CN105237470A - Method for preparing 2,5,6-trichloro-3-tirfluoromethylpyridine from DCTF rectifying short steaming residues - Google Patents
Method for preparing 2,5,6-trichloro-3-tirfluoromethylpyridine from DCTF rectifying short steaming residues Download PDFInfo
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
A method for preparing 2,5,6-trichloro-3-tirfluoromethylpyridine from DCTF rectifying short steaming residues can improve the resource utilization rate. The method comprises the following steps: converting polymers in the residues through in situ catalytic cracking and vacuum distillation by using the catalytic degradation function of a catalyst formed by alumina, silica, zirconia, 4A zeolite, magnesium oxide, mordenite and HZSM-5 zeolite on the polymers in the DCTF rectifying short steaming residues in order to form micro-molecular compounds and obtain 2,5,6-trichloro-3-tirfluoromethylpyridine-containing crude oil; and carrying out alkaline assistant aqueous solution washing on the 2,5,6-trichloro-3-tirfluoromethylpyridine-containing crude oil, carrying out reduced pressure rectification, carrying out refrigerating crystallization, carrying out vacuum filtration or centrifuging separation, carrying out solvent washing, and carrying out vacuum drying treatment to obtain a 2,5,6-trichloro-3-tirfluoromethylpyridine product with the mass percentage content being greater than 95% at a yield being 0.1-10% of the mass of the DCTF rectifying short steaming residues.
Description
Technical field
One involved in the present invention utilizes the short steaming residue of DCTF rectifying to prepare 2,5, the method of the chloro-3-5-flumethiazine of 6-tri-is a kind of novel method realizing chemical by-product resource utilization efficiency utilization that Minute Organic Synthesis field Fine Organic Chemical product prepare aspect.
Background technology
DCTF, chemistry 2,3-bis-chloro-5-trifluoromethylpyridine by name, No. CAS is 69045-84-7, the colourless transparent liquid of 1.55 (water is 1.0) that to be a kind of relative density under room temperature condition be.As a kind of important agricultural chemicals and medicine intermediate, DCTF not only can be used for the production of the Fluoric Herbicides such as fluazifop, the spirit of chlorine fluorine second standing grain, haloxyfop, and is also widely used in the production of the agricultural chemicals such as the fluorine-containing process for preparation of benzoylurea compounds such as fluazuron, UC 62644, chlorfluazuron and efficient germicide fluazinam and fluorine-containing medicines.Take DCTF as these agrochemicals that one of basic raw material is produced, not only there is the feature that drug effect is high, toxicity is low, but also have and pollute the distinguishing feature such as little and environmentally friendly, thus very fast in nearly more than ten years development.
The preparation of DCTF mainly contains following several method: (1) for raw material, first generates 2-amino-3-chloro-5-trichloromethylpyridine through chlorination with 2-amino-5-picoline, then through diazotization and Cu
2cl
2obtain 2,3-bis-chloro-5-trichloromethylpyridines Deng the diazo chlorine replacement reaction under catalyzer existence, finally under the catalyzer such as red precipitate or Mercury difluoride exists, obtain DCTF by 2,3-bis-chloro-5-trichloromethylpyridines and hydrogen fluoride reaction; (2) take CMP as raw material, first under photochemical catalysis, carry out pendant chlorine obtains 2-chloro-5-trichloromethylpyridine, under the catalysts such as Lewis acid, carry out chlorination on ring more further obtain 2,3-bis-chloro-5-trichloromethylpyridine, finally under the catalyzer such as red precipitate or Mercury difluoride exists, obtain DCTF by 2,3-bis-chloro-5-trichloromethylpyridines and hydrogen fluoride reaction; (3) with 3-picoline for raw material, first under photochemical catalysis, generate 3-nitrapyrin with chlorine reaction, under the catalysts such as Lewis acid, carry out chlorination on ring again obtain 2,3-bis-chloro-5-trichloromethylpyridine, finally under the catalyzer such as red precipitate or Mercury difluoride exists, obtain DCTF by 2,3-bis-chloro-5-trichloromethylpyridines and hydrogen fluoride reaction; (4) take CCMP as raw material, first carry out Light chlorimation and generate 2-chloro-5-trichloromethylpyridine, 2 are generated through thermal chlorination again under the catalysts such as Lewis acid, 3-bis-chloro-5-trichloromethylpyridine, finally under the catalyzer such as red precipitate or Mercury difluoride exists, obtain DCTF by 2,3-bis-chloro-5-trichloromethylpyridines and hydrogen fluoride reaction.Be wherein the technique of raw material production DCTF with CCMP, raw materials cost be low, reaction preference is high owing to having, numerous advantage such as good product quality and apply more extensive in the production of DCTF.
In the technique being raw material production DCTF with CCMP, 3-picoline or CMP, 2, the reaction mass that 3-bis-chloro-5-trichloromethylpyridine obtains with hydrogen fluoride reaction under the catalyzer such as red precipitate or Mercury difluoride exists first need carry out preliminary short distillation to generate the short steaming liquid containing DCTF, and then by carrying out further rectifying to obtain DCTF product to the short steaming liquid obtained.When carrying out preliminary short distillation to obtain the short steaming liquid containing DCTF to the reaction mass obtained with hydrogen fluoride reaction under the catalyzer such as red precipitate or Mercury difluoride exists by 2,3-bis-chloro-5-trichloromethylpyridine, the short steaming residue of a large amount of DCTF rectifying can be produced.Because the material in this rectifying short steaming residue is the substituted pyridine compounds and their polymkeric substance that molecular structure contain multiple halogen atom mostly, these contain the substituted pyridine compounds of multiple halogen atom and their polymkeric substance does not have incendivity or combustibility is extremely low, are thus difficult to carry out harmless treatment by simple incinerating method.How effectively to process the short steaming residue of DCTF rectifying, and realize separation and purification or the conversion of material contained by it, reduce the potentially contaminated hazardness that the production cost of DCTF and the short steaming residue of DCTF rectifying exist environment, and the effective rate of utilization fully improving resource day by day to become the problem of people's care in recent years.
The chloro-3-5-flumethiazine of 2,5,6-tri-, No. CAS is 80289-91-4, is one of important derivatives of DCTF, is also a kind of important fluoro-containing pesticide and medicine intermediate, can be used for the synthesis of multiple agrochemicals and medicine.2 are prepared utilizing the short steaming residue of DCTF rectifying, 5, in the research process of the chloro-3-5-flumethiazine of 6-tri-, contact a lot of relevant 2, 3-bis-chloro-5-trifluoromethylpyridine and 2, 5, the technical information of 6-tri-chloro-3-5-flumethiazine Synthesis and applications aspect, wherein there is mainly comprising of some reference value: " 2, the preparation of 3-bis-chloro-5-trichlorine (fluorine) picoline " (organic fluorine industry, 1st phase in 2010), " 2, the synthetic method of 3-bis-chloro-5-trifluoromethylpyridine is commented " (modern, 2nd phase in 2006), " 2, the study on the synthesis of 3-bis-chloro-5-trifluoromethylpyridine " (Hebei chemical industry, 3rd phase in 2003), " SomeNew2-Substituted5-trifluoromethylpyridines " (Heterecycles, 2nd phase in 1984), " synthesis 2, the progress of 3-bis-chloro-5-trifluoromethylpyridine " (chemical reagent, 6th phase in 2004), " novel pesticide UC 62644 " (agricultural chemicals, 4th phase in 1989), " Synthesisofhalogenatedpyridine " (J.Org.Chem., 25th phase in 1985), " novel method synthesis 2-chloro-5-trichloromethylpyridine " (Chemical Engineering Technology and exploitation, 5th phase in 2004), " application in pesticide synthesis of 3-picoline and derivative thereof " (agricultural chemicals, 6th phase in 1999), " Processforproducing3-chloro-5-trifluoromethylpyridines " (US4490543, 1984-12-25), " Preparationof3, 6-dichloro-2-trichloromethylpyridinebyvaporphasechlorina tionof6-chloro-2-trichloromethylpyridine " (US20040176607A1, 2004-09-09), " Preparationof2, 3-difluoro-5-(trifluoromethyl) pyridine " (US5073637, 1991-12-17).
Summary of the invention
One utilizes the short steaming residue of DCTF rectifying to prepare 2, 5, the invention of 6-tri-chloro-3-5-flumethiazine method, mainly pass through optical chlorinating reaction to realize, thermal chlorination reaction and fluoridation produce 2, in the technique of 3-bis-chloro-5-trifluoromethylpyridine, the short steaming residue of DCTF rectifying produced in a large number during the predistillation implemented before carrying out rectifying separation to the reaction mass containing DCTF after fluoridation effectively processes, and with it for one of basic raw material is to prepare agricultural chemicals and medicine intermediate 2, 5, the chloro-3-5-flumethiazine of 6-tri-, thus improve the effective rate of utilization of resource, reduce the potentially contaminated hazardness that the short steaming residue of rectifying that produces in the production cost of DCTF and DCTF production technique exists environment.
Technical scheme of the present invention is: the chloro-pyridine compounds existed in the short steaming residue of the DCTF rectifying utilizing DCTF production technique to produce, fluorinated pyridine compounds, the polymkeric substance that fluorine chloro-pyridine compounds is formed under the high temperature conditions and chloro-pyridine micromolecular compound, fluorinated pyridine micromolecular compound and fluorine chloro-pyridine micromolecular compound are in volatility, difference on solvability and boiling point, and by aluminium sesquioxide, silicon-dioxide, zirconium white, 4A zeolite, magnesium oxide, mordenite, HZSM-5 zeolite is that 0.01 ~ 50: 0.01 ~ 60: 0.001 ~ 10: 0.01 ~ 80: 0.001 ~ 10: 0.01 ~ 30: 0.01 ~ 10 catalyzer formed are to chloro-pyridine compounds in mass ratio, the catalyzed degradation function of the polymkeric substance that fluorine chloro-pyridine compounds and fluorinated pyridine compounds are formed under the high temperature conditions, be 0.01 ~ 20: 0.01 ~ 90 material to be joined in reactor respectively by the mass ratio of catalyzer and the short steaming residue of DCTF rectifying, to stir and by the means of DCTF rectifying short steaming residue catalytic pyrolysis in place and vacuum distilling under the condition of 0.001MPa ~ 0.101MPa vacuum tightness and 100 ~ 400 DEG C, promote the chloro-pyridine compounds be present in the short steaming residue of DCTF rectifying, the polymer conversion that fluorine chloro-pyridine compounds and fluorinated pyridine compounds are formed under the high temperature conditions is for comprising 2, the chloro-5-of 3-bis-(difluorochloromethyl) pyridine, 2, 3-bis-chloro-5-trichloromethylpyridine, 2, 3, 4, 6-tetra-chloro-5-trifluoromethylpyridine, 2, 3, the chloro-5-of 6-tri-(dichlorofluoromethyl) pyridine, 2, 3, the chloro-5-of 6-tri-(difluorochloromethyl) pyridine, 5, the chloro-3-4-hydroxymethylpiperidine of 6-bis--2-phenol, 2, the chloro-5-of 3-bis-(dichlorofluoromethyl) pyridine, Perchloropyridine, 2, 5, 6-tri-chloro-3-5-flumethiazine is at interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine micromolecular compound, and be separated with the polymkeric substance being difficult to cracking that the reaction mass containing DCTF carries out being formed in the short steamed journey of rectifying, thus obtain containing 2, the thick oil of the chloro-5-of 3-bis-(difluorochloromethyl) pyridine, containing 2, the thick oil of the chloro-5-of 3-bis-(difluorochloromethyl) pyridine is the mass percentage concentration that 0.01 ~ 10: 0.01 ~ 8: 0.01 ~ 10: 0.01 ~ 5: 0.001 ~ 8: 0.001 ~ 10 alkaline assistants formed are made into via sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia and sodium hydroxide is in mass ratio the solution washing of 0.01 ~ 20%, to realize the removal of its middle acid substance, by to after alkali liquid washing containing 2, the thick oil of the chloro-5-of 3-bis-(difluorochloromethyl) pyridine carries out rectification under vacuum successively and collects the fraction of 90 ~ 160 DEG C/100 ~ 1000Pa, freezing and crystallizing, vacuum filtration or centrifugation, realize 2, the chloro-5-of 3-bis-(difluorochloromethyl) pyridine and other chloro-pyridine compounds in thick oil are separated with fluorine chloro-pyridine compounds, and obtain the chloro-5-of 2,3-bis-(difluorochloromethyl) pyridine crude product, by by sherwood oil, ether, cyclohexane, octane-iso, benzene, toluene and dimethylbenzene are that 0.01 ~ 100: 0.001 ~ 20: 0.001 ~ 100: 0.01 ~ 50: 0.001 ~ 8: 0.001 ~ 10: 0.001 ~ 10 double solventss formed wash obtain through vacuum filtration or centrifugation 2 in mass ratio, 5, 6-tri-chloro-3-5-flumethiazine crude product, and under the condition of 0.001MPa ~ 0.101MPa vacuum tightness and-10 ~ 50 DEG C, vacuum-drying is carried out to the solid obtained, realize 2, 5, the purifying of the chloro-3-5-flumethiazine of 6-tri-, namely to obtain 2 relative to the yield of the short steaming mass of residue 0.1 ~ 10% of DCTF rectifying, 5, 6-tri-chloro-3-5-flumethiazine mass percentage is greater than 95% 2, 5, 6-tri-chloro-3-5-flumethiazine product.
Accompanying drawing explanation
Fig. 1 is the structural formula figure of 2,5,6-tri-chloro-3-5-flumethiazine product.
Fig. 2 is the MS figure of the chloro-3-5-flumethiazine of 2,5,6-tri-.
Specific implementation method
Provide some embodiments below, so that the invention will be further described.
Embodiment 1:
1000 grams of short steaming residues of DCTF rectifying and 100 grams are by aluminium sesquioxide, silicon-dioxide, zirconium white, 4A zeolite, magnesium oxide, mordenite, HZSM-5 zeolite is that 0.01: 30: 10: 20: 10: 0.01: 0.1 catalyzer formed joins in reactor together in mass ratio, stir and realize DCTF rectifying short steaming residue catalytic pyrolysis in place and vacuum distilling under the condition of 0.01MPa vacuum tightness and 400 DEG C, making to be present in the chloro-pyridine compounds in the short steaming residue of DCTF rectifying, the polymer conversion that fluorine chloro-pyridine compounds and fluorinated pyridine compounds are formed under the high temperature conditions is for comprising the chloro-3-5-flumethiazine of 2,5,6-tri-, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridine, the chloro-5-of 2,3,6-tri-(dichlorofluoromethyl) pyridine, the chloro-5-of 2,3,6-tri-(difluorochloromethyl) pyridine, the chloro-3-4-hydroxymethylpiperidine of 5,6-bis--2-phenol, the chloro-5-of 2,3-bis-(dichlorofluoromethyl) pyridine, Perchloropyridine, 2, the chloro-5-of 3-bis-(difluorochloromethyl) pyridine is at interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine micromolecular compound, and be separated with the polymkeric substance being difficult to cracking that the reaction mass containing DCTF carries out being formed in the short steamed journey of rectifying, thus obtain containing 2, the thick oil of 5,6-tri-chloro-3-5-flumethiazine, be that the solution washing of 0.1% is containing 2 by being mass percentage concentration that 0.1: 8: 0.01: 0.5: 4: 5 alkaline assistants formed are made in mass ratio by sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia and sodium hydroxide, 5, the thick oil of 6-tri-chloro-3-5-flumethiazine, to realize the removal of its middle acid substance, by to after alkali liquid washing containing 2,5, the thick oil of 6-tri-chloro-3-5-flumethiazine carries out rectification under vacuum successively and collects the fraction of 100 ~ 110 DEG C/100 ~ 1000Pa, freezing and crystallizing, vacuum filtration or centrifugation, realize 2,5,6-tri-chloro-3-5-flumethiazine and other chloro-pyridine compounds in thick oil are separated with fluorine chloro-pyridine compounds, and obtain 2,5,6-tri-chloro-3-5-flumethiazine crude product, by by sherwood oil, ether, cyclohexane, octane-iso, benzene, toluene and dimethylbenzene are that 0.01: 20: 0.1: 15: 0.001: 1: 0.1 double solvents formed washs obtained by vacuum filtration or centrifugation 2 in mass ratio, 5, 6-tri-chloro-3-5-flumethiazine crude product, and under the condition of 0.08MPa vacuum tightness and 20 DEG C, drying is carried out to the solid obtained, last to obtain 2 relative to the yield of the short steaming mass of residue 10% of DCTF rectifying, 5, 6-tri-chloro-3-5-flumethiazine mass percentage is 96% 2, 5, 6-tri-chloro-3-5-flumethiazine product.
Embodiment 2:
1000 grams of short steaming residues of DCTF rectifying and 50 grams are by aluminium sesquioxide, silicon-dioxide, zirconium white, 4A zeolite, magnesium oxide, mordenite, HZSM-5 zeolite is that 0.1: 2: 1: 0.1: 3: 0.1: 0.01 catalyzer formed joins in reactor together in mass ratio, stir and realize DCTF rectifying short steaming residue catalytic pyrolysis in place and vacuum distilling under the condition of 0.05MPa vacuum tightness and 350 DEG C, making to be present in the chloro-pyridine compounds in the short steaming residue of DCTF rectifying, the polymer conversion that fluorine chloro-pyridine compounds and fluorinated pyridine compounds are formed under the high temperature conditions is for comprising the chloro-3-5-flumethiazine of 2,5,6-tri-, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridine, the chloro-5-of 2,3,6-tri-(dichlorofluoromethyl) pyridine, the chloro-5-of 2,3,6-tri-(difluorochloromethyl) pyridine, the chloro-3-4-hydroxymethylpiperidine of 5,6-bis--2-phenol, the chloro-5-of 2,3-bis-(dichlorofluoromethyl) pyridine, Perchloropyridine, 2, the chloro-5-of 3-bis-(difluorochloromethyl) pyridine is at interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine compounds, and be separated with the polymkeric substance being difficult to cracking that the reaction mass containing DCTF carries out being formed in the short steamed journey of rectifying, thus obtain containing 2, the thick oil of 5,6-tri-chloro-3-5-flumethiazine, be that the solution washing of 1% is containing 2 by being mass percentage concentration that 1: 0.8: 0.1: 5: 0.4: 0.5 alkaline assistant formed is made in mass ratio by sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia and sodium hydroxide, 5, the thick oil of 6-tri-chloro-3-5-flumethiazine, to realize the removal of its middle acid substance, by to after alkali liquid washing containing 2,5, the thick oil of 6-tri-chloro-3-5-flumethiazine carries out rectification under vacuum successively and collects the fraction of 90 ~ 110 DEG C/100 ~ 1000Pa, freezing and crystallizing, vacuum filtration or centrifugation, realize 2,5,6-tri-chloro-3-5-flumethiazine and other chloro-pyridine compounds in thick oil are separated with fluorine chloro-pyridine compounds, and obtain 2,5,6-tri-chloro-3-5-flumethiazine crude product, by being that 100: 10: 0.1: 3: 8: 10: 10 double solventss formed wash obtained by vacuum filtration or centrifugation 2 in mass ratio by sherwood oil, ether, cyclohexane, octane-iso, benzene, toluene and dimethylbenzene, 5,6-tri-chloro-3-5-flumethiazine crude product, and under the condition of 0.10MPa vacuum tightness and 30 DEG C, drying is carried out to the solid obtained, last to obtain 2 relative to the yield of the short steaming mass of residue 1% of DCTF rectifying, 5,6-tri-chloro-3-5-flumethiazine mass percentage is 98.7% 2,5,6-tri-chloro-3-5-flumethiazine product.
Embodiment 3:
1000 grams of short steaming residues of DCTF rectifying and 10 grams are by aluminium sesquioxide, silicon-dioxide, zirconium white, 4A zeolite, magnesium oxide, mordenite, HZSM-5 zeolite is that 1: 0.2: 1: 0.01: 15: 10: 10 catalyzer formed join in reactor together in mass ratio, stir and realize DCTF rectifying short steaming residue catalytic pyrolysis in place and vacuum distilling under the condition of 0.09MPa vacuum tightness and 300 DEG C, making to be present in the chloro-pyridine compounds in the short steaming residue of DCTF rectifying, the polymer conversion that fluorine chloro-pyridine compounds and fluorinated pyridine compounds are formed under the high temperature conditions is for comprising the chloro-3-5-flumethiazine of 2,5,6-tri-, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridine, the chloro-5-of 2,3,6-tri-(dichlorofluoromethyl) pyridine, the chloro-5-of 2,3,6-tri-(difluorochloromethyl) pyridine, the chloro-3-4-hydroxymethylpiperidine of 5,6-bis--2-phenol, the chloro-5-of 2,3-bis-(dichlorofluoromethyl) pyridine, Perchloropyridine, 2, the chloro-5-of 3-bis-(difluorochloromethyl) pyridine is at interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine compounds, and be separated with the polymkeric substance being difficult to cracking that the reaction mass containing DCTF carries out being formed in the short steamed journey of rectifying, thus obtain containing 2, the thick oil of 5,6-tri-chloro-3-5-flumethiazine, be that the solution washing of 5% is containing 2 by being mass percentage concentration that 10: 0.01: 10: 5: 4: 10 alkaline assistants formed are made in mass ratio by sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia and sodium hydroxide, 5, the thick oil of 6-tri-chloro-3-5-flumethiazine, to realize the removal of its middle acid substance, by to after alkali liquid washing containing 2,5, the thick oil of 6-tri-chloro-3-5-flumethiazine carries out rectification under vacuum successively and collects the fraction of 100 ~ 120 DEG C/100 ~ 1000Pa, freezing and crystallizing, vacuum filtration or centrifugation, realize 2,5,6-tri-chloro-3-5-flumethiazine and other chloro-pyridine compounds in thick oil are separated with fluorine chloro-pyridine compounds, and obtain 2,5,6-tri-chloro-3-5-flumethiazine crude product, by being that 100: 0.02: 30: 50: 4: 0.5: 10 double solventss formed wash obtained by vacuum filtration or centrifugation 2 in mass ratio by sherwood oil, ether, cyclohexane, octane-iso, benzene, toluene and dimethylbenzene, 5,6-tri-chloro-3-5-flumethiazine crude product, and under the condition of 0.09MPa vacuum tightness and 20 DEG C, drying is carried out to the solid obtained, last to obtain 2 relative to the yield of the short steaming mass of residue 5% of DCTF rectifying, 5,6-tri-chloro-3-5-flumethiazine mass percentage is 98% 2,5,6-tri-chloro-3-5-flumethiazine product.
Embodiment 4:
1000 grams of short steaming residues of DCTF rectifying and 5 grams are by aluminium sesquioxide, silicon-dioxide, zirconium white, 4A zeolite, magnesium oxide, mordenite, HZSM-5 zeolite is that 30: 60: 0.01: 40: 3: 15: 10 catalyzer formed join in reactor together in mass ratio, stir and realize DCTF rectifying short steaming residue catalytic pyrolysis in place and vacuum distilling under the condition of 0.09MPa vacuum tightness and 300 DEG C, making to be present in the chloro-pyridine compounds in the short steaming residue of DCTF rectifying, the polymer conversion that fluorine chloro-pyridine compounds and fluorinated pyridine compounds are formed under the high temperature conditions is for comprising the chloro-3-5-flumethiazine of 2,5,6-tri-, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridine, the chloro-5-of 2,3,6-tri-(dichlorofluoromethyl) pyridine, the chloro-5-of 2,3,6-tri-(difluorochloromethyl) pyridine, the chloro-3-4-hydroxymethylpiperidine of 5,6-bis--2-phenol, the chloro-5-of 2,3-bis-(dichlorofluoromethyl) pyridine, Perchloropyridine, 2, the chloro-5-of 3-bis-(difluorochloromethyl) pyridine is at interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine compounds, and be separated with the polymkeric substance being difficult to cracking that the reaction mass containing DCTF carries out being formed in the short steamed journey of rectifying, thus obtain containing 2, the thick oil of 5,6-tri-chloro-3-5-flumethiazine, be that the solution washing of 10% is containing 2 by being mass percentage concentration that 10: 4: 5: 5: 3: 10 alkaline assistants formed are made in mass ratio by sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia and sodium hydroxide, 5, the thick oil of 6-tri-chloro-3-5-flumethiazine, to realize the removal of its middle acid substance, by to after alkali liquid washing containing 2,5, the thick oil of 6-tri-chloro-3-5-flumethiazine carries out rectification under vacuum successively and collects the fraction of 110 ~ 130 DEG C/100 ~ 1000Pa, freezing and crystallizing, vacuum filtration or centrifugation, realize 2,5,6-tri-chloro-3-5-flumethiazine and other chloro-pyridine compounds in thick oil are separated with fluorine chloro-pyridine compounds, and obtain 2,5,6-tri-chloro-3-5-flumethiazine crude product, by by sherwood oil, ether, cyclohexane, octane-iso, benzene, toluene and dimethylbenzene are that 100: 0.02: 0.01: 50: 4: 0.01: 5 double solventss formed wash obtained by vacuum filtration or centrifugation 2 in mass ratio, 5, 6-tri-chloro-3-5-flumethiazine crude product, and under the condition of 0.09MPa vacuum tightness and 20 DEG C, drying is carried out to the solid obtained, last to obtain 2 relative to the yield of the short steaming mass of residue 3% of DCTF rectifying, 5, 6-tri-chloro-3-5-flumethiazine mass percentage is 98.5% 2, 5, 6-tri-chloro-3-5-flumethiazine product.
Embodiment 5:
1000 grams of short steaming residues of DCTF rectifying and 3 grams are by aluminium sesquioxide, silicon-dioxide, zirconium white, 4A zeolite, magnesium oxide, mordenite, HZSM-5 zeolite is that 50: 30: 0.1: 37: 5: 18: 9 catalyzer formed join in reactor together in mass ratio, stir and realize DCTF rectifying short steaming residue catalytic pyrolysis in place and vacuum distilling under the condition of 0.098MPa vacuum tightness and 260 DEG C, making to be present in the chloro-pyridine compounds in the short steaming residue of DCTF rectifying, the polymer conversion that fluorine chloro-pyridine compounds and fluorinated pyridine compounds are formed under the high temperature conditions is for comprising the chloro-3-5-flumethiazine of 2,5,6-tri-, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridine, the chloro-5-of 2,3,6-tri-(dichlorofluoromethyl) pyridine, the chloro-5-of 2,3,6-tri-(difluorochloromethyl) pyridine, the chloro-3-4-hydroxymethylpiperidine of 5,6-bis--2-phenol, the chloro-5-of 2,3-bis-(dichlorofluoromethyl) pyridine, Perchloropyridine, 2, the chloro-5-of 3-bis-(difluorochloromethyl) pyridine is at interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine compounds, and be separated with the polymkeric substance being difficult to cracking that the reaction mass containing DCTF carries out being formed in the short steamed journey of rectifying, thus obtain containing 2, the thick oil of 5,6-tri-chloro-3-5-flumethiazine, be that the solution washing of 15% is containing 2 by being mass percentage concentration that 9: 8: 7: 5: 8: 10 alkaline assistants formed are made in mass ratio by sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia and sodium hydroxide, 5, the thick oil of 6-tri-chloro-3-5-flumethiazine, to realize the removal of its middle acid substance, by to after alkali liquid washing containing 2,5, the thick oil of 6-tri-chloro-3-5-flumethiazine carries out rectification under vacuum successively and collects the fraction of 100 ~ 120 DEG C/100 ~ 1000Pa, freezing and crystallizing, vacuum filtration or centrifugation, realize 2,5,6-tri-chloro-3-5-flumethiazine and other chloro-pyridine compounds in thick oil are separated with fluorine chloro-pyridine compounds, and obtain 2,5,6-tri-chloro-3-5-flumethiazine crude product, by by sherwood oil, ether, cyclohexane, octane-iso, benzene, toluene and dimethylbenzene are that 100: 0.02: 0.01: 50: 4: 0.01: 5 double solventss formed wash obtained by vacuum filtration or centrifugation 2 in mass ratio, 5, 6-tri-chloro-3-5-flumethiazine crude product, and under the condition of 0.09MPa vacuum tightness and 20 DEG C, drying is carried out to the solid obtained, last to obtain 2 relative to the yield of the short steaming mass of residue 3% of DCTF rectifying, 5, 6-tri-chloro-3-5-flumethiazine mass percentage is 98.5% 2, 5, 6-tri-chloro-3-5-flumethiazine product.
Claims (3)
1. the method utilizing DCTF rectifying short steaming residue to prepare the chloro-3-5-flumethiazine of 2,5,6-tri-, is characterized in that: the chloro-pyridine compounds existed in the short steaming residue of the DCTF rectifying utilizing DCTF production technique to produce, fluorinated pyridine compounds, the polymkeric substance that fluorine chloro-pyridine compounds is formed under the high temperature conditions and chloro-pyridine micromolecular compound, fluorinated pyridine micromolecular compound and fluorine chloro-pyridine micromolecular compound are in volatility, difference on solvability and boiling point, and by aluminium sesquioxide, silicon-dioxide, zirconium white, 4A zeolite, magnesium oxide, mordenite, HZSM-5 zeolite is that 0.01 ~ 50: 0.01 ~ 60: 0.001 ~ 10: 0.01 ~ 80: 0.001 ~ 10: 0.01 ~ 30: 0.01 ~ 10 catalyzer formed are to chloro-pyridine compounds in mass ratio, the catalyzed degradation function of the polymkeric substance that fluorine chloro-pyridine compounds and fluorinated pyridine compounds are formed under the high temperature conditions, by the means of DCTF rectifying short steaming residue catalytic pyrolysis in place and vacuum distilling under the condition of 0.001MPa ~ 0.101MPa vacuum tightness and 100 ~ 400 DEG C, promote the chloro-pyridine compounds be present in the short steaming residue of DCTF rectifying, the polymer conversion that fluorine chloro-pyridine compounds and fluorinated pyridine compounds are formed under the high temperature conditions is for comprising the chloro-3-5-flumethiazine of 2,5,6-tri-, the chloro-5-of 2,3-bis-(dichlorofluoromethyl) pyridine, the chloro-5-of 2,3-bis-(difluorochloromethyl) pyridine, the chloro-3-5-flumethiazine of 2,5,6-tri-, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridine, the chloro-5-of 2,3,6-tri-(dichlorofluoromethyl) pyridine, the chloro-3-4-hydroxymethylpiperidine of 5,6-bis--2-phenol, Perchloropyridine is at interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine compounds, and be separated with the polymkeric substance being difficult to cracking that the reaction mass containing DCTF carries out being formed in the short steamed journey of rectifying, thus the thick oil obtained containing 2,5,6-tri-chloro-3-5-flumethiazine, be that the solution washing of 0.01 ~ 20% is containing 2 by being mass percentage concentration that 0.01 ~ 10: 0.01 ~ 8: 0.01 ~ 10: 0.01 ~ 5: 0.001 ~ 8: 0.001 ~ 10 alkaline assistants formed are made in mass ratio by sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia and sodium hydroxide, 5, the thick oil of 6-tri-chloro-3-5-flumethiazine, to realize the removal of its middle acid substance, by to after alkali liquid washing containing 2,5, the thick oil of 6-tri-chloro-3-5-flumethiazine carries out rectification under vacuum successively and collects the fraction of 120 ~ 180 DEG C/100 ~ 1000Pa, freezing and crystallizing, vacuum filtration or centrifugation, realize 2,5,6-tri-chloro-3-5-flumethiazine and other chloro-pyridine compounds in thick oil are separated with fluorine chloro-pyridine compounds, and obtain 2,5,6-tri-chloro-3-5-flumethiazine crude product, by by sherwood oil, ether, hexanaphthene, octane-iso, benzene, toluene and dimethylbenzene are that 0.01 ~ 100: 0.001 ~ 20: 0.001 ~ 100: 0.01 ~ 50: 0.001 ~ 8: 0.001 ~ 10: 0.001 ~ 10 double solventss formed wash obtain through vacuum filtration or centrifugation 2 in mass ratio, 5, 6-tri-chloro-3-5-flumethiazine crude product, and under the condition of 0.001MPa ~ 0.101MPa vacuum tightness and-10 ~ 50 DEG C, vacuum-drying is carried out to the solid obtained, and realize 2, 5, the purifying of the chloro-3-5-flumethiazine of 6-tri-, namely 2 are obtained, 5, 6-tri-chloro-3-5-flumethiazine mass percentage is greater than 95% 2, 5, 6-tri-chloro-3-5-flumethiazine product.
2. one according to claim 1 utilizes the short steaming residue of DCTF rectifying to prepare 2,5, the method of the chloro-3-5-flumethiazine of 6-tri-, is characterized in that: the mass ratio being 0.01 ~ 50: 0.01 ~ 60: 0.001 ~ 10: 0.01 ~ 80: 0.001 ~ 10: 0.01 ~ 30: 0.01 ~ 10 catalyzer formed and the short steaming residue of DCTF rectifying in mass ratio by aluminium sesquioxide, silicon-dioxide, zirconium white, 4A zeolite, magnesium oxide, mordenite, HZSM-5 zeolite is 0.01 ~ 20: 0.01 ~ 90.
3. one according to claim 1 utilizes the short steaming residue of DCTF rectifying to prepare 2,5, the method of the chloro-3-5-flumethiazine of 6-tri-, it is characterized in that: to obtain 2 relative to the yield of the short steaming mass of residue 0.1 ~ 8% of DCTF rectifying, 5,2,5, the 6-tri-chloro-3-5-flumethiazine products that 6-tri-chloro-3-5-flumethiazine mass percentage is greater than 95%.
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