CN106699571A - Preparation method of 2,5-dichloroaniline - Google Patents

Preparation method of 2,5-dichloroaniline Download PDF

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Publication number
CN106699571A
CN106699571A CN201611019543.3A CN201611019543A CN106699571A CN 106699571 A CN106699571 A CN 106699571A CN 201611019543 A CN201611019543 A CN 201611019543A CN 106699571 A CN106699571 A CN 106699571A
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reaction
dichloroaniline
dichloro
benzenes
selectivity
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宋广亮
徐杰
朱红军
周慧
刘睿
何广科
黄诚
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Nanjing Tech University
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Nanjing Tech University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a preparation method of 2,5-dichloroaniline, and belongs to the field of compound preparation. Under the effects of oxidizing agents, aminating agents, metal complex catalysts and cocatalysts, 1,4-dichlorobenzene is used as raw materials; one from water, methanol, acetonitrile, acetic acid and ethyl alcohol or a composition of more than one in water, methanol, acetonitrile, acetic acid and ethyl alcohol is used as a solvent; reaction is carried out at the reaction temperature being 15 to 95 DEG C for 1 to 96h to obtain 2,5-dichloroaniline. The method provided by the invention has the advantages that the catalyst system has high oxidative amination reaction efficiency and high yield; the reaction conditions are relatively mild; the side reaction is little; products can be conveniently separated; the reaction time is greatly shortened; the preparation method can be popularized to large-scale industrial production.

Description

One kind 2,5- dichloroaniline preparation methods
Technical field
The present invention relates to a kind of method of the preparation of aromatic amine, specifically, be related to a kind of catalysis oxidation amination Isosorbide-5-Nitrae- The method that dichloro-benzenes prepares 2,5- dichloroanilines, belongs to compound manufacture field, especially agricultural chemicals, medicine and dyestuff intermediate Manufacturing technology.
Background technology
2,5- dichloroanilines are a kind of new mothproofing agents, be can be used in the middle of the dyestuffs such as synthesis 2,5- dichloroaniline -4- sulfonic acid Body, has a wide range of applications in dyestuff dyestuff is prepared, or manufacture nitrogen fertilizer potentiating agent N-2,5- dichlorophenyl succinamic acid, The important intermediate of herbicide dicamba and insecticide lufenuron.
The current preparation method of 2,5- dichloroanilines is mainly first nitrification by Isosorbide-5-Nitrae-dichloro-benzenes and obtains 2,5- dichloronitrobenzenes, Then 2,5- dichloronitrobenzenes are reduced with reducing agent again and is obtained.Research emphasis are concentrated mainly on and reduce this step, industrialized Method has iron powder reducing method, sodium sulfide reducing method and catalytic hydrogenation method, and wherein iron powder reducing method and sodium sulfide reducing method is because of the three wastes Amount is big, and environmental pollution is heavier to be eliminated substantially, and catalytic hydrogenation method is prevailing technology.
The Fan Guangyin of China West Normal University uses receiving that titanium carbide is loaded in Chinese invention patent ZL2014103088955 Rice metal makees catalyst, using hydrogen as reducing agent, the conversion ratio 100% of 2,5- dichloronitrobenzenes, the choosing of 2,5- dichloroanilines Selecting property is up to 99%.
Yuan Yuan of Yangnong Chemical Co., Ltd., Jiangsu et al. is disclosed in Chinese invention patent 201310292296.4 The production method of one kind 2,5- dichloroanilines, with 2,5- dichloronitrobenzenes be raw material, activated carbon supported palladium or platinum as catalysis, , used as auxiliary agent, hydrogen is used as reducing agent, and the selectivity of 2,5- dichloronitrobenzene conversion ratios and 2,5- dichloroaniline is reachable for ammoniacal liquor 99%, it is capable of achieving the automatic continuous production of 2,5- dichloroanilines.
Meng Mingyang of Shenyang Chemical Engineering Inst et al. 2006 exists《Finely and specialty chemicals》Report, is made by oneself using them Catalyst, 2- BCAs are anti-antichlor, are reduced with hydrogen to 2,5- dichloronitrobenzenes in methanol solution 2,5- dichloroanilines, obtain product content 99.3%, yield 96.2%.
Reported in United States Patent (USP) US4960936, it is hydrogenation catalyst to use Raney-Ni (Raney's nickel), and Formamidine acetate is to help Agent, is reduced to 2,5- dichloroanilines by 2,5- dichloronitrobenzenes in methyl alcohol, product 2 after reduction, and the purity of 5- dichloroanilines can Up to 99.6%.
Oliver Beswick are in the 45-51 of Catalysis Today 249 (2015) reports using activated carbon fiber-loaded Nano-sized iron oxide make catalyst, hydrazine hydrate makees reducing agent, 2,5- dichloronitrobenzenes can be reduced into 2,5- at a temperature of 333K Dichloroaniline, the conversion ratio of selectivity 100%, 2,5- dichloronitrobenzenes is up to 95%.
In sum, current 2,5- dichloroanilines preparation method is with Isosorbide-5-Nitrae-dichloro-benzenes as raw material, by nitrifying and reducing Two steps are obtained.Substantial amounts of acid waste water can be produced in traditional nitration processes, is needed to reach preferable yield in reducing process Temperature and pressure higher is used, and two-step reaction will increase cost, reduce economic benefit.It is badly in need of one kind for this with 1, 4- dichloro-benzenes is raw material, by one-pot oxidation amination, an amino is introduced directly on phenyl ring and obtains 2,5- dichloroanilines Method.It is introduced directly into amino on aromatic ring to be reacted aryl amination, what research was more at present is the direct aryl amination generation aniline of benzene.
Hebei University of Technology Zhang Yanhua et al. is in Chinese invention patent ZL201410751845.4 and ZL2014107514576 Disclosed in a kind of benzene and azanol the reactant salt method that directly prepares aniline, the vanadium dioxide or molybdenum dioxide supported using Carbon Materials Catalyst is made, aniline yield rate is respectively 41% and 54%, is selectively all higher than 99%.
Hu Changwei of Sichuan University et al. is in Chinese invention patent ZL2013103606790 and ZL2010102185663 A kind of method that benzene direct oxidation amination prepares aniline is disclosed, and with benzene as raw material, ammoniacal liquor is aminating agent, and hydrogen peroxide is oxidation Agent, water is solvent, and improved silica loaded copper oxide or TS-1 carried metals are catalyst one-step synthesis aniline, have the disadvantage benzene The relatively low only 6-10% of amine yield, selectivity is 60-85%.
Zhang Long of Changchun Polytechnic Univ. et al. provides a kind of benzene direct aminatin in Chinese invention patent CN2015101682055 The method of aniline processed, clothing benzene is raw material, and V-MCM-41 is catalyst, and azanol is aminating agent, and the selectivity of aniline is 100%, benzene The yield of amine is up to 77.5%.
Lisitsyn, Yu A are in Russian Journal of Physical Chemistry A, 86 (6), 1033- 1034；The method that a kind of 2012 methyl phenyl ethers anisole direct aminatins of report generate aminoanisole, the method is electrochemical method, with azanol Used as aminating agent, titanium tetrachloride makees catalyst, and water and acetic acid make solvent, and the ratio of P-nethoxyaniline and o-aminoanisole is 66∶34。
The aryl amination reaction that amino is introduced directly on phenyl ring is electrophilic reaction, is unfavorable for containing electron withdraw group on phenyl ring Reaction is carried out.There are two chlorine on the phenyl ring of Isosorbide-5-Nitrae-dichloro-benzenes, because strong electronic effect causes it to be difficult to carry out direct arylamine Change reaction generation 2,5- dichloroanilines, have not yet to see the document that the direct aryl amination of Isosorbide-5-Nitrae-dichloro-benzenes is generated 2,5- dichloroanilines Report.
The content of the invention
The present invention provides a kind of new method that Isosorbide-5-Nitrae-dichloro-benzenes direct oxidation amination is prepared 2,5- dichloroanilines.The method With Isosorbide-5-Nitrae-dichloro-benzenes as raw material, with metal complex as catalyst, constituted with co-catalyst TS-1 molecular sieves and quaternary ammonium salt compound Catalyst system and catalyzing, with oxygen, air, hydrogen peroxide or TBHP as oxidant, with water, methyl alcohol, ethanol, acetonitrile or second Acid is solvent, with ammoniacal liquor, ammonia, hydroxylamine hydrochloride, ammonium carbonate, ammonium hydrogen carbonate or ammonium sulfate as aminating agent, in reaction at 15-95 DEG C 1-96h, after being separated through routine, is obtained 2,5- dichloroanilines, and its yield spectra is in 10-95%.
The inventive method compared with the conventional method, with advantages below：
(1) this method replaces the nitrification-reduction two of original technique with oxidative amination one-step method with Isosorbide-5-Nitrae-dichloro-benzenes as raw material Footwork can effectively reduce production cost, improve the economic benefit of enterprise.
(2) it is oxidant to use environment-friendly oxygen, hydrogen peroxide, air or TBHP, using ammoniacal liquor, salt Sour azanol, ammonium carbonate, ammonium hydrogen carbonate or ammonium sulfate are aminating agent.The advantage is that oxidant is safe from harm to environment, aminating agent Cheap, reaction of atomic good economy performance is conducive to industrialized production.
(3) with water, methyl alcohol, ethanol, acetonitrile or acetic acid etc. as reaction medium, not only greatly reduce production cost, reduce Corrosion to equipment, and the discharge of nitrating wasting acid is also reduced, meet cleanly production, while in also improving production process Security.
(4) this method reaction condition is relatively mild, easy to operate, and safety coefficient is high.
Specific embodiment
Embodiment 1
In 100mL three neck round bottom flask, 14.7g Isosorbide-5-Nitraes-dichloro-benzenes, 0.02g vanadyl acetylacetonates, four fourths are sequentially added Base ammonium bromide 0.05g, TS-1 molecular sieve 0.1g, concentrated ammonia liquor 15mL, add acetonitrile 50mL, by the dioxygens of 10.0mL 30% under stirring Water droplet is added in reaction bulb, is reacted at 90 DEG C and is continued 5h.Reaction solution is cooled to room temperature by reaction after terminating, and is discharged, through HPLC Analysis, 2,5- dichloroaniline yields are 57%, selectivity 80%.
Embodiment 2
Specific course of reaction is same as Example 1, and difference is to change vanadyl acetylacetonate into acetyl acetone, and 2, 5- dichloroanilines yield is 50%, selectivity 92%.
Embodiment 3
Specific course of reaction is same as Example 1, and difference is to change vanadyl acetylacetonate into acetylacetone cobalt, and 2, 5- dichloroanilines yield is 67%, selectivity 85%.
Embodiment 4
Specific course of reaction is same as Example 1, and difference is to change vanadyl acetylacetonate into ranadylic phthalocyanine, 2,5- Dichloroaniline yield is 75%, selectivity 88%.
Embodiment 5
Specific course of reaction is same as Example 1, and difference is to change vanadyl acetylacetonate into Cobalt Phthalocyanine, 2,5- bis- Chloroaniline yield is 68%, selectivity 80%.
Embodiment 6
Specific course of reaction is same as Example 1, and difference is to change vanadyl acetylacetonate into phthalocyanine molybdenum, 2,5- bis- Chloroaniline yield is 53%, selectivity 72%.
Embodiment 7
Specific course of reaction is same as Example 1, and difference is to change vanadyl acetylacetonate into porphines cobalt, 2,5- bis- Chloroaniline yield is 55%, selectivity 83%.
Embodiment 8
Specific course of reaction is same as Example 1, and difference is to change vanadyl acetylacetonate into porphines molybdenum, 2,5- bis- Chloroaniline yield is 42%, selectivity 65%.
Embodiment 9
Specific course of reaction is same as Example 1, and difference is to change vanadyl acetylacetonate into porphines vanadyl, 2,5- Dichloroaniline yield is 79%, selectivity 95%.
Embodiment 10
Specific course of reaction is same as Example 1, and difference is to change ammoniacal liquor into 13.8g hydroxylamine hydrochlorides, 2,5- bis- Chloroaniline yield is 38%, selectivity 65%.
Embodiment 11
Specific course of reaction is same as Example 1, and difference is to change ammoniacal liquor into 13.2g ammonium sulfate, 2,5- dichloros Aniline yield rate is 25%, selectivity 38%.
Embodiment 12
Specific course of reaction is same as Example 1, and difference is to change ammoniacal liquor into 9.6g ammonium carbonates, 2,5- dichloro-benzenes Amine yield is 22%, selectivity 51%.
Embodiment 13
Specific course of reaction is same as Example 1, and difference is to change ammoniacal liquor into 13.8g ammonium hydrogen carbonate, 2,5- bis- Chloroaniline yield is 18%, selectivity 45%.
Embodiment 14
Specific course of reaction is same as Example 1, and difference is to change ammoniacal liquor into 68g ammonias, 2,5- dichloroanilines Yield is 15%, selectivity 83%..
Embodiment 15
Specific course of reaction is same as Example 1, and difference is to change hydrogen peroxide into 10mL TBHPs, 2,5- dichloroaniline yields are 56%, selectivity 96%.
Embodiment 16
Specific course of reaction is same as Example 1, and difference is to change hydrogen peroxide into 280g air, 2,5- dichloro-benzenes Amine yield is 10%, selectivity 98%.
Embodiment 17
Specific course of reaction is same as Example 1, and difference is to change hydrogen peroxide into 160g oxygen, 2,5- dichloro-benzenes Amine yield is 13%, selectivity 76%.
Embodiment 18
Specific course of reaction is same as Example 1, and difference is to change acetonitrile into acetic acid, 2,5- dichloroaniline yields It is 45%, selectivity 82%.
Embodiment 19
Specific course of reaction is same as Example 1, and difference is to change acetonitrile into methyl alcohol, 2,5- dichloroaniline yields It is 33%, selectivity 78%.
Embodiment 20
Specific course of reaction is same as Example 1, and difference is to change acetonitrile into ethanol, 2,5- dichloroaniline yields It is 27%, selectivity 80%.
Embodiment 21
Specific course of reaction is same as Example 1, and difference is to change acetonitrile into water, and 2,5- dichloroaniline yields are 11%, selectivity 93%.
Embodiment 22
Specific course of reaction is same as Example 1, and difference is to change TBAB into tetrabutylammonium chloride, 2,5- dichloroaniline yields are 20%, selectivity 87%.
Embodiment 23
Specific course of reaction is same as Example 1, and difference is to change TBAB into etamon chloride, 2,5- dichloroaniline yields are 18%, selectivity 75%.
Embodiment 24
Specific course of reaction is same as Example 1, and difference is to change TBAB into tetraethylammonium bromide, 2,5- dichloroaniline yields are 15%, selectivity 82%.
Embodiment 25
Specific course of reaction is same as Example 1, and difference is to change TBAB into chlorination triethyl group benzyl Base ammonium, 2,5- dichloroaniline yields are 35%, selectivity 66%.
Embodiment 26
Specific course of reaction is same as Example 1, and difference is to make reaction temperature into 30 DEG C, 2,5- bis- from 90 DEG C Chloroaniline yield is 36%, selectivity 88%.
Embodiment 27
Specific course of reaction is same as Example 1, and difference is that from 5h are extended into 48h, 2,5- bis- reaction time Chloroaniline yield is 68%, selectivity 54%.
Embodiment 28
Specific course of reaction is same as Example 1, and difference is to make vanadyl acetylacetonate consumption into 0.2g, 2,5- Dichloroaniline yield is 78%, selectivity 90%.
Although detailing the present invention with preferred embodiment, but it is not intended to limit the present invention.Any this area Technical staff, without departing from the spirit and scope of the present invention, should with various modification can be adapted with change.Therefore Protection scope of the present invention should be considered as appending claims limited range.

Claims (8)

1. one kind prepares 2,5- dichloroaniline methods, it is characterised in that with Isosorbide-5-Nitrae-dichloro-benzenes as initiation material, with metal complex It is major catalyst, TS-1 molecular sieves and quaternary ammonium salt are co-catalyst, under the collective effect of oxidant, aminating agent and solvent, in 1-96h is reacted at 15-95 DEG C, 2,5- dichloroanilines are obtained, its yield spectra is in 10-95%.
2. the method for claim 1, it is characterised in that metal complex is vanadyl acetylacetonate, acetyl acetone, second One or more groups in acyl acetone cobalt, ranadylic phthalocyanine, phthalocyanine molybdenum, Cobalt Phthalocyanine, porphines cobalt, porphines molybdenum and porphines vanadyl Close.
3. the method for claim 1, it is characterised in that quaternary ammonium salt is TBAB, tetrabutylammonium chloride, tetrem One or more combinations in ammonium chloride, tetraethylammonium bromide and 3-ethyl benzyl ammonium chloride.
4. the method for claim 1, it is characterised in that oxidant is air, oxygen, hydrogen peroxide and tert-butyl hydroperoxide One or more combinations in hydrogen.
5. the method for claim 1, it is characterised in that aminating agent is ammoniacal liquor, ammonia, hydroxylamine hydrochloride, ammonium sulfate, carbonic acid One or more combinations in ammonium and ammonium hydrogen carbonate.
6. the method for claim 1, it is characterised in that solvent be one kind in water, acetonitrile, methyl alcohol, ethanol and acetic acid or More than one combinations.
7. the method for claim 1, it is characterised in that the mol ratio of oxidant, aminating agent and solvent and Isosorbide-5-Nitrae-dichloro-benzenes Respectively 0.1~50,0.2~50 and 0.5~100 (mass ratio).
8. the method for claim 1, it is characterised in that the use of metal complex catalysts, quaternary ammonium salt and TS-1 molecular sieves Amount is respectively 0.001~2%, 0.001~5% and 0.05~10% (mass ratio) of Isosorbide-5-Nitrae-dichloro-benzenes.
CN201611019543.3A 2016-11-16 2016-11-16 Preparation method of 2,5-dichloroaniline Pending CN106699571A (en)

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CN109092308A (en) * 2018-10-11 2018-12-28 中国天辰工程有限公司 A kind of extruded moulding method of silicon dioxide carried copper oxide catalyst
CN109574853A (en) * 2017-09-29 2019-04-05 普济生物科技（台州）有限公司 For synthesizing method, catalyst and its application of amino benzenes compounds
CN111004128A (en) * 2019-12-05 2020-04-14 宁波巨化化工科技有限公司 Production process of 3, 5-dichloroaniline

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109574853A (en) * 2017-09-29 2019-04-05 普济生物科技（台州）有限公司 For synthesizing method, catalyst and its application of amino benzenes compounds
CN109092308A (en) * 2018-10-11 2018-12-28 中国天辰工程有限公司 A kind of extruded moulding method of silicon dioxide carried copper oxide catalyst
CN111004128A (en) * 2019-12-05 2020-04-14 宁波巨化化工科技有限公司 Production process of 3, 5-dichloroaniline

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