CN105523962A - Fluorobenzonitrile compound preparation method - Google Patents
Fluorobenzonitrile compound preparation method Download PDFInfo
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Abstract
The present invention provides a fluorobenzonitrile compound preparation method, fluorobenzonitrile compounds are as shown in the general formula (I), an objective product can be prepared from a general-formula-(II)-shown chlorobenzonitrile compound as a raw material by reacting with an anhydrous fluoride in the presence of an inert gas under high temperature high pressure reaction conditions and flashing a reaction product, wherein the objective product itself is used as a solvent. Due to use of the objective product itself as the solvent, a main component of the fluorine exchange reaction product only comprises the objective product, due to use of an inert gas pressurization method to improve the fluorine exchange reaction and product separation conditions, the product is separated and purified in the flashing manner, the reaction residual heat is rationally used, and the whole process is simple and feasible. The method is readily available in raw materials, simple in process, energy-saving, consumption-reducing, and more suitable for industrial scale production.
Description
Technical field
The present invention relates to the preparation method of fluoro benzonitrile compounds, belong to technical field of organic synthesis.
Background technology
The fluoro benzonitrile compounds that general formula is (I) is very important organic intermediate, is widely used in the fields such as medicine, agricultural chemicals, dyestuff, macromolecular material and liquid crystal material.Such as 2,4,5-trifluoro-benzene formonitrile HCNs can be used for producing oxytocin receptor antagonists, are the medicines being used for the treatment of premature labor.3,4,5-trifluoro-benzene formonitrile HCN can be used for synthesizing 1-(3,4,5-trifluorophenyl)-2-[trans-4 ˊ-(trans-4 ˊ-n-propyl) cyclohexyl] ethane, and this is a kind of good liquid crystal material.2,3,5,6-tetra fluoro benzene formonitrile HCN can be used for synthesizing transfluthrin, is the health pyrethrin insecticide of high-efficiency low-toxicity.2,3,4,5,6-penta fluoro benzene formonitrile HCN can be used for preparing fluoroquinolone compound class anti-bacterial drug sparfloxacin, good for husky star and Moxifloxacin etc.; Also can be used for synthetic pyrethroid insecticides transfluthrin and five Flumethrins etc.; Also can be used for the important agricultural chemicals of synthesis and medicine intermediate 2-pentafluorophenyl group benzoxazoles; Also can be used for the important monomer synthesizing multiple special macromolecular material, as octafluoro-4,4 ˊ-biphenyl dimethylamine and octafluoro-4,4 ˊ-biphenyl dicarboxylic acid etc.; Can also be converted to pentafluorobenzoic acid, penta fluoro benzene acid amides, penta fluoro benzene amine, pentafluorobenzaldehyde, Pentafluorophenol etc. by cyano group, the contraposition fluorine replacement also by cyano group obtains 4-alkoxyl group-2,3,5,6-tetra fluoro benzene formonitrile HCN, 4-aryloxy-2,3,5,6-tetra fluoro benzene formonitrile HCN, 4-amino-2,3,5,6-tetra fluoro benzene formonitrile HCN, 4-hydroxyl-2,3,5,6-tetra fluoro benzene formonitrile HCN and 4-sulfydryl-2,3,5,6-tetra fluoro benzene formonitrile HCN etc., these compounds are all very important chemical intermediates; Also can be used for synthesizing polyether nitrile speciality polymer material and tetrafluoro phenyl ester liquid crystal material etc.The fluoro-para-Phthalonitrile of 2,3-bis-, 2,5-bis-fluoro-para-Phthalonitriles and the fluoro-para-Phthalonitrile of 3,6-bis-all can be used as active antibacterial composition and are applied to cementation process.The fluoro-para-Phthalonitrile of 2,6-bis-can be used for producing efficient pesticides and other chemical, medicines etc.The fluoro-phthalonitrile of 3,4-bis-, 3,5-bis-fluoro-phthalonitriles, 3, the fluoro-phthalonitrile of 6-bis-and 4, the fluoro-phthalonitrile of 5-bis-all can be used for the high value pigment producing high light-fast fastness, and 3,4-bis-fluoro-phthalonitriles also can be used for producing medicine and antiseptic-germicide etc.2,3,5-trifluoro para-Phthalonitrile can be used for synthesis fluorophenyl methanol cyclopropane carboxylic ester low toxicity efficient pesticides.3,4,5-trifluoro phthalonitrile and 3,4,6-trifluoro phthalonitrile all can be used for the high value pigment producing high light-fast fastness, and 3,4,6-trifluoro phthalonitrile also can be used for synthesis quinolone antibiotic and phthalocyanine pigment and liquid crystal material.2,4,5-trifluoro Isophthalodinitrile can be used for synthesis carbostyril family antibacterial drugs, agrochemicals and industrial chemical etc.2,3,5,6-tetrafluoro terephthalonitrile can be used for synthesis medicine and agricultural chemicals, is the intermediate of synthetic pyrethroid insecticides transfluthrin and tefluthrin.3,4,5,6-tetrafluoro phthalonitrile and 2,4,5,6-tetrafluoro Isophthalodinitrile all can be used for synthesizing carbostyril family antibacterial drugs, 2,4,5,6-tetrafluoro Isophthalodinitrile also can be used for synthesizing the dyestuff with low-temperature reactivity, and 3,4,5,6-tetrafluoro phthalonitrile also can be used for the high value pigment producing high light-fast fastness.3-fluoro-1,4,5-benzene trimethylsilyl nitrile can be used for synthesis trimerization aromatic nitriles, it is synthetic dyestuff and inert ingredient important source material, in addition, the fluoro-Isosorbide-5-Nitrae of 3-, 5-benzene trimethylsilyl nitrile also can be used for manufacturing and has excellent thermotolerance and the thermosetting resin of mechanical property, and it has special purposes in light-weight electric mechanical material and electrical insulating material.Fluoro-1,3, the 5-benzene trimethylsilyl nitrile of 2,4,6-tri-can be used for preparing reactive dyestuffs.These use of a compound are extensive, and each tool function, plays important effect in fields such as medicine, agricultural chemicals, dyestuff, macromolecular material and liquid crystal materials.
At present, the fluoro benzonitrile compounds that general formula is (I) mainly first obtains the chloro-benzonitrile compounds of logical formula II through chlorination by cyanophenyl, benzene dicarbonitrile or benzene trimethylsilyl nitrile, the chloro-benzonitrile of logical formula II is again through halogen exchange occurring with Potassium monofluoride etc. and obtaining.
The production technique of chloro-benzonitrile compounds is quite ripe, and Perchlorobenzonitrile can be raw material by cyanophenyl, and the chloridization process provided by US3855264, US6034264, CN1273238 and CN1772724 etc. is produced; Tetrachloro phthalonitrile can be produced with the chloridization process that phthalonitrile is provided by US3497547, US4572806 and US5789582 etc.; Termil can be produced with the chloridization process that Isophthalodinitrile is provided by US3839401, US4485050, CN85101962 and CN104447407 etc.; Tetrachloro-p-phenylene's dimethoxy nitrile can be produced with the chloridization process that para-Phthalonitrile is provided by CN1844090; The chloridization process that other chloro-benzonitrile compounds provides by US6034264 is produced.Chloro-benzonitrile realizes serialization and large-scale production already in China, steady quality, and market resource is enriched.
Synthesis technique about fluoro benzonitrile compounds also has a large amount of bibliographical informations, mostly adopts chloro-benzonitrile compounds to be obtained in fluoro benzonitrile compounds by fluorine permutoid reaction.Wherein, GB1026290, JP59152361, JP59222463, JP6036453, JP60184057, US4684734, US6392084, JP2001131136, JP2004075556, JP2005112745, CN1772724, CN104151196 and non-patent literature 1 (J.Chem.Soc. (C), 1971,1341) etc. the method being obtained penta fluoro benzene formonitrile HCN by pentachlorobenzonitrile by fluorine permutoid reaction is both provided; US4684734, JP04321644, JP2001131136, JP2004075556 and JP2005112745 etc. also provide the fluoro benzonitrile that comprises trifluoro-benzene formonitrile HCN and the tetra fluoro benzene formonitrile HCN synthetic method by fluorine permutoid reaction; GB1026290, US3975424, US4684734, US5153350, US6362365, US6392084, JP2001131136, US7132561, JP2004075556, JP2005112745 and non-patent literature 2 (Bull.Chem.Soc.Japan., Vol.40,688) etc. also provide comprise difluorobenzene dimethoxy nitrile, trifluoro-benzene dimethoxy nitrile and tetra fluoro benzene dimethoxy nitrile fluorobenzene dimethoxy nitrile by the synthetic method of fluorine permutoid reaction.
In the prior art of this kind of fluorine permutoid reaction, the technological method mentioned is as follows.
(1) about the use of fluorizating agent
Fluorizating agent is the raw material that must use, and can be alkaline metal fluoride cpd or alkaline-earth metal fluoride, and wherein Potassium monofluoride uses the most general.Because moisture has negative affect to fluorine permutoid reaction, so usually use anhydrous fluorochemical.
(2) about the use of solvent
Solventless method is that the early literatures such as GB1026290 are mentioned.This method is due to reaction system thickness, and after experience pyroprocess, coking is serious, and product yield is not high.
Solvent method is that present most document adopted.Because solvent plays good dissemination in reaction process, inhibit high-temperature coking, product yield is improved.
Document mostly have employed aprotic polar solvent, mainly comprise N, dinethylformamide, N, N-diethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), dimethyl sulfone, tetramethylene sulfone, N-Methyl pyrrolidone, DMI and cyanobenzene etc., wherein, due to cyanobenzene Heat stability is good, use the most general.
By research, we find that fragrant fluorine cpd also as the solvent of this type of reaction, and can have no the report of this respect before this.
(3) about the use of catalyzer
Similar with the use of solvent, the early stage document such as GB1026290 does not also use catalyzer, solvent was used afterwards in reaction system, for improving mass transfer effect, also phase-transfer catalyst is brought into use, such as US6392084 etc. use crown ether-like catalyzer, JP59152361 mentions and uses polyethers catalyzer, CN104151196 mentions and uses quaternary ammonium salts catalyzer, JP04321644 uses season phosphine saline catalyst, although also have some documents such as CN1772724 to employ solvent, do not use catalyzer.
(4) about temperature of reaction
The difference of foundation reaction raw materials and working pressure, temperature of reaction is not quite similar, and the maximum temperature range that existing document provides is 120 ~ 550 DEG C.For solvent-free reaction system, minimum response temperature is higher than the fusing point of chloro-benzonitrile main raw material; For synthesis under normal pressure, maximum temperature should not exceed and comprise the reaction raw materials of solvent or the boiling point of product; For reaction with pressure, temperature of reaction wants high.
Usually, improve temperature of reaction and be conducive to fast reaction speed, but also easily cause high-temperature coking simultaneously.
(5) about reaction pressure
Only have GB1026290 to mention adopts decompression operation to react in solvent-free situation, have a small amount of documents such as JP59222463 also to mention to react at ambient pressure, most document reacts in the saturation steam pressure of reaction system, also react under having document to mention the saturated vapour pressure adopting and exceed reaction system, such as US6392084 mentions the pressure range of compressive reaction at 0 ~ 30kg/cm
2.
(6) about the control of raw material moisture
US3975424 etc. advocate that, moisture controlled below 0.2%, moisture controlled is obtained good reaction effect 0.02 ~ 0.05% time by Ma Suqin in " the fluoridation research of tetrachlorobenzene dimethoxy nitrile " [D] paper.
In this kind of fluorine permutoid reaction, because the chlorine on position between cyano group not easily reacts, so reaction time is all longer, however, also will have in product can not the intermediate of the fluorochlorobenzene nitrile of fluoro completely.In order to improve product yield, JP59222463 proposes the technique of fluorine permutoid reaction in two steps, supplements new fluorizating agent and solvent, and improves temperature of reaction, improve reaction effect with this at the second step of reaction.JP60184057 is then that the mode by the still liquid cover after extraction product being used for lower batch improves product yield.
About the extraction of the product after this kind of fluorine permutoid reaction, due in reaction system except product, also often have a large amount of solvents, the metal chloride of the by-product that also responds and intermediate product and tar etc., composition is complicated, and product separation is more difficult.In the prior art, following technical scheme is mainly taked.
(1) rectifying after first desalination
This mode all taked by most of document.Such as CN104151196 etc. adopt and first lower the temperature, and after refiltering the salt removing by-product, filtrate is through rectification under vacuum or atmospheric distillation, and other components such as point desolventizing, collect and obtain product.
This method at least will through filtering and rectifying two operating units, technique relative complex, and distillation operation difficulty is large, can not utilize very well residual heat of reaction.
(2) rectifying after first thick steaming
Some documents do not adopt filter type to remove the salt of by-product, but by straight run distillation except desalting.Such as US6392084 etc. adopt first underpressure distillation to obtain organic phase, and organic phase is again through atmospheric distillation, and other components such as point desolventizing, collect and obtain product.
This method at least will be steamed and rectifying two operating units through thick, technique relative complex, and distillation operation difficulty is large, steams be used to residual heat of reaction although thick, and twice distillation energy consumption is quite large.
(3) extracting, evaporating
For specific reaction system and product, also have and to adopt extracting, evaporating mode to extract product, such as US5153350 is first dilute with water reactant after the completion of reaction, and then extract at twice with the ethyl acetate of 1:1 and the mixed solvent of normal hexane, organic phase is first through anhydrous magnesium sulfate drying, 3,4,6-trifluoro phthalonitrile is obtained again after evaporation of solvent.
The characteristic that solvent is water-soluble and product relative volatility is little that this method utilizes reaction used, does not have broad applicability.This method at least will through dilution extraction, dry and evaporation three operating units, and technique is more complicated, and residual heat of reaction can not utilize very well.
(4) vacuum-sublimation
For specific reaction system and product, also to have take to distil extracts product, and such as GB1026290 adopts vacuum-sublimation to obtain tetrafluoro phthalonitrile after the completion of reaction.
This method utilizes the solvent-free characteristic distilled with product of reaction system, does not have broad applicability.This method advantage is vacuum-sublimation operating unit, and technique is simple and direct, is used to residual heat of reaction.
(5) crystallizing and drying is diluted
For specific reaction system and product, employing dilution crystallization mode extracts product in addition, such as US7132561 etc. first lower the temperature after the completion of reaction, and then add a certain amount of water and carry out dilution crystallization, now fractional crystallization thing drying obtains tetrafluoro terephthalonitrile.
The characteristic that solvent is water-soluble and product fusing point is high that this method utilizes reaction used, does not have broad applicability.This method at least will through dilution crystallization, filtration and dry three operating units, and technique is more complicated, and residual heat of reaction does not utilize.
As can be seen here, in the prior art, adopt the fluorine permutoid reaction technique of solvent to be commonplace and maturation, and the purifying technique of fluorinated product is complicated and various, rectification process after the first desalination of everybody more employings.
At present, prepare by fluorine permutoid reaction the fluoro benzonitrile compounds Technical comparing that general formula is (I) ripe, realized industrialization in China, quality product and stable yield.However, prior art still has larger improvements.Such as how to improve reaction effect by process modification, simplify lock out operation, and make full use of the thermal capacity of this high-temperature reaction process, reduce energy dissipation etc.
Summary of the invention
With logical formula II chloro-benzonitrile compounds for raw material, by the logical formula I fluoro benzonitrile compounds of fluorine permutoid reaction preparation, in this kind of reaction process, in order to improve reactive behavior, often need higher temperature condition, again because reaction controls by liquid-solid mass transfer, so the selection of solvent is very important.When selective solvent, need to consider the following aspects: (1) Heat stability is good, not easily the adverse effects such as decomposition or coking occur; (2) easily dry, be conducive to controlling the moisture in reaction system; (3) good to main raw material chloro-benzonitrile compounds solvability at reaction conditions, be conducive to improving liquid-solid interface mass transfer; (4) reaction product is easily separated.In the prior art, only mention and use cyanobenzene or other solvents, and the present invention and it is unlike proposing using the reaction product self of logical formula I fluoro benzonitrile compounds as reaction solvent, its tool has the following advantages: first it is thermally-stabilised is not accommodating doubtful; Secondly, because fragrant fluorine cpd have hydrophobic nature, easily drying is obtained; Having is exactly that itself and corresponding (II) chloro-benzonitrile compounds main raw material thing intermiscibility are good again, is conducive to improving liquid-solid interface mass transfer; Its maximum benefit need not be separated solvent after reaction, and product is easily purified.
The present invention reaction and product separation condition design on different with prior art.The reaction that such as prior art proposes is that the saturation steam pressure of normal pressure or reaction system is carried out, and the present invention reacts under adopting the rare gas element pressurized conditions such as nitrogen, its advantage is: the rare gas elementes such as (1) employing nitrogen add the side reaction that pressure energy fully avoids the active gas such as oxygen to cause; (2) adopt the rare gas elementes such as nitrogen to add the vaporization of pressure energy suppression solvent, thus ensure that solvent plays a role more fully; (3) pressurization is conducive to the sensible heat improving effecting reaction system, favourable to fast reaction speed, simultaneously for more energy is accumulated in product flash distillation.The present invention due to reaction after product more single, so product separation adopts flash distillation just can obtain purer product, do not resemble separating technology used in the prior art and bother.
Technical scheme of the present invention is as follows:
A kind of preparation method of the fluoro benzonitrile compounds as shown in logical formula I, with logical formula II chloro-benzonitrile compounds for raw material, in the presence of an inert gas, using target product self as solvent, react with anhydrous fluorochemical under high temperature, condition of high voltage, obtain target product through flash distillation;
Wherein, the integer of m=1 ~ 3; The integer of m+n=4 ~ 6.
In technique scheme, as preferably, described rare gas element is selected from least one in nitrogen, helium, argon gas.
In technique scheme, described solvent refers to the one in the fluoro benzonitrile compounds shown in logical formula I, namely by target product that this technical scheme will obtain.As target product be penta fluoro benzene formonitrile HCN time, in reaction raw materials, add the penta fluoro benzene formonitrile HCN of specified amount as dissolution with solvents raw material.
In technique scheme, as preferably, the mass ratio of described solvent and raw material is 1:1 ~ 10, is more preferably 1:3 ~ 8.
In technique scheme, as preferably, when reacting, described temperature of reaction controls at 160 ~ 550 DEG C.
In technique scheme, as preferably, when reacting, described reaction pressure controls at 0.2 ~ 5MPa, more preferably controls at 0.5 ~ 4MPa.
In technique scheme, as preferably, described anhydrous fluorochemical is selected from alkaline metal fluoride cpd or alkaline-earth metal fluoride, and wherein said alkaline metal fluoride cpd is selected from least one in Potassium monofluoride, Sodium Fluoride, lithium fluoride, rubidium fluoride or cesium fluoride; Described alkaline-earth metal fluoride is selected from least one in Calcium Fluoride (Fluorspan), magnesium fluoride and barium fluoride.
In technique scheme, as preferably, after the completion of reaction, by reaction mass vacuum flashing, obtain target product.
In technique scheme, as preferably, during described flash distillation, system internal pressure is down to gauge pressure-0.1 ~ 0MPa by virgin state.
In technique scheme, as preferably, during described flash distillation, steam the temperature range between product temperatur condenses to product fusing point by virgin state to boiling point, described temperature range does not comprise fusing point and the boiling point of product.
The reaction principal product (i.e. target product) of logical formula I fluoro benzonitrile compounds is introduced reaction system as solvent by the present invention, not only reduce the kind of the raw material resources that reaction uses, and the mode product separation of flash distillation can be adopted after the completion of reaction, thus achieve and economize on resources, simplify product separation technique and energy-saving and cost-reducing object.
The present invention can use catalyzer in reaction process, also can not use catalyzer.When a phase transfer catalyst is used, favourable to fast reaction speed, but have disadvantageous effect to product separation; Do not use catalyst reaction can carry out smoothly in the same old way, and very favourable to product separation.
The difference of the present invention and existing fluoro benzonitrile compounds technology of preparing is the following aspects:
(1) solvent used is different
Prior art has two kinds of situations, and a class does not use solvent, reacts easy coking in this case; Another kind of is use the aprotic polar solvents such as cyanobenzene, and product separation technics comparing is complicated in this case;
And the present invention only uses product as the solvent of reaction, both avoiding reacting when not using solvent easy coking problem, having solved again the problem of the product separation complex process brought because using other solvents;
(2) pressure condition used is reacted different
Prior art often adopts the saturation steam pressure of normal pressure or reaction system to carry out in fluorine exchange procedure, owing to lacking enough protection of inert gas, easily produces oxidation side reaction;
The present invention adopts rare gas element to be forced into higher than reaction system saturated vapor pressure condition originally in fluorine exchange procedure, is conducive to anti-oxidation side reaction, reduces solvent evaporation to ensure that it plays one's part to the full, and improve the heat energy deposit of reaction system;
(3) mode of product extraction is different
Prior art, after fluorine permutoid reaction terminates, often adopts and first slightly steams rectifying again, or the mode that first decrease temperature crystalline is purified again, complex technical process, and energy consumption is larger;
The present invention, after fluorine permutoid reaction terminates, makes full use of the thermal capacity of material self, only just can obtain the higher product of purity by flash distillation, reasonable energy utilization, simple process.
In sum, the present invention proposes a kind of new preparation process of logical formula I fluoro benzonitrile compounds.Novel process to react target product for solvent, and adopts rare gas element pressuring method to improve fluorine permutoid reaction and product separation condition, and product separation is purified and adopted the mode of flash distillation, and Appropriate application residual heat of reaction, whole simple process is feasible.Method raw material provided by the invention is easy to get, and technique is simple and direct, energy-saving and cost-reducing, thus is more suitable for commercial scale production.
Accompanying drawing explanation
Accompanying drawing 1 width of the present invention.
Fig. 1 is preparation method's schema of fluoro benzonitrile compounds of the present invention;
Wherein:
AF: anhydrous fluorochemical;
CBN: chloro-benzonitrile compounds;
FBN: fluoro benzonitrile compounds;
NG: rare gas element.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.In following embodiment, if no special instructions, the experimental technique used is ordinary method, and material therefor, reagent etc. all can be bought from biological or chemical company.
Fig. 1 is preparation method's schema of fluoro benzonitrile compounds of the present invention, and wherein AF is anhydrous fluorochemical; CBN is chloro-benzonitrile compounds; FBN is fluoro benzonitrile compounds; NG is rare gas element.Be specially: drop into AF, CBN and FBN respectively in reactor, pass into the air in NG eliminating reactor, under NG exists, under high temperature, condition of high voltage, carry out fluorine permutoid reaction, reaction product obtains target product FBN through flash distillation.Exhaust gas of flash evaporation can carry out the degree of depth via the absorption system of cold well and adsorber and air collector composition and catch long-pending product, and by residual gas through collecting in order to reuse.Flash distillation waste residue can through to burn or solvent wash or dissolving, extraction, crystallization, the mode such as centrifugal reclaim Industrial Salt.
The preparation of embodiment 1 penta fluoro benzene formonitrile HCN
1. fluoridize: fluoridize in autoclave to the 10L being furnished with flash condenser and reception still, drop into pentachlorobenzonitrile 1000g (3.6mol), anhydrous potassium fluoride 1280g (21.6mol) and penta fluoro benzene formonitrile HCN 3000g (15.4mol) respectively, nitrogen replacement three times, get rid of the air in still, nitrogen is suppressed to 1MPa, airtight, in whipped state by behind still temperature rise to 280 ~ 300 DEG C, insulation 20h, reactor gauge pressure is up to 2.1MPa, do gas chromatographic analysis to still liquid sample, penta fluoro benzene formonitrile HCN content is 95.6%.
2. flash distillation: first the flash condenser received on still and tail gas gathering device are led to heat-eliminating medium precooling, then the flash distillation outlet valve fluoridizing autoclave is slowly opened, control flash condenser condensate temperature and do not exceed 50 ~ 60 DEG C, the still pressure drop of autoclave to be fluorinated is to normal pressure, be decompressed to-0.085MPa again, steam and steam to no longer including fraction, receive product 3603g, through gas chromatographic analysis, penta fluoro benzene formonitrile HCN content is 98.5%.
The preparation of embodiment 2 penta fluoro benzene formonitrile HCN
1. fluoridize: fluoridize in autoclave to the 10L being furnished with flash condenser and reception still, drop into pentachlorobenzonitrile 1000g (3.6mol), anhydrous potassium fluoride 1280g (21.6mol) and penta fluoro benzene formonitrile HCN 5000g (25.6mol) respectively, nitrogen replacement three times, get rid of the air in still, nitrogen is suppressed to 1MPa, airtight, in whipped state by behind still temperature rise to 320 ~ 340 DEG C, insulation 20h, reactor gauge pressure is up to 2.8MPa, do gas chromatographic analysis to still liquid sample, penta fluoro benzene formonitrile HCN content is 98.7%.
2. flash distillation: first the flash condenser received on still and tail gas gathering device are led to heat-eliminating medium precooling, then the flash distillation outlet valve fluoridizing autoclave is slowly opened, control flash condenser condensate temperature and do not exceed 50 ~ 60 DEG C, the still pressure drop of autoclave to be fluorinated is to normal pressure, be decompressed to-0.085MPa again, steam and steam to no longer including fraction, receive product 5624g, through gas chromatographic analysis, penta fluoro benzene formonitrile HCN content is 99.0%.
The preparation of embodiment 3 penta fluoro benzene formonitrile HCN
1. fluoridize: fluoridize in autoclave to the 10L being furnished with flash condenser and reception still, drop into pentachlorobenzonitrile 1000g (3.6mol), anhydrous potassium fluoride 1280g (21.6mol) and penta fluoro benzene formonitrile HCN 4000g (20.5mol) respectively, nitrogen replacement three times, get rid of the air in still, nitrogen is suppressed to 1MPa, airtight, in whipped state by behind still temperature rise to 240 ~ 250 DEG C, insulation 8h, reactor gauge pressure is up to 1.6MPa, do gas chromatographic analysis to still liquid sample, penta fluoro benzene formonitrile HCN content is 95.1%.
2. flash distillation: first the flash condenser received on still and tail gas gathering device are led to heat-eliminating medium precooling, then the flash distillation outlet valve fluoridizing autoclave is slowly opened, control flash condenser condensate temperature and do not exceed 50 ~ 60 DEG C, distillation is stopped after flashing off 653g product, product is through gas chromatographic analysis, and penta fluoro benzene formonitrile HCN content is 98.4%.
The preparation of embodiment 4 penta fluoro benzene formonitrile HCN
1. fluoridize: the residual middle input pentachlorobenzonitrile 1000g (3.6mol) of the flash vaporization kettle to embodiment 3 and anhydrous potassium fluoride 1072g (18.1mol), nitrogen replacement three times, get rid of the air in still, nitrogen is suppressed to 1MPa, airtight, in whipped state by behind still temperature rise to 240 ~ 250 DEG C, insulation 8h, reactor gauge pressure is up to 1.6MPa, does gas chromatographic analysis to still liquid sample, and penta fluoro benzene formonitrile HCN content is 95.4%.
2. flash distillation: first the flash condenser received on still and tail gas gathering device are led to heat-eliminating medium precooling, then the flash distillation outlet valve fluoridizing autoclave is slowly opened, control flash condenser condensate temperature and do not exceed 50 ~ 60 DEG C, distillation is stopped after flashing off 645g product, product is through gas chromatographic analysis, and penta fluoro benzene formonitrile HCN content is 98.7%.
The preparation of embodiment 5 tetrafluoro phthalonitrile
1. fluoridize: fluoridize in autoclave to the 10L being furnished with flash condenser and reception still, drop into tetrachloro phthalonitrile 1000g (3.7mol), anhydrous potassium fluoride 1020g (17.2mol) and tetrafluoro phthalonitrile 4000g (19.8mol) respectively, nitrogen replacement three times, get rid of the air in still, nitrogen is suppressed to 0.5MPa, airtight, in whipped state by behind still temperature rise to 360 ~ 380 DEG C, insulation 18h, reactor gauge pressure is up to 1.3MPa, do gas chromatographic analysis to still liquid sample, tetrafluoro phthalonitrile content is 96.3%.
2. flash distillation: first the flash condenser received on still and tail gas gathering device are led to heat-eliminating medium precooling, then the flash distillation outlet valve fluoridizing autoclave is slowly opened, control flash condenser condensate temperature and do not exceed 85 ~ 95 DEG C, the still pressure drop of autoclave to be fluorinated is to normal pressure, be decompressed to-0.085MPa again, steam and steam to no longer including fraction, receive product 4640g, through gas chromatographic analysis, tetrafluoro phthalonitrile content is 98.6%.
Claims (10)
1. the preparation method of the fluoro benzonitrile compounds as shown in logical formula I, with logical formula II chloro-benzonitrile compounds for raw material, in the presence of an inert gas, using target product self as solvent, react with anhydrous fluorochemical under high temperature, condition of high voltage, obtain target product through flash distillation;
Wherein, the integer of m=1 ~ 3; The integer of m+n=4 ~ 6.
2. preparation method according to claim 1, is characterized in that, described rare gas element is selected from least one in nitrogen, helium, argon gas.
3. preparation method according to claim 1, is characterized in that, described solvent is the one in the fluoro benzonitrile compounds shown in logical formula I.
4. the preparation method according to claim 1 or 3, is characterized in that, the mass ratio of described solvent and raw material is 1:1 ~ 10.
5. preparation method according to claim 1, is characterized in that, during described reaction, temperature of reaction controls at 160 ~ 550 DEG C.
6. preparation method according to claim 1, is characterized in that, during described reaction, pressure-controlling is at 0.2 ~ 5MPa.
7. preparation method according to claim 1, is characterized in that, described anhydrous fluorochemical is selected from alkaline metal fluoride cpd or alkaline-earth metal fluoride.
8. preparation method according to claim 7, is characterized in that, described alkaline metal fluoride cpd is selected from least one in Potassium monofluoride, Sodium Fluoride, lithium fluoride, rubidium fluoride or cesium fluoride; Described alkaline-earth metal fluoride is selected from least one in Calcium Fluoride (Fluorspan), magnesium fluoride or barium fluoride.
9. preparation method according to claim 1, is characterized in that, after the completion of reaction, when carrying out flash distillation to reaction product, system internal pressure is down to gauge pressure-0.1 ~ 0MPa by virgin state.
10. the preparation method according to claim 1 or 9, is characterized in that, during described flash distillation, steams the temperature range between product temperatur condenses to product fusing point by virgin state to boiling point.
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| CN115260009A (en) * | 2021-04-29 | 2022-11-01 | 新岸诺亚（北京）催化科技有限公司 | Preparation method of m-fluorophenol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115260009A (en) * | 2021-04-29 | 2022-11-01 | 新岸诺亚（北京）催化科技有限公司 | Preparation method of m-fluorophenol |
| CN115260009B (en) * | 2021-04-29 | 2023-11-24 | 新岸诺亚（北京）催化科技有限公司 | Preparation method of m-fluorophenol |
| CN115260010B (en) * | 2021-04-29 | 2023-11-24 | 新岸诺亚（北京）催化科技有限公司 | Method for preparing m-fluorophenol from 2, 6-difluorobenzonitrile |
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Inventor after: Hou Guang Inventor after: Jiang Dianbao Inventor before: Hou Guang Inventor before: Jiang Dianping |