CN110078691A - The recovery method of catalyst in a kind of heterocyclic Friedel-Crafts reaction - Google Patents
The recovery method of catalyst in a kind of heterocyclic Friedel-Crafts reaction Download PDFInfo
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- CN110078691A CN110078691A CN201910365865.0A CN201910365865A CN110078691A CN 110078691 A CN110078691 A CN 110078691A CN 201910365865 A CN201910365865 A CN 201910365865A CN 110078691 A CN110078691 A CN 110078691A
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- alchlor
- reaction
- aluminium
- friedel
- amine complex
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- 238000005727 Friedel-Crafts reaction Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 24
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title description 11
- 238000011084 recovery Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- 239000004411 aluminium Substances 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004064 recycling Methods 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008929 regeneration Effects 0.000 claims abstract description 9
- 238000011069 regeneration method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000003480 eluent Substances 0.000 claims abstract description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 150000008365 aromatic ketones Chemical class 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000012530 fluid Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- -1 aluminium amine Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims 1
- 150000001555 benzenes Chemical class 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 abstract description 6
- 230000003213 activating effect Effects 0.000 abstract description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004577 thatch Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- AFEHRRMDHLUKNM-UHFFFAOYSA-N C1=CC=C(C=C1)C2=C(C=CC=C2Cl)C(=O)Cl Chemical compound C1=CC=C(C=C1)C2=C(C=CC=C2Cl)C(=O)Cl AFEHRRMDHLUKNM-UHFFFAOYSA-N 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- MZJJVLUJDRSMRX-UHFFFAOYSA-N 1-benzothiophene;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2SC=CC2=C1 MZJJVLUJDRSMRX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000003143 atherosclerotic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 238000005648 named reaction Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- SGDMQXAOPGGMAH-UHFFFAOYSA-N phenol;thiophene Chemical class C=1C=CSC=1.OC1=CC=CC=C1 SGDMQXAOPGGMAH-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
-
- 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 invention discloses a kind of methods of alchlor in recycling heterocyclic Friedel-Crafts reaction, it is under argon gas or nitrogen protection, solvent is added in heterocyclic Friedel-Crafts reaction container, sequentially add alchlor, substituted benzene, replace acyl chlorides, 0.5~10h is stirred to react under the conditions of -30~80 DEG C, aminate is being directly added into reaction system, 0.5~10h is stirred to react under the conditions of -30~80 DEG C, filtering, separation, solid is the amine complex of aluminium, filtered fluid is corresponding aromatic ketone product solution, solid is eluted with solvent identical with reaction system, eluent and product solution merging treatment, regeneration treatment is carried out to the amine complex of aluminium, obtain alchlor and aminate, the present invention breaks the complex system of product and alchlor in Friedel-Crafts reaction, form the amine complex of new aluminium, make Product is separated with alchlor, carries out regeneration activating to the amine complex of aluminium, new alchlor and complexing agent are prepared in separation, and it can be used repeatedly for the alchlor and complexing agent of recycling.
Description
Technical field
The invention belongs to methodology of organic synthesis technical fields, more particularly, to a kind of anti-with the amine complexing agent recycling Fu Ke of aluminium
The method for answering middle aluminum trichloride catalyst.
Background technique
Friedel-Crafts reaction is one of the classical name reaction in organic synthesis, is existed in lewis acids such as aluminum trichloride (anhydrous)s
Under, aromatic hydrocarbons and alkyl halide act on, and electrophilic substitution reaction occur on aromatic ring, hydrogen atom is replaced by alkyl, generates alkylaromatic hydrocarbon
Reaction, referred to as one Crafts alkylation of Fu's column Dare reaction (Friedel-Crafts alkylation)；Aromatic hydrocarbons and carboxylic acid halides or
Acid anhydrides acts on, and the hydrogen atom on aromatic ring is replaced by acyl group, generates the reaction of arone, and referred to as Fu's column Dare~Kerafyrm thatch is acylated
It reacts (Friede-Crafts acylation).The reaction of Fu column Dare Kerafyrm thatch is alkylation and acylation reaction, is referred to as
Fu column Dare Kerafyrm thatch reacts abbreviation Friedel-Crafts reaction, is widely used in the synthesis of aromatic ketone.But its post-processing approach is related to
Acidic materials cause aluminium wastewater largely to generate, and processing difficulty causes serious pollution to the environment.Its common processing method is as follows:
1, a certain amount of water after the reaction was completed, is pre-chilled, is slowly added thereto reaction solution, is put when continuous cooling is to exclude to be quenched
Heat out, the acid gas generated when being quenched is mainly quenched the absorption of the water in system, until being quenched completely；After the reaction was completed, with
Ice water or brine ice cooling, are slowly added dropwise water, the heat released when continuous cooling is to exclude to be quenched, the acid gas master generated when being quenched
The water being quenched in system absorbs, until being quenched completely；
2, it is directly poured into when lab scale in the trash ice that a small amount of concentrated hydrochloric acid is added, end is quenched within 3-5 minutes, liquid separation simultaneously extracts, rotation
Dry and crude product.1kg is identical as lab scale when operating, and quenching time 0.5 hour；When 5kg processing, a certain amount of water is pre-cooled in 2-5
Degree, low vacuum are repeatedly pumped into reaction solution to be quenched, and investment speed is determined by temperature in the kettle, and quenching time 3 hours；150 kilograms
When, with 5kg operating method, quenching time 8 hours.The initiation of vacuum is not only to be pumped into the necessary condition of reaction solution in kettle, and
The acid gas escaped in kettle is extracted out together, operates smoke-free and tasteless.
Wherein the aluminium ion in catalyst alchlor is the key factor for influencing treatment process, and aluminium ion is both sexes chemical combination
Object generates meta-aluminic acid under acid condition, and water is readily soluble；Aluminium hydroxide is generated under alkaline condition, is insoluble in water, and forms aluminium hydroxide
Afterwards, it and is difficult to be completely converted into meta-aluminic acid.Here it is many Friedel-Crafts reactions (friedel-crafts reaction) in processing, encounters floccule and congee
The reason of shape object, extremely hardly possible is filtered again partially.It once encountered 2 tons of reaction kettle to be quenched by 2 methods, and obtained a kettle atherosclerotic object, at all
Filter motionless, after being handled under high pressure with filter press, still with the presence of superfine micro- insoluble matter, finally helpless natural subsidence one week, is taken
Upper layer, the batt layer comprising portion of product discard in vain.To avoid generating floccule, improved processing method is in the water of pre-cooling
A certain proportion of hydrochloric acid is added, usually adds by 1:50, is i.e. 50 parts of water, a concentrated hydrochloric acid is added.The side of further save the cost
Method is to replace hydrochloric acid with the water for absorbing this reaction end gas, effect is identical.The property of product determines the processing side after reaction is quenched
Method.For product insoluble or sl. sol. in solvent and sour water, directly filters, wash and dry, obtain crude product, here situation ratio
It is more rare；For dissolution or readily soluble product in solvent, direct liquid separation, a small amount of solvent extraction water phase, salt washes organic phase, dry
Dry, precipitation obtains crude product, and the overwhelming majority, which reacts, is applicable in such case；For in sour water dissolution or it is readily soluble, repeatedly extracted with solvent
It takes, dry and precipitation obtains crude product, such case is difficult to see substantially.
The Friedel-Crafts reaction of Aluminium Trichloride as Catalyst is widely used, but its post-processing is always the project that everybody studies.No matter adopting
With which kind of above-mentioned post-processing approach, the processing of aluminium wastewater is the core environmental issue for needing to solve.Aluminium wastewater most has at present
The processing method of effect is to be prepared into containing aluminium flocculating agent, and the flocculation for wastewater treatment plant needs.But it does not solve fundamentally
The recycling problem of aluminium, a large amount of aluminium ions are still discharged in water, cause the loss and environment water pollution of aluminium.Therefore how to make Fu Ke anti-
Aluminum trichloride catalyst in answering obtains recycling Reusability, is always scholar and expert's problem of concern in the industry,
To very good solution, research significance is very great.
Summary of the invention
Trichlorine in a kind of recycling heterocyclic Friedel-Crafts reaction is provided it is an object of the invention to improve the deficiency of prior art
The method for changing aluminium, selects the complexing agent of suitable aluminium, breaks the complex system of product and alchlor in Friedel-Crafts reaction, formed new
The amine complex of aluminium, separates product with alchlor, carries out regeneration activating to the amine complex of aluminium, new three are prepared in separation
Aluminium chloride and complexing agent, it can be used repeatedly for the alchlor and complexing agent of recycling.
The object of the present invention is achieved like this, a method of alchlor in recycling heterocyclic Friedel-Crafts reaction, it is special
Point is that solvent is added in heterocyclic Friedel-Crafts reaction container under argon gas or nitrogen protection, sequentially adds alchlor, replaces
Benzene replaces acyl chlorides, is stirred to react 0.5~10h under the conditions of -30~80 DEG C, aminate is being directly added into reaction system,
0.5~10h is stirred to react under the conditions of -30~80 DEG C, filtering, separation, solid is the amine complex of aluminium, and filtered fluid is corresponding
Aromatic ketone product solution elutes solid with solvent identical with reaction system, eluent and product solution merging treatment,
Regeneration treatment is carried out to the amine complex of aluminium, obtains alchlor and aminate, the solvent is methylene chloride, two chloroethenes
The long one kind of alkane, nitrobenzene, carbon disulfide, the aminate are one of ammonia, liquefied ammonia, ammonium chloride；It is specific as follows anti-
It answers shown in formula:
Reaction equation 1:
Reaction equation 2:
Reaction equation 3:
In formula: R1、R2、R3、R4、R5It can be separately or concurrently are as follows: various alkyl, alkoxy, aryl, cyclohexyl, alkyl
Cyclohexyl, the aryl that aryl, alkyl-substituted cyclohexyl, the alkoxy of substituted aryl, alkoxy substitution replace replace
Cyclohexyl, hydrogen substituent group.
In order to further realize the purpose of the present invention, reaction material ratio can be are as follows: replace acyl chlorides: alchlor: solvent: amine
Compound=1mol:0.5~5mol:10~5000ml:0.5~20mol.
In order to further realize the purpose of the present invention, can be the amine complex to aluminium carry out regeneration treatment be
Under nitrogen or the protection of argon gas or vacuum state, the amine complex of aluminium is added in reaction vessel or reaction bed, stirring, control temperature
Degree reacts 0~20h between 40~500 DEG C, heats regeneration treatment, and aminate and tri-chlorination are collected in reaction of decomposing respectively
Aluminium.
Compared with the prior art the present invention has following distinguishing feature and a good effect: 1. the present invention is based on alchlor works
It is used in Friedel-Crafts reaction for catalyst, using the ammino-complex of aluminium, alchlor in complex reaction system makes alchlor
It is separated with product, achievees the purpose that recycle alchlor, the alchlor of recycling can be repeatedly used for the reaction, it is possible to reduce three
The whole usage amount of aluminium chloride.
2. the present invention has preferable environment friendly, the process being hydrolyzed in the past using acid water is avoided, is reduced
Harm of the acid brine waste of Friedel-Crafts reaction post-processing to environment；
The specific data comparison of the method for the present invention and traditional treatment method is as follows:
Statistics indicate that the present invention can have effectively to using alchlor to do the alchlor in the Friedel-Crafts reaction of catalyst
Recovering effect, can be widely applied in such reaction.
Maximum feature of the invention is: the alchlor in reaction system is recycled, and it can be used repeatedly.With previous report
There is biggish difference in road, does not use acid water hydrolysis, reduces harm of the brine waste to environment.
Specific embodiment
The present invention is further described with reference to embodiments, it should be noted that embodiment below is only for clear
Understand the present invention, the present invention is not limited to this embodiment.
Properties of product test item and test equipment:
Thermogravimetric analysis is tested by Oniversal V2.4F TA Instruments type thermogravimetric analyzer, and DSC is by TA DSC
The measurement of Q20 type differential scanning instrument.
Absorption spectrum is measured by UV-4802 type dual-beam ultraviolet-uisible spectrophotometer, fluorescence spectrum and fluorescent quantum effect
Rate is by 970CRT fluorescence spectrophotometer measurement.
Japanese Shimadzu LC-10ATvp type high pressure liquid chromatograph (methanol: acetonitrile=2:1, flow velocity 1ml/min)；Day island proper
Saliva GC-14C, GC-17A gas chromatograph (DB-1 type pillar)；Japanese Shimadzu GCMS-2014C type mass spectrograph.
Embodiment 1, a method of alchlor in recycling heterocyclic Friedel-Crafts reaction, the present embodiment is for recycling benzo
The method of catalyst alchlor, route are as follows in pentanone Friedel-Crafts reaction:
In formula: R1、R2、R3、R4、R5For H base.
Reaction process: under argon gas protection, alchlor 74.2g, methylene chloride 50ml are sequentially added into there-necked flask, cooling
To -30 DEG C, 120g 2- phenyl-chlorobenzoyl chloride is added dropwise, is added dropwise, -30 DEG C stirring insulation reaction 1 hour.Into reaction flask
Ammonia 29g is added, stirs 2h.Solid is precipitated, filters, drying obtains the amine complex 92g of aluminium after filter cake dichloromethane eluent.
Filtrate concentration, obtains benzo pentanone 97g, yield 98%.
Alchlor recycling: into three-necked flask, the amine complex 92g of aluminium is sequentially added, opens stirring, vacuum state
Under, it is heated to 400 DEG C, keeps the temperature 3h, after Temperature fall, obtain alchlor 74g, yield 100%.Fusing point: 190-192
℃.It is collected simultaneously ammonia 27g.It is recycled and reused for above-mentioned reaction, identification confirms that the alchlor of recycling may be reused.
Embodiment 2, a method of alchlor in recycling heterocyclic Friedel-Crafts reaction, the present embodiment is for recycling benzo
The method of catalyst alchlor, route are as follows in thiophene phenols Friedel-Crafts reaction:
In formula: R1、R2, be H base.
Reaction process: under argon gas protection, alchlor 74.2g, methylene chloride 50ml are sequentially added into there-necked flask, cooling
To -30 DEG C, 128.2g 5- substituent group-valeric chloride is added dropwise, is added dropwise, -30 DEG C stirring insulation reaction 1 hour.To reaction flask
Middle addition ammonia 29g stirs 2h.Solid is precipitated, filters, drying obtains the amine complex of aluminium after filter cake dichloromethane eluent
92g.Filtrate concentration, obtains benzo thiophene phenol and hept- 1- ketone 107g, yield 98%.
Alchlor recycling: into three-necked flask, the amine complex 92g of aluminium is sequentially added, opens stirring, vacuum state
Under, it is heated to 400 DEG C, keeps the temperature 3h, after Temperature fall, obtain alchlor 74g, yield 100%.Fusing point: 190-193
℃.It is collected simultaneously ammonia 27g.It is recycled and reused for above-mentioned reaction, identification confirms that the alchlor of recycling may be reused.
Embodiment 3, a method of alchlor in recycling heterocyclic Friedel-Crafts reaction, the present embodiment is for recycling benzo
The method of catalyst alchlor, route are as follows in pentanone Friedel-Crafts reaction:
In formula: R1、R2For H base.
Reaction process: under argon gas protection, alchlor 74.2g, methylene chloride 50ml are sequentially added into there-necked flask, cooling
To -30 DEG C, 125.9g 2- phenyl-chlorobenzoyl chloride is added dropwise, is added dropwise, -30 DEG C stirring insulation reaction 1 hour.To reaction flask
Middle addition ammonia 35g stirs 2h.Solid is precipitated, filters, drying obtains the amine complex of aluminium after filter cake dichloromethane eluent
109.2g.Filtrate concentration, obtains benzofuran and cycloheptyl -1- ketone 103.3g, yield 97%.
Alchlor recycling: into three-necked flask, the amine complex 109.2g of aluminium is sequentially added, opens stirring, vacuum shape
Under state, it is heated to 400 DEG C, keeps the temperature 3h, after Temperature fall, obtains alchlor 74g, yield 100%.Fusing point: 190-193
℃.It is collected simultaneously ammonia 27g.It is recycled and reused for above-mentioned reaction, identification confirms that the alchlor of recycling may be reused.
Claims (3)
1. a kind of method of alchlor in recycling heterocyclic Friedel-Crafts reaction, it is characterized in that under argon gas or nitrogen protection, miscellaneous
Solvent is added in ring class Friedel-Crafts reaction container, sequentially adds alchlor, substituted benzene, replace acyl chlorides, in -30~80 DEG C of conditions
Under be stirred to react 0.5~10h, aminate is being directly added into reaction system, is being stirred to react 0.5 under the conditions of -30~80 DEG C
~10h, filtering, separation, solid be aluminium amine complex, filtered fluid be corresponding aromatic ketone product solution, to solid with it is anti-
The identical solvent of system is answered to be eluted, eluent and product solution merging treatment carry out regeneration treatment to the amine complex of aluminium,
Obtain alchlor and aminate, one kind that the solvent is methylene chloride, dichloroethanes, nitrobenzene, carbon disulfide are long, institute
The aminate stated is one of ammonia, liquefied ammonia；Shown in reaction equation specific as follows:
Reaction equation 1:
Reaction equation 2:
Reaction equation 3:
In formula: R1、R2、R3、R4、R5It can be separately or concurrently are as follows: various alkyl, alkoxy, aryl, cyclohexyl, alkyl replace
Aryl, alkoxy replace aryl, alkyl-substituted cyclohexyl, alkoxy replace cyclohexyl, aryl replace ring
Hexyl, hydrogen substituent group.
2. a kind of method for recycling alchlor in heterocyclic Friedel-Crafts reaction according to claim 1, it is characterised in that: reaction
Expect ratio are as follows: replace acyl chlorides: alchlor: solvent: aminate=1mol:0.5~5mol:10~5000ml:0.5~20mol.
3. a kind of method for recycling alchlor in heterocyclic Friedel-Crafts reaction according to claim 1, it is characterised in that: described
To carry out regeneration treatment to the amine complex of aluminium, by the amine complex of aluminium, added under nitrogen or the protection of argon gas or vacuum state
Enter in reaction vessel or reaction bed, stirring, control temperature react 0~20h between 40~500 DEG C, heat regeneration treatment, occur
Aminate and alchlor are collected in decomposition reaction respectively.
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| CN111892548A (en) * | 2020-07-24 | 2020-11-06 | 利安隆（中卫）新材料有限公司 | Process for preparing 2,4, 6-tris (2-hydroxy-4-n-hexyloxyaryl) -1,3, 5-triazine and intermediates thereof |
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