CN109647530A - With the method for supported catalyst synthesis alpha-alcohol ketone intermediate - Google Patents

With the method for supported catalyst synthesis alpha-alcohol ketone intermediate Download PDF

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Publication number
CN109647530A
CN109647530A CN201811580721.9A CN201811580721A CN109647530A CN 109647530 A CN109647530 A CN 109647530A CN 201811580721 A CN201811580721 A CN 201811580721A CN 109647530 A CN109647530 A CN 109647530A
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Prior art keywords
supported catalyst
alcohol ketone
ketone intermediate
catalyst synthesis
alpha
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Inventor
王福泉
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Jiaocheng Zhaochen Coal Coke Co Ltd
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Jiaocheng Zhaochen Coal Coke Co Ltd
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    • 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
    • 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
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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

Abstract

The present invention relates to technical field of organic synthesis, and in particular to a method of alpha-alcohol ketone intermediate is synthesized with supported catalyst；Specially aromatic compound and acyl chlorides utilize the preparation method of load aluminum trichloride catalyst；Preparation method provided by the invention avoids directly using aluminum trichloride (anhydrous), avoids handling brought a large amount of acid waste waters containing aluminium after the reaction, simplifies process, technological operation is simple, in the case where environmental protection is increasingly harsh, meets the trend of green large-scale production.

Description

With the method for supported catalyst synthesis alpha-alcohol ketone intermediate
Technical field
The present invention relates to technical field of organic synthesis, and in particular to a kind of to synthesize alpha-alcohol ketone intermediate with supported catalyst Method.
Background technique
Alpha-hydroxy ketone is the chief component of ultraviolet photocureable material, be widely used in electronics, optical fiber, printing, The various fields such as packaging, adhesive, coating and composite material.Its representative products has 1173,184,651 and 2959 etc., these productions The features such as product are with efficiency of initiation height, the high and low smell of solubility, low pollution, stability are good, color inhibition, and solidify material in ultraviolet light It is used widely in material.
Under normal conditions, the intermediate for preparing Alpha-hydroxy ketone does catalyst, after reaction, body with aluminum trichloride (anhydrous) System becomes homogeneous, needs that cryosel acid solution is added into reaction solution to wash, and decomposes arone-aluminum chloride complex, then into one Step purification obtains product.Aluminum trichloride (anhydrous) is the higher catalyst of activity, but there is some ask in the actual production process Topic: 1) reaction needs the catalyst measured, and reacts and release a large amount of heat, to equipment requirement harshness；2) after reacting, reaction solution is in Homogeneously, complicated post-processing is needed；3) a large amount of acid is excluded in last handling process, alkali, causes environmental pollution；4) to production equipment It causes to corrode；5) for overactive aromatic ring and high activity raw material, the selectivity of reaction is not high.Therefore it finds environmentally safe Catalyst, develop more environmentally friendly process route and production technology, have realistic meaning.
Anhydrous AlCl3It is a kind of very high acylation catalyst of activity, it is big to there is catalyst amount in actual production, and three Fei Duo, not the disadvantages of recoverable, especially for the aromatic ring that some comparisons are active, using AlCl3Catalyst is made, is often selected Selecting property is not high, and the three wastes are especially more, so as to cause the waste of raw material and resource.
Other louis catalysts, cut both ways, TiCl4、SnCl4、BF3Diethyl ether solution price, and using dangerous； Anhydrous FeCl3 catalytic efficiency is relatively low.
Summary of the invention
The present invention is the catalyst AlCl used in the preparation method for solve existing alpha-alcohol ketone intermediate3, dosage is big, Three take more, and there are prices for not recyclable and other louis catalysts, and use unsafe technical problem, provide a kind of use The method that supported catalyst synthesizes alpha-alcohol ketone intermediate, by anhydrous AlCl3It is loaded to obtain support type on different carriers AlCl3, to make it have good regenerability and environmental-friendly performance.It avoids and directly uses aluminum trichloride (anhydrous) institute band The biggish factor of risk come avoids environmental protection, cost problem caused by the acid gas generated in reaction process and post-processing, makes Must operate becomes simple many, is more suitable for industrialized production.
In order to solve the above technical problems, the technical scheme adopted by the invention is as follows:
A method of alpha-alcohol ketone intermediate, the structural formula of the alpha-alcohol ketone intermediate such as formula I are synthesized with supported catalyst It is shown
Formula I
Wherein: Ar is selected to be replaced by C1-C12 alkyl, C1-C4 alkoxy, alkylthio group, halogen, cyano, 2- hydroxyl-oxethyl Phenyl ring or naphthalene nucleus；R1、R2It is respectively selected from C1-C7 alkyl or R1、R2Connect into the naphthenic base of C3-C8；
The following steps are included:
1) Ar is mixed with the acyl chlorides for drafting combination；
2) load alchlor is added in the mixed substance of step 1) to react, is vigorously stirred in reaction process；.
Further, the mass ratio of the material of acyl chlorides and Ar used is 1:5.
Further, the reaction of step 2 carries out in the presence of an organic.The acid of organic solvent reply structure shown in formula I has one Determine solvability, preferably low boiling point solvent, be conducive to lower consumption, facilitates recycling.
Preferably, the organic solvent is arene.
Preferably, the aromatic hydrocarbon is benzene or toluene.
Further, load alchlor used in step 2 is by the way that chloroform is added in carrier and is protected in argon gas Under, it adds aluminum trichloride (anhydrous) and is reacted, then through cooling, filtering, dry and be made.The carrier is SiO2, shell it is poly- Sugar, chitin, acetylated crustacyanin or resin.Preferably chitin and acetylated crustacyanin.
Further, the additional amount that alchlor is loaded in step 2 is the amount of the substance of mixed material in step 1) 1.1-1.5 times.
The method of supported catalyst synthesis alpha-alcohol ketone intermediate of the present invention, the reaction temperature of the step 2 are 0-60 DEG C, 25-35 DEG C of preferable temperature.
Further the alpha-alcohol ketone intermediate prepared by the method for supported catalyst synthesis alpha-alcohol ketone intermediate is 2- methyl-1-phenyl-1- acetone, cyclohexyl phenyl ketone, 1-(4-(2- hydroxy ethoxy) phenyl-2- methyl-1-acetone.
Compared with prior art the invention has the following advantages:
Compared with traditional traditional Friedel-Crafts reaction, preparation method of the present invention is had the advantages that
1 without consuming excessive water to decompose.
2) after reaction, by filtering or being centrifuged, most aluminium salts can be filtered, it is useless avoids the formation of a large amount of aluminium salt Liquid.
3) good dispersion degree, avoid hot-spot reaction, caused by risk factor.
4) the aluminium salt filter residue of carrier attachment, can after further treatment, recycling and reusing, and traditional aluminum trichloride (anhydrous) is then It is unrenewable.
5) reaction efficiency is higher, and yield is higher with purity, operates more easy thus whole more environmentally-friendly.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
AlCl3/ chitin, AlCl3The synthesis of/acetylated crustacyanin
It is ground with 200g, soda acid, washing, alcohol wash the chitin after processing and drying (at 100 DEG C, being dried in vacuo 1d), investment In 5000mL three-necked flask, the dried chloroform of 3000ml is added, under argon gas protection, is added 90g aluminum trichloride (anhydrous), at 60 DEG C 3d is reacted, is cooled to room temperature, under argon gas protection, filtering, 80 DEG C of vacuum drying 4h are put into the preservation of argon atmosphere chest.
Same method, the AlCl that can be made3/ acetylated crustacyanin.
Wherein AlCl3/ chitin, AlCl3The load capacity of/acetylated crustacyanin is 2.58mmol/g, 2.24mmol/g.
Embodiment 2
Cyclohexyl phenyl ketone (AlCl3/ chitin catalysis) synthesis
Weigh the 7.75g AlCl of the preparation of embodiment 13/ chitin (20mmol) is put into 100ml three-necked flask, argon gas protection Under, cyclohexyl formyl chloride (18mmol), benzene (90mmol) is added, is cooled to 10 degree, then heats to 25 DEG C, GC or TLC are detected Progress, after reaction, filtering, filtrate use 100ml ice water to handle again, and layering, washing is neutral, and anhydrous sodium sulfate dries, filters, Low-boiling point material is distilled, then further rectifying, obtains product.
The nuclear magnetic spectrogram data of products obtained therefrom are as follows:
1HNMR(400MHz,CDCl3):δ7.93(d,2H),7.55-7.48(m,H),7.49-7.41(m,2H),
3.31-3.20(m,1H),1.92-1.77(m,4H),1.78-1.70(m,1H),1.56-1.22(m,5H)。
Embodiment 3:
Cyclohexyl phenyl ketone (AlCl3/ acetylated crustacyanin catalysis) synthesis
Weigh the 8.93g AlCl of the preparation of embodiment 13/ acetylated crustacyanin (20mmol) is put into 100ml three-necked flask, argon gas Under protection, cyclohexyl formyl chloride (18mmol), benzene (90mmol) is added, is cooled to 10 degree, then heats to 35 DEG C, GC or TLC Detection progress, after reaction, filtering, filtrate use 100ml ice water to handle again, and layering, washing is neutral, and anhydrous sodium sulfate is dry, Low-boiling point material is distilled in filtering, and then further rectifying, obtains product.
The nuclear magnetic spectrogram data of products obtained therefrom are as follows:
1HNMR(400MHz,CDCl3):δ7.90(d,2H),7.56-7.49(m,H),7.51-7.40(m,2H),
3.30-3.19(m,1H),1.91-1.76(m,4H),1.77-1.68(m,1H),1.54-1.20(m,5H)。
Embodiment 4
2- methyl-1-phenyl-1- acetone (AlCl3/ chitin catalysis) synthesis
Weigh the 7.75g AlCl of the preparation of embodiment 13/ chitin (20mmol) is put into 100ml three-necked flask, argon gas protection Under, isobutyryl chloride (18mmol), benzene (90mmol) is added, is cooled to 10 degree, then heats to 60 DEG C, GC or TLC detect progress, After reaction, it filters, filtrate uses 100ml ice water to handle again, and layering, washing is neutral, and anhydrous sodium sulfate dries, filters, and distills Low-boiling point material, then further rectifying, obtains product.
The nuclear magnetic spectrogram data of products obtained therefrom are as follows:
1HNMR(400MHz,CDCl3):δ7.93(d,2H),7.53(t,H),7.45(t,2H),3.61-3.58(m,1H),1.22 (d,6H)。
Embodiment 5:
2- methyl-1-phenyl-1- acetone (AlCl3/ acetylated crustacyanin catalysis) synthesis
Weigh the 8.93g AlCl of the preparation of embodiment 13/ acetylated crustacyanin (20mmol) is put into 100ml three-necked flask, argon gas Under protection, isobutyryl chloride (18mmol), benzene (90mmol) is added, is cooled to 10 degree, then heats to 40 DEG C, GC or TLC are detected Progress, after reaction, filtering, filtrate use 100ml ice water to handle again, and layering, washing is neutral, and anhydrous sodium sulfate dries, filters, Low-boiling point material is distilled, then further rectifying, obtains product.
The nuclear magnetic spectrogram data of products obtained therefrom are as follows:
1HNMR(400MHz,CDCl3):δ7.92(d,2H),7.52(t,H),7.46(t,2H),3.63-3.61(m,1H),1.24 (d,6H)。

Claims (10)

1. a kind of method with supported catalyst synthesis alpha-alcohol ketone intermediate, the structural formula such as formula of the alpha-alcohol ketone intermediate Shown in I
Formula I
Wherein: Ar is selected to be replaced by C1-C12 alkyl, C1-C4 alkoxy, alkylthio group, halogen, cyano, 2- hydroxyl-oxethyl Phenyl ring or naphthalene nucleus；R1、R2It is respectively selected from C1-C7 alkyl or R1、R2Connect into the naphthenic base of C3-C8;
Characterized by comprising the following steps:
1) Ar is mixed with the acyl chlorides for drafting combination；
2) load alchlor is added in the mixed substance of step 1) to react, is vigorously stirred in reaction process；.
2. the method according to claim 1 with supported catalyst synthesis alpha-alcohol ketone intermediate, which is characterized in that used The mass ratio of the material of acyl chlorides and Ar are 1:5.
3. the method according to claim 1 with supported catalyst synthesis alpha-alcohol ketone intermediate, which is characterized in that step 2) reaction carries out in the presence of an organic.
4. the method according to claim 3 with supported catalyst synthesis alpha-alcohol ketone intermediate, which is characterized in that institute Stating organic solvent is arene.
5. the method according to claim 4 with supported catalyst synthesis alpha-alcohol ketone intermediate, which is characterized in that institute Stating organic solvent is benzene or toluene.
6. the method according to claim 1 with supported catalyst synthesis alpha-alcohol ketone intermediate, which is characterized in that step 2) load alchlor used in be by the way that chloroform and under protection of argon gas is added in carrier, add aluminum trichloride (anhydrous) into Capable reaction is dried and is made then through cooling, filtering.
7. the method according to claim 1 with supported catalyst synthesis alpha-alcohol ketone intermediate, which is characterized in that step 2) additional amount of load alchlor is 1.1-1.5 times of the amount of the substance of mixed material in step 1) in.
8. the method according to claim 6 with supported catalyst synthesis alpha-alcohol ketone intermediate, which is characterized in that described Carrier is SiO2, chitosan, chitin, acetylated crustacyanin or resin.
9. the method according to claim 1 with supported catalyst synthesis alpha-alcohol ketone intermediate, which is characterized in that described The reaction temperature of step 2 is 0-60 DEG C.
10. the method according to claim 1 with supported catalyst synthesis alpha-alcohol ketone intermediate, which is characterized in that institute Stating alpha-alcohol ketone intermediate is 2- methyl-1-phenyl-1- acetone, cyclohexyl phenyl ketone, 1-(4-(2- hydroxy ethoxy) phenyl- 2- methyl-1-acetone.
CN201811580721.9A 2018-12-24 2018-12-24 With the method for supported catalyst synthesis alpha-alcohol ketone intermediate Pending CN109647530A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482834A1 (en) * 1990-10-20 1992-04-29 Takasago International Corporation Process for producing alpha-hydroxyketones
CN101125807A (en) * 2007-08-20 2008-02-20 常州沃富斯农化有限公司 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone and preparation method for intermediate thereof
CN101333263A (en) * 2008-07-30 2008-12-31 南通新昱化工有限公司 Macromolecule polyfunctional alpha-alcohol ketone photoinitiator and producing method thereof
CN101643398A (en) * 2009-09-07 2010-02-10 湖南先伟实业有限公司 Preparation method of 2,3,4,4'-tetrahydroxyldiphenylketone
CN101786016A (en) * 2010-03-06 2010-07-28 中北大学 Preparation method and application method of novel immobilized Lewis acid catalyst
CN102015603A (en) * 2008-05-09 2011-04-13 蓝宝迪有限公司 Process for the preparation of aromatic alpha-hydroxy ketones
CN102020726A (en) * 2010-11-18 2011-04-20 长沙新宇高分子科技有限公司 Macromolecule difunctional group alpha-hydroxy-ketone photoinitiator and preparation method thereof
CN102320946A (en) * 2011-07-19 2012-01-18 湖北工业大学 Preparation method of 2-hydroxy arone compound
CN104591991A (en) * 2014-12-05 2015-05-06 沈阳师范大学 Preparation method for hydroxy ketone bifunctional photoinitiator

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482834A1 (en) * 1990-10-20 1992-04-29 Takasago International Corporation Process for producing alpha-hydroxyketones
CN101125807A (en) * 2007-08-20 2008-02-20 常州沃富斯农化有限公司 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone and preparation method for intermediate thereof
CN102015603A (en) * 2008-05-09 2011-04-13 蓝宝迪有限公司 Process for the preparation of aromatic alpha-hydroxy ketones
CN101333263A (en) * 2008-07-30 2008-12-31 南通新昱化工有限公司 Macromolecule polyfunctional alpha-alcohol ketone photoinitiator and producing method thereof
CN101643398A (en) * 2009-09-07 2010-02-10 湖南先伟实业有限公司 Preparation method of 2,3,4,4'-tetrahydroxyldiphenylketone
CN101786016A (en) * 2010-03-06 2010-07-28 中北大学 Preparation method and application method of novel immobilized Lewis acid catalyst
CN102020726A (en) * 2010-11-18 2011-04-20 长沙新宇高分子科技有限公司 Macromolecule difunctional group alpha-hydroxy-ketone photoinitiator and preparation method thereof
CN102320946A (en) * 2011-07-19 2012-01-18 湖北工业大学 Preparation method of 2-hydroxy arone compound
CN104591991A (en) * 2014-12-05 2015-05-06 沈阳师范大学 Preparation method for hydroxy ketone bifunctional photoinitiator

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Application publication date: 20190419