg ethyl alcohol in a kettle, and 500kg o-nitrochlorobenzene and 7.5kg cetyl is added
Dimethyl benzyl ammonium chloride catalyst is opened and stirs and be heated to 65 DEG C, and the sodium hydroxide that 110kg is then added dropwise into reaction is molten
Liquid and 0.5kg hydrogen peroxide are detected with high resolution gas chromatography instrument and are reacted, finally obtain etherification product o-nitrophenetole；
2) etherification product in step 1) is cooled to room temperature, makes oily aqueous phase separation, divided and organic phase is gone to be washed with water, washed
Organic phase vacuum distillation afterwards, must be etherified oil；
3) etherificate oil, 12kg thunder Buddhist nun obtained in 500kg methanol, step 2) catalytic hydrogenation reaction: are added in autoclave
Nickel, 15kg distilled water, heating stirring after replacing hydrogen, heating temperature are 100 DEG C, are detected and are reacted with high resolution gas chromatography instrument, directly
Terminate to reaction；
4) the catalytic hydrogenation reaction system in step 3) being cooled to room temperature, filtered, the catalyst circulation filtered out uses,
Filtrate decompression distills to obtain the crude product of o-phenetidine；
5) crude product obtained in step 4) is obtained into o-phenetidine, the yield of o-phenetidine by rectifying
It is 96.1%, purity 99.5%, the yield of by-product aniline is 1.0%.
Embodiment 3
1) etherification reaction: being added 550kg methanol in a kettle, and 500kg o-nitrochlorobenzene and 2.5kg tetrabutyl bromine is added
Change ammonium and the cetalkonium chloride (mass ratio of tetrabutylammonium bromide and cetalkonium chloride
It for 2:1), opens and stirs and be heated to 60 DEG C, the sodium hydroxide solution and 0.2kg hydrogen peroxide of 100kg are then added dropwise into reaction,
It is detected and is reacted with high resolution gas chromatography instrument, finally obtain etherification product ortho-nitroanisole；
2) etherification product in step 1) is cooled to room temperature, makes oily aqueous phase separation, divided and organic phase is gone to be washed with water, washed
Organic phase vacuum distillation afterwards, must be etherified oil；
3) etherificate oil, 10kg thunder Buddhist nun obtained in 500kg toluene, step 2) catalytic hydrogenation reaction: are added in autoclave
Nickel, 12kg distilled water, heating stirring after replacing hydrogen, heating temperature are 90 DEG C, are detected and are reacted with high resolution gas chromatography instrument, until
Reaction terminates；
4) the catalytic hydrogenation reaction system in step 3) being cooled to room temperature, filtered, the catalyst circulation filtered out uses,
Filtrate decompression distills to obtain the crude product of o-aminoanisole；
5) crude product obtained in step 4) is obtained into o-aminoanisole, the yield of o-aminoanisole by rectifying
It is 97.3%, purity 99.7%, the yield of by-product aniline is 0.5%.
Embodiment 4
1) etherification reaction: being added 550kg methanol in a kettle, and 500kg o-nitrochlorobenzene and 2.5kg tetrabutyl bromine is added
Change ammonium and the cetalkonium chloride (mass ratio of tetrabutylammonium bromide and cetalkonium chloride
It for 1:1), opens and stirs and be heated to 60 DEG C, the sodium hydroxide solution and 0.2kg hydrogen peroxide of 100kg are then added dropwise into reaction,
It is detected and is reacted with high resolution gas chromatography instrument, finally obtain etherification product ortho-nitroanisole；
2) etherification product in step 1) is cooled to room temperature, makes oily aqueous phase separation, divided and organic phase is gone to be washed with water, washed
Organic phase vacuum distillation afterwards, must be etherified oil；
3) etherificate oil, 10kg thunder Buddhist nun obtained in 500kg toluene, step 2) catalytic hydrogenation reaction: are added in autoclave
Nickel, 12kg distilled water, heating stirring after replacing hydrogen, heating temperature are 90 DEG C, are detected and are reacted with high resolution gas chromatography instrument, until
Reaction terminates；
4) the catalytic hydrogenation reaction system in step 3) being cooled to room temperature, filtered, the catalyst circulation filtered out uses,
Filtrate decompression distills to obtain the crude product of o-aminoanisole；
5) crude product obtained in step 4) is obtained into o-aminoanisole, the yield of o-aminoanisole by rectifying
It is 96.5%, purity 99.6%, the yield of by-product aniline is 0.8%.
Embodiment 5
1) etherification reaction: being added 550kg methanol in a kettle, and 500kg o-nitrochlorobenzene and 2.5kg tetrabutyl bromine is added
Change ammonium and the cetalkonium chloride (mass ratio of tetrabutylammonium bromide and cetalkonium chloride
It for 3:1), opens and stirs and be heated to 60 DEG C, the sodium hydroxide solution and 0.2kg hydrogen peroxide of 100kg are then added dropwise into reaction,
It is detected and is reacted with high resolution gas chromatography instrument, finally obtain etherification product ortho-nitroanisole；
2) etherification product in step 1) is cooled to room temperature, makes oily aqueous phase separation, divided and organic phase is gone to be washed with water, washed
Organic phase vacuum distillation afterwards, must be etherified oil；
3) etherificate oil, 10kg thunder Buddhist nun obtained in 500kg toluene, step 2) catalytic hydrogenation reaction: are added in autoclave
Nickel, 12kg distilled water, heating stirring after replacing hydrogen, heating temperature are 90 DEG C, are detected and are reacted with high resolution gas chromatography instrument, until
Reaction terminates；
4) the catalytic hydrogenation reaction system in step 3) being cooled to room temperature, filtered, the catalyst circulation filtered out uses,
Filtrate decompression distills to obtain the crude product of o-aminoanisole；
5) crude product obtained in step 4) is obtained into o-aminoanisole, the yield of o-aminoanisole by rectifying
It is 96.3%, purity 99.4%, the yield of by-product aniline is 0.9%.
Embodiment 6
1) etherification reaction: being added 550kg methanol in a kettle, and 500kg o-nitrochlorobenzene and 2.5kg tetrabutyl bromine is added
Change ammonium, open and stir and be heated to 60 DEG C, the sodium hydroxide solution and 0.2kg hydrogen peroxide of 100kg are then added dropwise into reaction, uses
The detection reaction of high resolution gas chromatography instrument, finally obtains etherification product ortho-nitroanisole；
2) etherification product in step 1) is cooled to room temperature, makes oily aqueous phase separation, divided and organic phase is gone to be washed with water, washed
Organic phase vacuum distillation afterwards, must be etherified oil；
3) etherificate oil, 10kg thunder Buddhist nun obtained in 500kg toluene, step 2) catalytic hydrogenation reaction: are added in autoclave
Nickel, 12kg distilled water, heating stirring after replacing hydrogen, heating temperature are 90 DEG C, are detected and are reacted with high resolution gas chromatography instrument, until
Reaction terminates；
4) the catalytic hydrogenation reaction system in step 3) being cooled to room temperature, filtered, the catalyst circulation filtered out uses,
Filtrate decompression distills to obtain the crude product of o-aminoanisole；
5) crude product obtained in step 4) is obtained into o-aminoanisole, the yield of o-aminoanisole by rectifying
It is 94.1%, purity 99.1%, the yield of by-product aniline is 2.6%.
Comparative example 1
1) etherification reaction: being added 550kg methanol in a kettle, and 500kg o-nitrochlorobenzene and 2.5kg tetrabutyl bromine is added
Change ammonium and the cetalkonium chloride (mass ratio of tetrabutylammonium bromide and cetalkonium chloride
It for 2:1), opens and stirs and be heated to 60 DEG C, the sodium hydroxide solution of 100kg is then added dropwise into reaction, with efficient gas phase color
Spectrometer detection reaction, finally obtains etherification product ortho-nitroanisole；
2) etherification product in step 1) is cooled to room temperature, makes oily aqueous phase separation, divided and organic phase is gone to be washed with water, washed
Organic phase vacuum distillation afterwards, must be etherified oil；
3) etherificate oil, 10kg thunder Buddhist nun obtained in 500kg toluene, step 2) catalytic hydrogenation reaction: are added in autoclave
Nickel, 12kg distilled water, heating stirring after replacing hydrogen, heating temperature are 90 DEG C, are detected and are reacted with high resolution gas chromatography instrument, until
Reaction terminates；
4) the catalytic hydrogenation reaction system in step 3) being cooled to room temperature, filtered, the catalyst circulation filtered out uses,
Filtrate decompression distills to obtain the crude product of o-aminoanisole；
5) crude product obtained in step 4) is obtained into o-aminoanisole, the yield of o-aminoanisole by rectifying
It is 95.5%, purity 99.1%, the yield of by-product aniline is 2.5%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (4)
1. the preparation method that one kind can reduce the adjacent amino phenylate of by-product, it is characterised in that described method includes following steps:
1) etherification reaction: in etherifying agent, o-nitrochlorobenzene and quaternary ammonium salt catalyst is added, opens and stirs and be heated to 55-65
DEG C, a certain amount of acid binding agent solution and hydrogen peroxide are then added dropwise into reaction, is detected and is reacted with high resolution gas chromatography instrument, final
To etherification product adjacent nitro phenylate；
Wherein, quaternary ammonium salt catalyst is the composition of tetrabutylammonium bromide and cetalkonium chloride, the tetrabutyl
The mass ratio of ammonium bromide and cetalkonium chloride is 1-3:1；The mass ratio of o-nitrochlorobenzene and hydrogen peroxide is
1:0.0001-0.001；The mass ratio of o-nitrochlorobenzene and etherifying agent is 1:1-1.5；Quaternary ammonium salt catalyst and o-nitrochlorobenzene
Mass ratio is 0.001-0.015:1；Neighbour's amino phenylate is o-aminoanisole, o-phenetidine；The adjacent nitro
Phenylate is ortho-nitroanisole, o-nitrophenetole；
2) etherification product in step 1) is cooled to room temperature, makes oily aqueous phase separation, divided and organic phase is gone to be washed with water, after washing
Organic phase vacuum distillation, must be etherified oil；
3) catalytic hydrogenation reaction: be added in autoclave organic solvent, etherificate oil, catalyst Raney's nickel obtained in step 2),
Distilled water, heating stirring after replacing hydrogen are detected with high resolution gas chromatography instrument and are reacted, until reaction terminates；
4) the catalytic hydrogenation reaction system in step 3) is cooled to room temperature, filtered, the catalyst circulation filtered out uses, filtrate
Vacuum distillation obtains the crude product of adjacent amino phenylate；
5) crude product obtained in step 4) is obtained into adjacent amino phenylate by rectifying.
2. method according to claim 1, which is characterized in that etherifying agent described in step 1) is any in methanol or ethyl alcohol
Kind.
3. method according to claim 1, which is characterized in that acid binding agent described in step 1) is sodium hydroxide, sodium carbonate, carbon
One of sour magnesium, ammonium carbonate, sodium bicarbonate, magnesia, calcium oxide are a variety of.
4. according to claim 3 the method, which is characterized in that acid binding agent described in step 1) is sodium hydroxide.
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| CN110724063B (en) * | 2019-11-21 | 2022-08-23 | 南京先进生物材料与过程装备研究院有限公司 | Method for preparing o-aminoanisole by adopting micro-flow field reaction technology |
| CN111187168A (en) * | 2019-12-12 | 2020-05-22 | 中卫市鑫三元化工有限公司 | Clean production process for producing nitrobenzene alkoxy ether by using nitrohalogenated benzene |
| CN113264840B (en) * | 2021-05-10 | 2023-03-24 | 河北旭阳能源有限公司 | Efficient environment-friendly production process of o-aminoanisole |
| CN114736128A (en) * | 2022-03-10 | 2022-07-12 | 青岛科技大学 | Method for preparing o-aminophenyl ether |
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Denomination of invention: A method for preparing o-aminophenyl ether that can reduce by-products Granted publication date: 20190212 Pledgee: Industrial Bank Co.,Ltd. Taizhou Branch Pledgor: JIANGSU ZHONGDAN CHEMICAL TECHNOLOGY Co.,Ltd. Registration number: Y2024980013262 |