CN104649890A - Preparation method of 2,4-dichloro-5-fluorobenzoyl chloride - Google Patents
Preparation method of 2,4-dichloro-5-fluorobenzoyl chloride Download PDFInfo
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- CN104649890A CN104649890A CN201510083439.XA CN201510083439A CN104649890A CN 104649890 A CN104649890 A CN 104649890A CN 201510083439 A CN201510083439 A CN 201510083439A CN 104649890 A CN104649890 A CN 104649890A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
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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
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
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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
- 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
Abstract
The invention relates to a method for synthesizing 2,4-dichloro-5-fluorobenzoyl chloride suitable for industrialized production. According to the method, the yield of the product can be further increased, a process route can be simplified, and the method is suitable for industrialized production.
Description
Technical field
The present invention relates to the method for the chloro-5-fluorobenzoyl chloride of a kind of synthesis 2,4-bis-, particularly relate to a kind of working load phospho-wolframic acid/ZrO
2the method of zeolite magnetic coupling carried catalyst synthesis 2,4-bis-chloro-5-fluorobenzoyl chloride.
Background technology
2,4-bis-chloro-5-fluorobenzoyl chloride molecular formula is C
7h
2cl
3fO, molecular weight is 227.5, No. CAS is 86393-34-2.2,4-bis-chloro-5-fluorobenzoyl chloride is generally colourless or micro-yellow liquid, and boiling point is 143-144 DEG C (35mmHg).Mainly as medicine intermediate, for the synthesis of the medicines such as Broad spectrum antibiotics Ciprofloxacin, antipsychotic drug Triperidol.
Because the demand of 2,4-bis-chloro-5-fluorobenzoyl chloride is increasing, develop multiple synthesis route.
The people (" 2; synthesis of the chloro-5-fluorobenzoyl chloride of 4-bis-" such as Bian name, the people such as Bian name, chemical engineer, the 6th phase in 2007,48-49 and 64 page) to several 2,4-bis-chloro-5-fluorobenzoyl chloride synthetic method is commented, and first uses 2,4 dichloro fluorobenzene synthesis 2, the chloro-5-fluorobenzoic acid of 4-bis-, then uses thionyl chloride to carry out chloride.Wherein in the chloro-5-fluorobenzoic acid of synthesis 2,4-bis-, refer to and use 2,4 dichloro fluorobenzene to be raw material, with AlCl
3for catalyzer with NaClO solution for the chloro-5-fluorobenzoic acid of 2,4-bis-prepared by oxygenant, yield is 80%.In the method for the chloro-5-fluorobenzoic acid of other synthesis 2,4-bis-, use nitric acid, sulfuric acid and hydrogen peroxide as oxygenant, or employ cyanidization agent, or use diazotization process.But AlCl
3easy distillation cohesion also absorbs water from air, and unfavorable to reaction, nitric acid, sulfuric acid and hydrogen peroxide propose higher requirement as oxygenant to reactor, and needed for fluoro diazonium salt, decomposition temperature is higher, and overall yield of reaction is lower.
People's (" Ciprofloxacin intermediates 2 such as temperature new people, the synthesis of the chloro-5-fluorobenzoyl chloride of 4-bis-", the people such as temperature new people, Jining Medical College journal, 23rd volume the 2nd phase, 21-22 page, 2000 06 month) propose a kind of 2, the preparation method of the chloro-5-fluorobenzoyl chloride of 4-bis-, first 1 is used, the chloro-4-fluorobenzene of 3-bis-and Acetyl Chloride 98Min. react preparation 2 under the existence of aluminum chloride, the chloro-5-fluoro acetophenone of 4-bis-, then 2, the chloro-5-fluoro acetophenone of 4-bis-prepares 2 under nitric acid effect, the chloro-5-fluorobenzoic acid of 4-bis-, last 2, the chloro-5-fluorobenzoic acid of 4-bis-uses thionyl chloride acidylate to prepare 2, the chloro-5-fluorobenzoyl chloride of 4-bis-.But thionyl chloride very easily reacts with water, needs absolute guarantee anhydrous in acylation reaction, oxidizing reaction needs to carry out under the existence of excessive nitric acid.
US5241111A discloses 2,4 dichloro fluorobenzene at AlCl
3with CCl under catalysis
4trichloromethyl is introduced in reaction, then adds H
2sO
4hydrolysis obtain the chloro-5-fluorobenzoic acid of 2,4-bis-, then with SOCl
2chloride obtains the chloro-5-fluorobenzoyl chloride of 2,4-bis-.The method the first step generates the by product (FCl of about 30%
2c
6h
2)
2cCl
2, cause product separation difficulty, poor product quality.Meanwhile, the method use thionyl chloride, and thionyl chloride very easily reacts with water, need absolute guarantee anhydrous in acylation reaction.
As above all there is the problems such as operational path is long, the use of severe poisonous chemicals, yield in existing technique, is difficult to realize suitability for industrialized production.
Summary of the invention
For the above-mentioned problems in the prior art, technical problem to be solved by this invention is to provide a kind of synthesis 2 being suitable for suitability for industrialized production newly, the method of the chloro-5-fluorobenzoyl chloride of 4-bis-, for this purpose, the technical solution used in the present invention is: first with 2,4-dichlor fluorbenzene is raw material, 2 are obtained with carbon tetrachloride reaction under the existence of composite zeolite solid super acid catalyst, 4-bis-chloro-5-fluorine trichlorotoluene zotrichloride, then under the catalytic condition of iron trichloride, be obtained by reacting the chloro-5-fluorobenzoyl chloride of 2,4-bis-.The present invention can improve product yield further, and avoids the use of the strong acid such as sulfuric acid, nitric acid, hydrochloric acid and severe poisonous chemicals, simplifies operational path, is suitable for suitability for industrialized production.
According to one embodiment of the invention, the invention provides the method for the chloro-5-fluorobenzoyl chloride of a kind of synthesis 2,4-bis-, said method comprising the steps of:
(A) in reactor, add 2,4 dichloro fluorobenzene, composite zeolite solid super acid catalyst and tetracol phenixin, back flow reaction obtains 2,4-bis-chloro-5-fluorine trichlorotoluene zotrichloride;
(B) by reactor cooling to room temperature, directly add deionized water without product separation, at 20-40 DEG C hydrolysis obtain the chloro-5-fluorobenzoyl chloride of 2,4-bis-.
According to one embodiment of the invention, invention furthermore provides the method for the chloro-5-fluorobenzoyl chloride of a kind of synthesis 2,4-bis-, said method comprising the steps of:
(A) in reactor, add 2,4 dichloro fluorobenzene, composite zeolite solid super acid catalyst and tetracol phenixin, back flow reaction obtains 2,4-bis-chloro-5-fluorine trichlorotoluene zotrichloride;
(B) by reactor cooling to room temperature, directly add deionized water and iron(ic) chloride without product separation, at 20-40 DEG C hydrolysis obtain the chloro-5-fluorobenzoyl chloride of 2,4-bis-.
According to one embodiment of the invention, relative to every mole 2 in step (A), 4-dichlor fluorbenzene uses 40-200 gram of composite zeolite solid super acid catalyst, preferably uses 80-150 gram of composite zeolite solid super acid catalyst relative to every mole of 2,4 dichloro fluorobenzene.
According to one embodiment of the invention, in step (A), the mol ratio of tetracol phenixin and 2,4 dichloro fluorobenzene is 10:1.
According to one embodiment of the invention, composite zeolite solid super acid catalyst used in this application is prepared as follows: step 1: Natural Zeolite Support pre-treatment; Step 2: synthesizing porous level zeolite; Step 3: the magnetic of zeolite is modified; Step 4: prepare load phosphotungstic acid/ZrO
2zeolite magnetic coupling carried catalyst.
Step 1 carries out the pre-treatment of Natural Zeolite Support, comprises following operation:
(1.1) to Natural Zeolite Support after 450 DEG C of-650 DEG C of calcination process, carry out exchange process with the ammonium salt solution containing ammonium nitrate, volatile salt or ammonium sulfate that ammonium concentration is 0.05 ~ 1.0mol/L, the liquid-solid volume ratio of ammonium salt solution and zeolite is 3:1 ~ 5:1; Swap time is 30 minutes to 60 hours, the zeolite after exchanging with deionized water wash, then carries out drying and 450 DEG C-650 DEG C calcination process again;
(1.2) carrier reaming: the zeolite that step (1.1) obtains is put into HCl, HNO that concentration is 0.05 ~ 6mol/L
3, H
2sO
4or the solution of citric acid; Soak 6-10 hour, with deionized water wash to neutral, dry, obtain pretreated carrier 450 DEG C of-650 DEG C of roastings.
According to one embodiment of the invention, wherein said natural zeolite is mordenite, natrolite, chabazite, faujusite, is preferably mordenite.
Step 2 carries out the synthesis of porous level zeolite, comprises following operation:
(2.1) under protection of inert gas, comonomer and initiator are joined dissolving in medium and obtain reaction solution, and in 70 ~ 80 DEG C of reaction 6 ~ 10h, obtain the dispersion system of polymer microballoon;
(2.2) mix by the mass ratio 1: 10 ~ 20: 0.5 ~ 3 of dispersion system, silicon sol, non-silicon sol, then stir, at room temperature naturally place, to complete its gelation process;
(2.3) again through centrifugation, be cooled to room temperature, washing, suction filtration, drying, 450 DEG C of-650 roasting obtain porous level zeolite;
Wherein, described comonomer is vinyl monomer, comprises maleic anhydride, vinylbenzene and vinyl acetate between to for plastic, and the mol ratio of comonomer is maleic anhydride: vinylbenzene: vinyl acetate between to for plastic is 1:1-2:1-2, and in reaction solution, the mass concentration of monomer is 10% ~ 30%;
Described initiator is organo-peroxide or azo-compound, the preferred dialkyl peroxide of organic peroxide evocating agent (such as di-t-butyl peroxide, dicumyl peroxide), acyl class superoxide (such as dibenzoyl peroxide, lauroyl peroxide), hydroperoxide (such as isopropyl benzene hydroperoxide, tertbutyl peroxide), ester class superoxide (such as peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester), two carbonic ether superoxide (such as di-isopropyl peroxydicarbonates, di-cyclohexylperoxy dicarbonate), the preferred Diisopropyl azodicarboxylate of azoic compound initiator (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile), in reaction solution, the mass concentration of initiator is 0.1% ~ 0.5%.
Described medium is C
1-C
12the mixing solutions of alkyl alcohol and acetone, volume ratio is: 1:1-1.5.Wherein said C
1-C
12alkyl alcohol particular methanol, ethanol, butanols, Virahol, especially preferred alcohol and Virahol.
Described silicon sol is selected from tetraethoxy, isopropyl titanate or zirconium-n-propylate, and described non-silicon sol is selected from sodium aluminate, aluminum nitrate, aluminium secondary butylate, trimethyl carbinol aluminium, aluminum ethylate and aluminum isopropylate.
Or step 2 comprises following operation:
(2.1) HNO is used
3solution and H
2o
2solution carries out modification to carbon nano tube surface, obtains the carbon nanotube of surface modification.
(2.2) by non-silicon precursor sol solution and cetyl trimethylammonium bromide (CTAB), after being dissolved in dehydrated alcohol respectively, remix together and stir 0.5-1.5 hour, obtains mixed system 1; By the triblock copolymer (P123) of polyoxyethylene-poly-oxypropylene polyoxyethylene with add H through above-mentioned modified carbon nano-tube
2sO
4with in HCl mixing solutions, in stirred at ambient temperature until P123 melts completely, add the precursor aqueous solution that the silicon sol that is dissolved in dehydrated alcohol obtains, stir 2-3 hour, obtain mixed system 2;
(2.3) by mixed system 1 and 2-in-1 and and after mixing, at 95-105 DEG C, Hydrothermal Synthesis 40-50 hour, finally takes out, and is cooled to room temperature, washing, suction filtration, drying, roasting, obtain the Porous materials of two kinds of presomas with double-pore structure.
Described silicon sol is selected from tetraethoxy, isopropyl titanate or zirconium-n-propylate, and non-silicon sol is selected from sodium aluminate, aluminum nitrate, aluminium secondary butylate, trimethyl carbinol aluminium, aluminum ethylate and aluminum isopropylate.
Step 3 is that magnetic is modified, and comprises the following steps: be n (Fe by mol ratio
3+): n (Fe
2+) be the FeSO of 1:0.7-0.5
47H
2o, Fe
2(SO
4)
3, or n (Fe
3+): n (Fe
2+) be the FeCl of 1:0.7-0.5
36H
2o, FeCl
2dissolve in deionized water, add cetyl trimethylammonium bromide, under an inert atmosphere, regulate pH to 9-10; In the solution after adjustment pH, add the zeolite deriving from step 1 and step 2, after dropping tetraethyl orthosilicate completes, stir 6 hours, then add TiSO
4, adjust pH to 13, dropping limit, limit is stirred, and leaves standstill, utilize magnetic resolution, and wash away impurity with acetone, afterwards, the magnetic solid super acidic catalyst obtained is put into baking oven after completing, and dries at 105 DEG C.
According to one embodiment of the invention, the weight ratio that adds of the zeolite of step 1 and step 2 is 1:4-1:1, and the weight ratio that adds of the zeolite of preferred steps 1 and step 2 is 2:3.
Step (4) is load phosphotungstic acid/ZrO
2, comprise the following steps: by Zr (NO
3)
4be dissolved in deionized water, be mixed with the zirconium nitrate aqueous solution that mass concentration is 30-40% (preferably 40%), join in the zirconium nitrate aqueous solution by the zeolite that abovementioned steps (3) obtains, violent stirring, to even suspension, then instills ammoniacal liquor and makes Zr (OH)
4uniform deposition on zeolite, leach throw out and wash, 100-110 DEG C dries, then in air atmosphere 350-450 DEG C of roasting; The Salkowski's solution being 10 % by weight by aforementioned zeolite concentration in air atmosphere after 350-450 DEG C of roasting floods 8 hours, then evaporating water, 100-110 DEG C of oven dry, then 200-400 DEG C of (preferably 300 DEG C) roasting in air atmosphere, obtains load phosphotungstic acid/ZrO
2zeolite.
According to one embodiment of the invention, zirconic charge capacity is the 5-10% of weight zeolite, and phospho-wolframic acid charge capacity is the 5-10% of weight zeolite.
The catalyzer adopting present method to prepare has following beneficial effect:
1. adopt natural zeolite to mix mutually with synthetic zeolite, reduce use cost, simultaneously multistage pore size distribution avoids homogeneous narrow and small duct in single molecular sieve and is unfavorable for that macromole participates in reaction, hinders generation diffusion and the generation carbon distribution of product and reactant.
2., owing to having carried out expanding treatment to zeolite, be both beneficial to the catalytic activity improving zeolite, be more conducive to, after follow-up coated magneticsubstance, still keeping the rate of diffusion in duct.
3. adopt template original position to prepare zeolite molecular sieve, cosolvent made by the alcohol that have employed corresponding hydrolyzate, not only in the process of synthesis, hydrolytic process has been relaxed by the adjustment of solvent, and be conducive to the sedimentation growth of copolymer microsphere, polyalcohol microspherulite diameter is homogeneous, and the single template of molecular weight distribution is orderly, by controlling reaction times and solvent ratio, the size of adjustable ethene copolymer, can obtain the macropore template of different size.
4. utilize modified carbon nano-tube to obtain mesoporous material for template.
5., after coated magnetic material, by magnetic force, catalyzer high efficiency separation from product out, can be overcome the shortcoming of catalyzer not easily Separation and Recovery after the reaction.
6. magneticsubstance appearance is coated with protective layer, can protect magnetic particle when reacting.
7. modified component in-situ preparation can be overlying on zeolite surface by the inventive method, each component disperses is effective, and be conducive to the effect playing each component, synergy is better.
8. load phosphotungstic acid/ZrO
2further enhancing the acidity of zeolite, can be effective in the chemical reaction needing to use acid, 2, in the preparation process of the chloro-5-fluorobenzoyl chloride of 4-bis-, avoid using the strong acid such as sulfuric acid, nitric acid, hydrochloric acid to be hydrolyzed acidifying, can conventional reactor be used, avoid aforementioned use aluminum chloride Problems existing simultaneously.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, the following specific embodiment of the present invention is described, but the present invention is limited to absolutely not these examples.The following stated is only the good embodiment of the present invention, only for explaining the present invention, therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
The test of zeolite catalyst strength of acid of the present invention is undertaken by Hammett indicator method.Use anhydrous cyclohexane as solvent, compound concentration is 0.1%-0.5% indicator solution.Drip indicator to dry catalyst surface and observe colour-change during mensuration: if color changes, showing that catalyzer reaches the strength of acid of the indicator of use, now changing acid stronger indicator and measure, until color no longer changes.The maximal acid intensity that can reach is the strength of acid of this catalyzer.
Below by way of concrete test examples, preparation method of the present invention and effect thereof are described.
The preparation of composite zeolite solid super acid catalyst
Step (1): zeolite pre-treatment
A1
To mordenite carrier after 450 DEG C of calcination process, adding with containing ammonium concentration is that 1.0mol/L ammonium nitrate solution carries out exchange process, ammonium salt solution and the liquid-solid volume ratio of zeolite are 4:1, swap time is 6 hours, repeat 4 times, mordenite after exchanging with deionized water wash, then carry out drying and 450 DEG C of calcination process again;
The zeolite of aforementioned calcination process is again put into the H that concentration is 6mol/L
2sO
4soak 6 hours in solution, with deionized water wash to neutral, drier, within 8 hours, obtain pretreated carrier 450 DEG C of roastings.
A2
To mordenite carrier after 650 DEG C of calcination process, adding with containing ammonium concentration is that 0.05mol/L ammoniumsulphate soln carries out exchange process, ammonium salt solution and the liquid-solid volume ratio of zeolite are 3:1, swap time is 30 hours, repeat 10 times, mordenite after exchanging with deionized water wash, then carry out drying and 650 DEG C of calcination process again;
The zeolite of aforementioned calcination process again being put into concentration is that the salpeter solution of 0.05mol/L soaks 12 hours, with deionized water wash to neutral, drier, within 8 hours, obtain pretreated carrier 650 DEG C of roastings.
A3
To mordenite carrier after 550 DEG C of calcination process, adding with containing ammonium concentration is that 0.5mol/L sal volatile carries out exchange process, ammonium salt solution and the liquid-solid volume ratio of zeolite are 4:1, swap time is 60 hours, mordenite after exchanging with deionized water wash, then carry out drying and 550 DEG C of calcination process again;
The zeolite of aforementioned calcination process again being put into concentration is that the hydrochloric acid soln of 4mol/L soaks 10 hours, with deionized water wash to neutral, drier, within 8 hours, obtain pretreated carrier 550 DEG C of roastings.
Step (2): the synthesis 1 of porous level zeolite
B1
Under protection of inert gas, the maleic anhydride of mol ratio 1:1:1, vinylbenzene and vinyl acetate between to for plastic and dibenzoyl peroxide are joined ethanol and acetone volume ratio is dissolve in the mixed solvent of 1:1 to obtain reaction solution, in reaction solution, the mass concentration of initiator is 0.1%, and in 70 DEG C of reactions 6 hours, obtain the dispersion system of polymer microballoon;
By dispersion system, tetraethoxy silicon sol and aluminum nitrate according to 1: 10: 0.5 mass ratio mix, then stir, at room temperature naturally place, to complete gelation process;
Again through centrifugation, be cooled to room temperature, washing, suction filtration, drying, 450 DEG C of roastings obtain porous level zeolite for 6 hours.
B2
Under protection of inert gas, the maleic anhydride of mol ratio 1:2:2, vinylbenzene and vinyl acetate between to for plastic and dibenzoyl peroxide are joined ethanol and acetone volume ratio is dissolve in the mixed solvent of 1:1.5 to obtain reaction solution, in reaction solution, the mass concentration of initiator is 0.5%, and in 80 DEG C of reactions 10 hours, obtain the dispersion system of polymer microballoon;
By dispersion system, tetraethoxy silicon sol and aluminum nitrate according to 1: 20: 3 mass ratio mix, then stir, at room temperature naturally place, to complete gelation process;
Again through centrifugation, be cooled to room temperature, washing, suction filtration, drying, 650 DEG C of roastings obtain porous level zeolite for 5 hours.
B3
Under protection of inert gas, the maleic anhydride of mol ratio 1:2:2, vinylbenzene and vinyl acetate between to for plastic and dibenzoyl peroxide are joined ethanol and acetone volume ratio is dissolve in the mixed solvent of 1:1.5 to obtain reaction solution, in reaction solution, the mass concentration of initiator is 0.3%, and in 80 DEG C of reactions 8 hours, obtain the dispersion system of polymer microballoon;
By dispersion system, tetraethoxy silicon sol and aluminum nitrate according to 1: 15: 1.5 mass ratio mix, then stir, at room temperature naturally place, to complete gelation process;
Again through centrifugation, be cooled to room temperature, washing, suction filtration, drying, 550 DEG C of roastings obtain porous level zeolite for 5 hours.
Step (2): the synthesis 2 of porous level zeolite
B'1
Use dense HNO
3with 30% mass concentration H
2o
2modification is carried out to carbon nano tube surface (external diameter about 6nm), obtains the carbon nanotube of surface modification.
Stir 0.5 hour together with remix after aluminum nitrate is dissolved in dehydrated alcohol respectively with cetyl trimethylammonium bromide (CTAB), obtain mixed system 1; By the triblock copolymer (P123) of polyoxyethylene-poly-oxypropylene polyoxyethylene with add dense H through above-mentioned modified carbon nano-tube
2sO
4with in HCl mixing solutions, in stirred at ambient temperature until P123 melts completely, add the teos solution being dissolved in dehydrated alcohol, stir 3 hours, obtain mixed system 2;
By mixed system 1 and 2-in-1 and and after mixing, reinstall reactor, in 95 DEG C of Hydrothermal Synthesiss 50 hours, finally take out, be cooled to room temperature, washing, suction filtration, drying, roasting, obtain the zeolite of two kinds of presomas with double-pore structure,
Amount ratio is, carbon nanotube: aluminum nitrate: CTAB: triblock copolymer: tetraethyl silicate=2g:2g:3g:1g:2ml.
B'2
Use dense HNO
3with 30% mass concentration H
2o
2modification is carried out to carbon nano tube surface (external diameter about 6nm), obtains the carbon nanotube of surface modification.
Stir 1.5 hours together with remix after aluminum nitrate is dissolved in dehydrated alcohol respectively with cetyl trimethylammonium bromide (CTAB), obtain mixed system 1; By the triblock copolymer (P123) of polyoxyethylene-poly-oxypropylene polyoxyethylene with add dense H through above-mentioned modified carbon nano-tube
2sO
4with in HCl mixing solutions, in stirred at ambient temperature until P123 melts completely, add the teos solution being dissolved in dehydrated alcohol, stir 2 hours, obtain mixed system 2;
By mixed system 1 and 2-in-1 and and after mixing, reinstall reactor, in 105 DEG C of Hydrothermal Synthesiss 40 hours, finally take out, be cooled to room temperature, washing, suction filtration, drying, roasting, obtain the zeolite of two kinds of presomas with double-pore structure.
Amount ratio is, carbon nanotube: aluminum nitrate: CTAB: triblock copolymer: tetraethyl silicate=2g:2g:3g:1g:2ml.
B'3
Use dense HNO
3with 30% mass concentration H
2o
2modification is carried out to carbon nano tube surface (external diameter about 6nm), obtains the carbon nanotube of surface modification.
Stir 1 hour together with remix after aluminum nitrate is dissolved in dehydrated alcohol respectively with cetyl trimethylammonium bromide (CTAB), obtain mixed system 1; By the triblock copolymer (P123) of polyoxyethylene-poly-oxypropylene polyoxyethylene with add dense H through above-mentioned modified carbon nano-tube
2sO
4with in HCl mixing solutions, in stirred at ambient temperature until P123 melts completely, add the teos solution being dissolved in dehydrated alcohol, stir 2.5 hours, obtain mixed system 2;
By mixed system 1 and 2-in-1 and and after mixing, reinstall reactor, in 100 DEG C of Hydrothermal Synthesiss 45 hours, finally take out, be cooled to room temperature, washing, suction filtration, drying, roasting, obtain the zeolite of two kinds of presomas with double-pore structure.
Amount ratio is, carbon nanotube: aluminum nitrate: CTAB: triblock copolymer: tetraethyl silicate=2g:2g:3g:1g:2ml.
Step (3): magnetic is modified
C1
Be n (Fe by mol ratio
3+): n (Fe
2+) be the FeSO of 1:0.7
47H
2o and Fe
2(SO
4)
3dissolve in deionized water, add cetyl trimethylammonium bromide, under an inert atmosphere, regulate pH to 9; In the solution after adjustment pH, add the zeolite deriving from step 1 and step 2, after dropping tetraethyl orthosilicate completes, stir 6 hours, then add TiSO
4, adjust pH to 13, dropping limit, limit is stirred, and leaves standstill, utilize magnetic resolution, and wash away impurity with acetone, afterwards, the magnetic solid super acidic catalyst obtained is put into baking oven after completing, and dries at 105 DEG C.
C2
Be n (Fe by mol ratio
3+): n (Fe
2+) be the FeSO of 1:0.5
47H
2o and Fe
2(SO
4)
3dissolve in deionized water, add cetyl trimethylammonium bromide, under an inert atmosphere, regulate pH to 10; In the solution after adjustment pH, add the zeolite deriving from step 1 and step 2, after dropping tetraethyl orthosilicate completes, stir 6 hours, then add TiSO
4, adjust pH to 13, dropping limit, limit is stirred, and leaves standstill, utilize magnetic resolution, and wash away impurity with acetone, afterwards, the magnetic solid super acidic catalyst obtained is put into baking oven after completing, and dries at 100 DEG C.
C3
Be n (Fe by mol ratio
3+): n (Fe
2+) be the FeCl of 1:0.7
36H
2o and FeCl
2dissolve in deionized water, add cetyl trimethylammonium bromide, under an inert atmosphere, regulate pH to 9; In the solution after adjustment pH, add the zeolite deriving from step 1 and step 2, after dropping tetraethyl orthosilicate completes, stir 6 hours, then add TiSO
4, adjust pH to 13, dropping limit, limit is stirred, and leaves standstill, utilize magnetic resolution, and wash away impurity with acetone, afterwards, the magnetic solid super acidic catalyst obtained is put into baking oven after completing, and dries at 110 DEG C.
Step (4): phospho-wolframic acid/ZrO
2load
D1
By Zr (NO
3)
4be dissolved in deionized water, be mixed with the zirconium nitrate aqueous solution that mass concentration is 30%, join in the zirconium nitrate aqueous solution by the zeolite that abovementioned steps (3) obtains, violent stirring, to even suspension, then instills ammoniacal liquor and makes Zr (OH)
4uniform deposition on zeolite, leach throw out and wash, 100 DEG C of oven dry, then 450 DEG C of roastings in air atmosphere.The Salkowski's solution being 10 % by weight by aforementioned zeolite concentration in air atmosphere after 350 DEG C of roastings floods 8 hours, then evaporating water, 100 DEG C of oven dry, and then 300 DEG C of roastings in air atmosphere, obtain load phosphotungstic acid/ZrO
2zeolite.
D2
By Zr (NO
3)
4be dissolved in deionized water, be mixed with the zirconium nitrate aqueous solution that mass concentration is 40%, then join in the zirconium nitrate aqueous solution by the zeolite that abovementioned steps (3) obtains, violent stirring, to even suspension, then instills ammoniacal liquor and makes Zr (OH)
4uniform deposition on zeolite, leach throw out and wash, 105 DEG C of oven dry, then 350 DEG C of roastings in air atmosphere.The Salkowski's solution being 10 % by weight by aforementioned zeolite concentration in air atmosphere after 350 DEG C of roastings floods 8 hours, then evaporating water, 110 DEG C of oven dry, and then 400 DEG C of roastings in air atmosphere, obtain load phosphotungstic acid/ZrO
2zeolite.
D3
By Zr (NO
3)
4be dissolved in deionized water, be mixed with the zirconium nitrate aqueous solution that mass concentration is 35%, then join in the zirconium nitrate aqueous solution by the zeolite that abovementioned steps (3) obtains, violent stirring, to even suspension, then instills ammoniacal liquor and makes Zr (OH)
4uniform deposition on zeolite, leach throw out and wash, 110 DEG C of oven dry, then 400 DEG C of roastings in air atmosphere.The Salkowski's solution being 10 % by weight by aforementioned zeolite concentration in air atmosphere after 350 DEG C of roastings floods 8 hours, then evaporating water, 105 DEG C of oven dry, and then 200 DEG C of roastings in air atmosphere, obtain load phosphotungstic acid/ZrO
2zeolite.
Table 1: catalyst characterization
Wherein, preparation process refers to the step that catalyst preparing uses, such as A1B1C1D1 refers to and uses abovementioned steps A1, B1, C1 and D1 preparation respectively, natural zeolite and synthetic zeolite ratio refer to by step (3) middle select the zeolite ratio of different step 1 and step 2 to obtain natural zeolite and synthetic zeolite ratio.
The preparation of the chloro-5-fluorobenzoyl chloride of 2,4-bis-
The preparation of embodiment 1:2,4-bis-chloro-5-fluorine trichlorotoluene zotrichloride
194ml (2mol) tetracol phenixin and 33 grams of (0.2mol) 2 are added in the reactor of 2L, 4-dichlor fluorbenzene, then in reactor, add the catalyzer 8 in 50 grams of aforementioned tables 1, reaction is reacted 30 minutes under reflux, subsequently reaction mixture be cooled to room temperature and pour in frozen water, organic layer is separated circumstances in which people get things ready for a trip spectrum analysis of going forward side by side, and finds 2, the 4-bis-chloro-5-fluorine trichlorotoluene zotrichlorides containing 94% in product.
The preparation of the chloro-5-fluorobenzoyl chloride of embodiment 2:2,4-bis-
194ml (2mol) tetracol phenixin and 33 grams of (0.2mol) 2 are added in the reactor of 2L, 4-dichlor fluorbenzene, then in reactor, add the catalyzer 8 in 16 grams of aforementioned tables 1, reaction is reacted 30 minutes under reflux, subsequently by reactor cooling to room temperature, 200 ml deionized water are added in reaction system, 40 DEG C of reactions 1 hour, collected the cut of 143-144 DEG C (35mmHg) by distillation after reaction terminates, obtain 39.1 grams of micro-yellow liquids, yield 86.0%.
Carry out mass spectroscopy and ultimate analysis to products therefrom, acquired results is as follows:
Mass spectrum: m/z:225.92 (100.0%), 227.91 (95.9%), 229.91 (30.6%), 226.92 (7.6%), 228.92 (7.3%), 231.91 (3.3%), 230.91 (2.3%).
Results of elemental analyses: C, 36.97; H, 0.89; Cl, 46.76; F, 8.35; O, 7.03.Molecular weight of product is: 227.44.
The preparation of the chloro-5-fluorobenzoyl chloride of embodiment 3:2,4-bis-
Repeat embodiment 2, difference is the catalyzer 8 in use 30 grams of aforementioned tables 1, obtains 39.3 grams of micro-yellow liquids, yield 86.3%.
The preparation of the chloro-5-fluorobenzoyl chloride of embodiment 4:2,4-bis-
Repeat embodiment 2, difference is to use reuses 8 later catalyzer 8, and final reaction obtains 38.3 grams of micro-yellow liquids, yield 84.2%.
The preparation of the chloro-5-fluorobenzoyl chloride of embodiment 5:2,4-bis-
Repeat embodiment 1, difference is the catalyzer 11 used in aforementioned table 1, and final reaction obtains 39.1 grams of micro-yellow liquids, yield 86.0%.
The preparation of the chloro-5-fluorobenzoyl chloride of embodiment 6:2,4-bis-
Repeat embodiment 2, difference is to use reuses 8 later catalyzer 11, and final reaction obtains 38.4 grams of micro-yellow liquids, yield 84.5%.
The preparation of the chloro-5-fluorobenzoyl chloride of embodiment 7:2,4-bis-
Repeat embodiment 2, after difference is to add deionized water, add 20 grams of iron(ic) chloride in addition, 30 DEG C of reactions 1 hour, collected the cut of 143-144 DEG C (35mmHg) after reaction terminates by distillation, obtain 41.1 grams of micro-yellow liquids, yield 90.3%.
The preparation of the chloro-5-fluorobenzoyl chloride of embodiment 8:2,4-bis-
Repeat embodiment 2, difference is that catalyzer uses the catalyzer 11 in aforementioned table 1, and after adding deionized water, in addition 20 grams of iron(ic) chloride are added, 30 DEG C of reactions 1 hour, collected the cut of 143-144 DEG C (35mmHg) after reaction terminates by distillation, obtain 41.6 grams of micro-yellow liquids, yield 91.5%.
The preparation of the chloro-5-fluorobenzoyl chloride of embodiment 9:2,4-bis-
Repeat embodiment 7, difference is that catalyzer uses and reuses 8 later catalyzer 11, is collected the cut of 143-144 DEG C (35mmHg), obtain 41.0 grams of micro-yellow liquids, yield 90.1% after reaction terminates by distillation.
Claims (10)
1. the method for the chloro-5-fluorobenzoyl chloride of synthesis 2,4-bis-, said method comprising the steps of:
(A) in reactor, add 2,4 dichloro fluorobenzene, composite zeolite solid super acid catalyst and tetracol phenixin, back flow reaction obtains 2,4-bis-chloro-5-fluorine trichlorotoluene zotrichloride;
(B) by reactor cooling to room temperature, directly add deionized water without product separation, at 20-40 DEG C hydrolysis obtain the chloro-5-fluorobenzoyl chloride of 2,4-bis-.
2. the method for the chloro-5-fluorobenzoyl chloride of synthesis 2,4-bis-, said method comprising the steps of:
(A) in reactor, add 2,4 dichloro fluorobenzene, composite zeolite solid super acid catalyst and tetracol phenixin, back flow reaction obtains 2,4-bis-chloro-5-fluorine trichlorotoluene zotrichloride;
(B) by reactor cooling to room temperature, directly add deionized water and iron(ic) chloride without product separation, at 20-40 DEG C hydrolysis obtain the chloro-5-fluorobenzoyl chloride of 2,4-bis-.
3. method according to claim 1 and 2, wherein said composite zeolite solid super acid catalyst is prepared by following steps:
(1) Zeolite support pre-treatment, comprises following operation:
(1.1) to Natural Zeolite Support after 450 DEG C of-650 DEG C of calcination process, carry out exchange process with the ammonium salt solution containing ammonium nitrate, volatile salt or ammonium sulfate that ammonium concentration is 0.05 ~ 1.0mol/L, the liquid-solid volume ratio of ammonium salt solution and zeolite is 3:1 ~ 5:1; Swap time is 30 minutes to 60 hours, the zeolite after exchanging with deionized water wash, then carries out drying and 450 DEG C-650 DEG C calcination process again; Described natural zeolite is mordenite;
(1.2) carrier reaming: the zeolite that step (1.1) obtains is put into HCl, HNO that concentration is 0.05 ~ 6mol/L
3, H
2sO
4or soak 6-10 hour in citric acid, with deionized water wash to neutral, dry, obtain pretreated carrier 450 DEG C of-650 DEG C of roastings;
(2) synthesis of porous level zeolite, comprises following operation:
(2.1) under protection of inert gas, comonomer and initiator are joined dissolving in medium and obtain reaction solution, and in 70 ~ 80 DEG C of reaction 6 ~ 10h, obtain the dispersion system of polymer microballoon;
(2.2) mix by the mass ratio 1: 10 ~ 20: 0.5 ~ 3 of dispersion system, silicon sol, non-silicon sol, then stir, at room temperature naturally place, to complete its gelation process;
(2.3) again through centrifugation, be cooled to room temperature, washing, suction filtration, drying, 450 DEG C of-650 roasting obtain porous level zeolite;
Wherein, described comonomer is vinyl monomer, comprises maleic anhydride, vinylbenzene and vinyl acetate between to for plastic, and the mol ratio of comonomer is maleic anhydride: vinylbenzene: vinyl acetate between to for plastic is 1:1-2:1-2, and in reaction solution, the mass concentration of monomer is 10% ~ 30%;
Described initiator is organo-peroxide or azo-compound, the wherein preferred dialkyl peroxide of organic peroxide evocating agent (such as di-t-butyl peroxide, dicumyl peroxide), acyl class superoxide (such as dibenzoyl peroxide, lauroyl peroxide), hydroperoxide (such as isopropyl benzene hydroperoxide, tertbutyl peroxide), ester class superoxide (such as peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester) or two carbonic ether superoxide (such as di-isopropyl peroxydicarbonates, di-cyclohexylperoxy dicarbonate), the preferred Diisopropyl azodicarboxylate of azoic compound initiator (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile), in reaction solution, the mass concentration of initiator is 0.1% ~ 0.5%,
Described medium is C
1-C
12the mixing solutions of alkyl alcohol and acetone, volume ratio is: 1:1-1.5, described C
1-C
12alkyl alcohol particular methanol, ethanol, butanols, Virahol, especially preferred alcohol and Virahol;
Described silicon sol is selected from tetraethoxy, isopropyl titanate or zirconium-n-propylate, and described non-silicon sol is selected from sodium aluminate, aluminum nitrate, aluminium secondary butylate, trimethyl carbinol aluminium, aluminum ethylate and aluminum isopropylate;
(3) magnetic is modified, and comprises the following steps:
Be n (Fe by mol ratio
3+): n (Fe
2+) be the FeSO of 1:0.7-0.5
47H
2o, Fe
2(SO
4)
3, or n (Fe
3+): n (Fe
2+) be the FeCl of 1:0.7-0.5
36H
2o, FeCl
2dissolve in deionized water, add cetyl trimethylammonium bromide, under an inert atmosphere, regulate pH to 9-10; In the solution after adjustment pH, add the zeolite deriving from step 1 and step 2, after dropping tetraethyl orthosilicate completes, stir 6 hours, then add TiSO
4, adjust pH to 13, dropping limit, limit is stirred, and leaves standstill, utilize magnetic resolution, and wash away impurity with acetone, afterwards, the magnetic solid super acidic catalyst obtained is put into baking oven after completing, and dries at 100-110 DEG C; Wherein the weight ratio that adds of the zeolite of step 1 and step 2 is 1:4-1:1;
(4) phospho-wolframic acid/ZrO
2load, comprise the following steps:
By Zr (NO
3)
4be dissolved in deionized water, be mixed with the zirconium nitrate aqueous solution that mass concentration is 30-40%, join in the zirconium nitrate aqueous solution by the zeolite that abovementioned steps (3) obtains, violent stirring, to even suspension, then instills ammoniacal liquor and makes Zr (OH)
4uniform deposition on zeolite, leach throw out and wash, 100-110 DEG C dries, then in air atmosphere 350-450 DEG C of roasting;
The Salkowski's solution being 10 % by weight by aforementioned zeolite concentration in air atmosphere after 350-450 DEG C of roasting floods 8 hours, then evaporating water, 100-110 DEG C of oven dry, and then 200-400 DEG C of roasting in air atmosphere, obtains load phosphotungstic acid/ZrO
2zeolite.
4. method according to claim 1 and 2, wherein said composite zeolite solid super acid catalyst is prepared by following steps:
(1) Zeolite support pre-treatment, comprises following operation:
(1.1) to Natural Zeolite Support after 450 DEG C of-650 DEG C of calcination process, carry out exchange process with the ammonium salt solution containing ammonium nitrate, volatile salt or ammonium sulfate that ammonium concentration is 0.05 ~ 1.0mol/L, the liquid-solid volume ratio of ammonium salt solution and zeolite is 3:1 ~ 5:1; Swap time is 30 minutes to 60 hours, the zeolite after exchanging with deionized water wash, then carries out drying and 450 DEG C-650 DEG C calcination process again; Described natural zeolite is mordenite;
(1.2) carrier reaming: the zeolite that step (1.1) obtains is put into HCl, HNO that concentration is 0.05 ~ 6mol/L
3, H
2sO
4or soak 6-10 hour in citric acid, with deionized water wash to neutral, dry, obtain pretreated carrier 450 DEG C of-650 DEG C of roastings;
(2) synthesis of porous level zeolite, comprises following operation:
(2.1) HNO is used
3and H
2o
2modification is carried out to carbon nano tube surface, obtains the carbon nanotube of surface modification,
(2.2) stir 0.5-1.5 hour together with remix after non-silicon sol being dissolved in dehydrated alcohol respectively with cetyl trimethylammonium bromide (CTAB), obtain mixed system 1; By the triblock copolymer (P123) of polyoxyethylene-poly-oxypropylene polyoxyethylene with join H through the carbon nanotube of above-mentioned surface modification
2sO
4with in HCl mixing solutions, in stirred at ambient temperature until P123 melts completely, add the precursor aqueous solution that the silicon sol that is dissolved in dehydrated alcohol obtains, stir 2-3 hour, obtain mixed system 2;
(2.3) by mixed system 1 and 2-in-1 and and after mixing, at 95-105 DEG C, Hydrothermal Synthesis 40-50 hour, finally takes out, and is cooled to room temperature, washing, suction filtration, drying, roasting, obtain the zeolite of two kinds of presomas with double-pore structure,
Described silicon sol is selected from tetraethoxy, isopropyl titanate or zirconium-n-propylate, and non-silicon sol is selected from sodium aluminate, aluminum nitrate, aluminium secondary butylate, trimethyl carbinol aluminium, aluminum ethylate and aluminum isopropylate;
(3) magnetic is modified, and comprises the following steps:
Be n (Fe by mol ratio
3+): n (Fe
2+) be the FeSO of 1:0.7-0.5
47H
2o, Fe
2(SO
4)
3, or n (Fe
3+): n (Fe
2+) be the FeCl of 1:0.7-0.5
36H
2o, FeCl
2dissolve in deionized water, add cetyl trimethylammonium bromide, under an inert atmosphere, regulate pH to 9-10; In the solution after adjustment pH, add the zeolite deriving from step 1 and step 2, after dropping tetraethyl orthosilicate completes, stir 6 hours, then add TiSO
4, adjust pH to 13, dropping limit, limit is stirred, and leaves standstill, utilize magnetic resolution, and wash away impurity with acetone, afterwards, the magnetic solid super acidic catalyst obtained is put into baking oven after completing, and dries at 105 DEG C; Wherein the weight ratio that adds of the zeolite of step 1 and step 2 is 1:4-1:1;
(4) phospho-wolframic acid/ZrO
2load, comprise the following steps:
By Zr (NO
3)
4be dissolved in deionized water, be mixed with the zirconium nitrate aqueous solution that mass concentration is 30-40%, join in the zirconium nitrate aqueous solution by the zeolite that abovementioned steps (3) obtains, violent stirring, to even suspension, then instills ammoniacal liquor and makes Zr (OH)
4uniform deposition on zeolite, leach throw out and wash, 100-110 DEG C dries, then in air atmosphere 350-450 DEG C of roasting;
The Salkowski's solution being 10 % by weight by aforementioned zeolite concentration in air atmosphere after 350-450 DEG C of roasting floods 8 hours, then evaporating water, 100-110 DEG C of oven dry, and then 200-400 DEG C of roasting in air atmosphere, obtains load phosphotungstic acid/ZrO
2zeolite.
5., according to the method in claim 3-4 described in any one, it is characterized in that zirconic charge capacity is the 5-10% of weight zeolite, phospho-wolframic acid charge capacity is the 5-10% of weight zeolite.
6. according to the method in claim 3-4 described in any one, it is characterized in that in step (3), the weight ratio that adds of the zeolite of step 1 and step 2 is 2:3.
7., according to the method in claim 3-4 described in any one, it is characterized in that in step (4), by Zr (NO
3)
4be dissolved in deionized water and be mixed with the zirconium nitrate aqueous solution that mass concentration is 40%.
8. according to the method in claim 3-4 described in any one, it is characterized in that in step (4), the maturing temperature after dipping Salkowski's solution is 300 DEG C.
9. according to the method in claim 3-4 described in any one, it is characterized in that in step (A), relative to every mole 2,4-dichlor fluorbenzene uses 40-200 gram of composite zeolite solid super acid catalyst, preferably use 80-150 gram of composite zeolite solid super acid catalyst relative to every mole of 2,4 dichloro fluorobenzene.
10. according to the method in claim 3-4 described in any one, it is characterized in that in step (A), the mol ratio of tetracol phenixin and 2,4 dichloro fluorobenzene is 10:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175245A (en) * | 2015-10-22 | 2015-12-23 | 山东国邦药业股份有限公司 | Synthesis method of 2,4-dichloro-5-fluorobenzoyl chloride |
| CN108299150A (en) * | 2018-01-29 | 2018-07-20 | 江苏佳麦化工有限公司 | The synthetic method of 4- n-butylbenzene formyl chlorides |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04149143A (en) * | 1990-10-09 | 1992-05-22 | Asahi Glass Co Ltd | New production of fluorobenzotrichlorides |
| US5241111A (en) * | 1989-11-17 | 1993-08-31 | Asahi Glass Company Ltd. | Processes for producing 5-fluorobenzoic acids and their intermediates |
| CN101786020A (en) * | 2010-02-05 | 2010-07-28 | 江苏工业学院 | Phosphotungstic acid modified catalyst, preparation method and application in acrolein preparation thereof |
-
2015
- 2015-02-15 CN CN201510083439.XA patent/CN104649890B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5241111A (en) * | 1989-11-17 | 1993-08-31 | Asahi Glass Company Ltd. | Processes for producing 5-fluorobenzoic acids and their intermediates |
| JPH04149143A (en) * | 1990-10-09 | 1992-05-22 | Asahi Glass Co Ltd | New production of fluorobenzotrichlorides |
| CN101786020A (en) * | 2010-02-05 | 2010-07-28 | 江苏工业学院 | Phosphotungstic acid modified catalyst, preparation method and application in acrolein preparation thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175245A (en) * | 2015-10-22 | 2015-12-23 | 山东国邦药业股份有限公司 | Synthesis method of 2,4-dichloro-5-fluorobenzoyl chloride |
| CN105175245B (en) * | 2015-10-22 | 2017-07-18 | 山东国邦药业股份有限公司 | A kind of synthetic method of the fluorobenzoyl chloride of 2,4 dichloro 5 |
| CN108299150A (en) * | 2018-01-29 | 2018-07-20 | 江苏佳麦化工有限公司 | The synthetic method of 4- n-butylbenzene formyl chlorides |
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