CN105884679A - Method for preparing 5, 6-dichloro-3-hydroxymethylpyridine-2-phenol from DCTF rectification and short-steaming residues - Google Patents
Method for preparing 5, 6-dichloro-3-hydroxymethylpyridine-2-phenol from DCTF rectification and short-steaming residues Download PDFInfo
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- CN105884679A CN105884679A CN201610193177.7A CN201610193177A CN105884679A CN 105884679 A CN105884679 A CN 105884679A CN 201610193177 A CN201610193177 A CN 201610193177A CN 105884679 A CN105884679 A CN 105884679A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—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
- 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
Abstract
The invention discloses a method for preparing 5, 6-dichloro-3-hydroxymethylpyridine-2-phenol from DCTF rectification and short-steaming residues, and by means of the method, the resource utilization rate can be raised. The method comprises the following steps of by means of the function of a catalyst constituted by aluminum oxide, silica, zirconium oxide, 4A zeolite, magnesium oxide, mordenite and HZSM-5 zeolite for conducting catalytic degradation on the DCTF rectification and short-steaming residues, converting polymer in the residues into small molecule compounds through in-site catalytic splitting and vacuum distillation, so that crude oil containing 5, 6-dichloro-3-hydroxymethylpyridine-2-phenol is obtained; sequentially treating the crude oil containing 5, 6-dichloro-3-hydroxymethylpyridine-2-phenol through the methods of washing via an alkaline auxiliary agent aqueous solution, pressure-reduced rectification, freezing crystallization, vacuum filtration or centrifugal separation, washing via solvent and vacuum drying, so that a 5, 6-dichloro-3-hydroxymethylpyridine-2-phenol product with the mass percentage content greater than 95% is obtained at the yield of 0.1-5% the mass of the DCTF rectification and short-steaming residues.
Description
Technical field
One involved in the present invention utilizes DCTF rectification short steaming residue to prepare 5, the method for 6-bis-chloro-3-hydroxymethylpyridine-2-phenol,
It is that Minute Organic Synthesis field Fine Organic Chemical product are prepared a kind of novel chemical by-product resource that realizes of aspect and efficiently utilized
Method.
Background technology
DCTF, chemistry entitled 2,3-bis-chloro-5-trifluoromethylpyridine, No. CAS is to be a kind of under 69045-84-7, room temperature condition
Relative density is the colourless transparent liquid of 1.55 (water is 1.0).As a kind of important pesticide and medicine intermediate, DCTF is not
But can be used for the production of the Fluoric Herbicides such as fluazifop, chlorine fluorine second standing grain spirit, haloxyfop, and at fluazuron, determine worm
The production of the pesticide such as the fluorine-containing process for preparation of benzoylurea compounds such as grand, chlorfluazuron and efficient germicide fluazinam and fluorine-containing medicines also have wide
General application.These agricultural chemicals produced one of with DCTF as base stock, not only have the feature that drug effect is high, toxicity is low,
But also have and pollute the distinguishing features such as little and environmentally friendly, thus very fast in the development of nearly more than ten years.
The preparation of DCTF mainly has following several method: (1), with 2-amino-5-picoline as raw material, first generates 2-through chlorination
Amino-3-chloro-5-trichloromethylpyridine, then through diazotising and Cu2Cl2Obtain Deng the diazo chlorine replacement reaction in the presence of catalyst
2,3-bis-chloro-5-trichloromethylpyridines, finally by 2 in the presence of the catalyst such as mercury oxide or Mercury difluoride., 3-bis-chloro-5-trichloromethyl
Pyridine and hydrogen fluoride reaction obtain DCTF；(2) with chloro--methylpyridine as raw material, first under photocatalysis, pendant chlorine is carried out
Obtain 2-chloro-5-trichloromethylpyridine, then under the catalysts such as lewis acid, carry out chlorination on ring further obtain 2,3-dichloro
-5-trichloromethyl pyridine, finally by 2 in the presence of the catalyst such as mercury oxide or Mercury difluoride., 3-bis-chloro-5-trichloromethylpyridine and fluorine
Change hydrogen reaction and obtain DCTF；(3) with 3-picoline as raw material, first under photocatalysis, 3-trichloromethyl is generated with chlorine reaction
Pyridine, then under the catalysts such as lewis acid, carry out chlorination on ring obtain 2,3-bis-chloro-5-trichloromethylpyridine, finally at oxygen
Passing through 2 in the presence of changing the catalyst such as hydrargyrum or Mercury difluoride., 3-bis-chloro-5-trichloromethylpyridine and hydrogen fluoride reaction obtain DCTF；(4)
With 2-vhloro-5-chloromethylpyridine as raw material, first carry out Light chlorimation and generate 2-chloro-5-trichloromethylpyridine, then be catalyzed at lewis acid etc.
Generating 2 through thermal chlorination under agent catalysis, 3-bis-chloro-5-trichloromethylpyridine, finally in the presence of the catalyst such as mercury oxide or Mercury difluoride.
By 2,3-bis-chloro-5-trichloromethylpyridine and hydrogen fluoride reaction obtain DCTF.Wherein raw with 2-vhloro-5-chloromethylpyridine for raw material
The technique producing DCTF, due to there is numerous advantages such as cost of material is low, reaction selectivity is high, good product quality and at DCTF
Production in apply the most extensive.
In with 2-vhloro-5-chloromethylpyridine, 3-picoline or chloro--methylpyridine for the technique of raw material production DCTF, 2,3-
The reaction mass that two chloro-5-trichloromethylpyridines obtain with hydrogen fluoride reaction in the presence of the catalyst such as mercury oxide or Mercury difluoride., needs elder generation
Carry out preliminary short distillation to generate containing the short steaming liquid of DCTF, the most again by the short steaming liquid obtained is carried out further rectification with
Obtain DCTF product.To by 2,3-bis-chloro-5-trichloromethylpyridine in the presence of the catalyst such as mercury oxide or Mercury difluoride. with fluorination
Hydrogen reaction obtains reaction mass when carrying out the shortest short steaming liquid being distilled to yield containing DCTF, can produce substantial amounts of DCTF rectification
Short steaming residue.Owing to the material in this rectification short steaming residue is the substituted-pyridines containing multiple halogen atoms on molecular structure mostly
Compound and their polymer, these substituted pyridine compounds containing multiple halogen atom and their polymer do not have combustion
Burning property or combustibility are extremely low, thus are difficult to carry out harmless treatment by simple incinerating method.The most effectively process DCTF
Rectification short steaming residue, and realize the isolated and purified of its contained substance or convert, reduce production cost and the DCTF rectification of DCTF
The potential pollution hazardness that environment is existed by short steaming residue, and the effective rate of utilization fully improving resource becomes the most day by day
The problem being concerned about for people.
Pesticide and medicine intermediate 5, the research of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol is prepared utilizing DCTF rectification short steaming residue
Cheng Zhong, contacts a lot of relevant 2, and 3-bis-chloro-5-trifluoromethylpyridine and 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol is prepared and application side
The technical data in face, wherein have some reference value specifically includes that " preparations of 2,3-bis-chloro-5-trichlorine (fluorine) picolines "
(Organic fluoride industry, the 1st phase in 2010), " synthetic method of 2,3-bis-chloro-5-trifluoromethylpyridines is commented " (modern, 2006
Year the 2nd phase), " study on the synthesis of 2,3-bis-chloro-5-trifluoromethylpyridines " (Hebei chemical industry, the 3rd phase in 2003), " Some New
2-Substituted 5-trifluoromethylpyridines " (Heterecycles, the 2nd phase in 1984), " synthesis 2, the chloro-5-of 3-bis-tri-
The progress of Fluoromethylpyridin " and (chemical reagent, the 6th phase in 2004), " novel pesticide UC 62644 " (pesticide, 1989
4th phase), " Synthesis of halogenated pyridine " (J.Org.Chem., the 25th phase in 1985), " new method synthesize
2-chloro-5-trichloromethylpyridine " (Chemical Engineering Technology and exploitation, the 5th phase in 2004), " 3-picoline and derivant thereof are closed at pesticide
Application in one-tenth " (pesticide, the 6th phase in 1999), " Process for producing
3-chloro-5-trifluoromethylpyridines " (US 4490543,1984-12-25), " Preparation of
3,6-dichloro-2-trichloromethylpyridine by vapor phase chlorination of
6-chloro-2-trichloromethylpyridine " (US 20040176607 A1,2004-09-09), " Preparation of
2,3-difluoro-5-(trifluoromethyl) pyridine " (US 5073637,1991-12-17).
Summary of the invention
One utilizes DCTF rectification short steaming residue to prepare 5, and the invention of the method for 6-bis-chloro-3-hydroxymethylpyridine-2-phenol is mainly
Realize being reacted by optical chlorinating reaction, thermal chlorination and fluorination reaction produces 2, in the technique of 3-bis-chloro-5-trifluoromethylpyridine to fluorine
The short steaming of DCTC produced in a large number when changing the predistillation implemented before the reacted reaction mass containing DCTF carries out rectification separation is residual
Slag is effectively treated, and one of with it as base stock to prepare pesticide and medicine intermediate 5,6-bis-chloro-3-hydroxymethylpyridine-2-
Phenol, thus it is short to improve the rectification produced in the effective rate of utilization of resource, the production cost reducing DCTF and DCTF production technology
Steam the potential pollution hazardness that environment is existed by residue.
The technical scheme is that and utilize chloro present in the DCTF rectification short steaming residue produced in DCTF production technology
Polymer that pyridine compounds and their, fluorinated pyridine compounds, fluorine chloro-pyridine compounds are formed under the high temperature conditions and chloro
Pyridines micromolecular compound, fluorinated pyridine micromolecular compound and fluorine chloro-pyridine micromolecular compound are in volatility, molten
Solve property and boiling point on difference, and by aluminium sesquioxide, silicon dioxide, zirconium oxide, 4A zeolite, magnesium oxide, modenite,
HZSM-5 zeolite be in mass ratio 0.01～50: 0.01～60: 0.001～10: 0.01～80: 0.001～10: 0.01～30: 0.01～
10 constitute catalyst to chloro-pyridine compounds, fluorine chloro-pyridine compounds and fluorinated pyridine compounds in hot conditions
The catalytic degradation function of the polymer of lower formation, by the mass ratio of catalyst Yu DCTF rectification short steaming residue be 0.01～
Material is added separately in reactor by 20: 0.01～90, stirring and 0.001MPa～0.101MPa vacuum and 100～
By DCTF rectification short steaming residue catalytic pyrolysis in place and the means of vacuum distilling under conditions of 400 DEG C, promote to be present in DCTF
Chloro-pyridine compounds, fluorine chloro-pyridine compounds and fluorinated pyridine compounds in rectification short steaming residue are in hot conditions
The polymer conversion of lower formation for comprising 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol, 2,5,6-tri-chloro-3-trifluoromethyl pyridines, 2,3-bis-
Chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridines, 2,3,6-tri-chloro-5-(dichlorofluoromethyl) pyridines, 2,3,6-
Three chloro-5-(difluorochloromethyl) pyridines, 2,3-bis-chloro-5-(dichlorofluoromethyl) pyridine, Pentachloropyridine, 2, the chloro-5-of 3-bis-(two
Fluorine chloromethyl) pyridine is at interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine compounds, and anti-with containing DCTF
The polymer being difficult to crack answering material to be formed during carrying out the short steaming of rectification separates, thus obtains containing 5,6-bis-chloro-3-methylol pyrrole
The crude oil of pyridine-2-phenol；Containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol is via sodium carbonate, potassium carbonate, sodium bicarbonate, carbonic acid
Hydrogen potassium, ammonium hydrogen carbonate and sodium hydroxide are 0.01～10: 0.01～8: 0.01～10: 0.01～5: 0.001～8: 0.001～10 in mass ratio
The mass percentage concentration that is made into of alkaline assistant constituted be 0.01～20% solution washing after, then to after alkali liquid washing containing 5,6-
The crude oil of two chloro-3-hydroxymethylpyridine-2-phenol carry out successively rectification under vacuum and collect 140～180 DEG C/0.667～the fraction of 2.67kPa,
Freezing and crystallizing, vacuum filter or centrifugation, it is achieved 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol and other chloro-pyridine classes in crude oil
Compound and the separation of fluorine chloro-pyridine compounds, and obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product；By by oil
Ether, ether, hexamethylene, isobutyltrimethylmethane., benzene, toluene and dimethylbenzene be in mass ratio 0.01～100: 0.001～20: 0.001～
The double solvents washing that 100: 0.01～50: 0.001～8: 0.001～10: 0.001～10 are constituted obtains through vacuum filtration or centrifugation
5 arrived, 6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product, and in 0.001MPa～0.101MPa vacuum and the condition of-10～50 DEG C
Under the solid obtained is vacuum dried, and realize 5, the purification of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol, i.e. with relative to DCTF
Rectification short steaming mass of residue 0.1～5% yield obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol weight/mass percentage composition is more than 95%
5,6-bis-chloro-3-hydroxymethylpyridine-2-phenolic products.
Accompanying drawing explanation
Fig. 1 is 5, the structural formula figure of 6-bis-chloro-3-hydroxymethylpyridine-2-phenolic product.
Fig. 2 is 5, the MS figure of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol.
Specific implementation method
Some embodiments are given below, so that the invention will be further described.
Embodiment 1:
1000 grams of DCTF rectification short steaming residues and 100 grams are by aluminium sesquioxide, silicon dioxide, zirconium oxide, 4A zeolite, oxygen
Changing magnesium, modenite, HZSM-5 zeolite is that 0.01: 30: 10: 20: 10: 0.01: 0.1 catalyst constituted adds together in mass ratio
In reactor, stirring also realizes DCTF rectification short steaming residue under conditions of 0.01MPa vacuum and 400 DEG C and is catalyzed in place
Cracking and vacuum distilling, make chloro-pyridine compounds, the fluorine chloro-pyridine class chemical combination being present in DCTF rectification short steaming residue
The polymer conversion that thing and fluorinated pyridine compounds are formed under the high temperature conditions for comprising 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol,
2,5,6-tri-chloro-3-trifluoromethyl pyridines, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridines, 2,3,6-
Three chloro-5-(dichlorofluoromethyl) pyridines, 2,3,6-tri-chloro-5-(difluorochloromethyl) pyridines, 2, the chloro-5-of 3-bis-(dichlorofluoromethyl)
Pyridine, Pentachloropyridine, 2,3-bis-chloro-5-(difluorochloromethyl) pyridine is at interior chloro-pyridine micromolecular compound and fluorine chloro
Pyridine compounds and their, and the polymer being difficult to crack carrying out with the reaction mass containing DCTF being formed during the short steaming of rectification separates,
Thus obtain containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol；By by sodium carbonate, potassium carbonate, sodium bicarbonate, bicarbonate
Potassium, ammonium hydrogen carbonate and sodium hydroxide are that the mass percentage concentration that 0.1: 8: 0.01: 0.5: 4: 5 alkaline assistants constituted are made into is in mass ratio
The solution washing of 0.1% contain 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol, then to after alkali liquid washing containing 5,6-bis-chloro-3-hydroxyl
The crude oil of picoline-2-phenol carries out rectification under vacuum successively and collects 140～180 DEG C/0.667～the fraction of 2.67kPa, freezing knot
Brilliant, vacuum filters or centrifugation, it is achieved 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol and other chloro-pyridine compounds in crude oil
With the separation of fluorine chloro-pyridine compounds, and obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product；By by petroleum ether, second
Ether, hexamethylene, isobutyltrimethylmethane., benzene, toluene and dimethylbenzene are the compound molten of 0.01: 20: 0.1: 15: 0.001: 1: 0.1 composition in mass ratio
Agent washing filtered by vacuum or be centrifugally separating to obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product, and in 0.08MPa vacuum
Spend and the solid obtained be dried, finally with the receipts relative to DCTF rectification short steaming mass of residue 5% under conditions of 30 DEG C
Rate obtains 5, and 6-bis-chloro-3-hydroxymethylpyridine-2-phenol weight/mass percentage composition is the 5 of 96%, 6-bis-chloro-3-hydroxymethylpyridine-2-phenolic product.
Embodiment 2:
1000 grams of DCTF rectification short steaming residues and 50 grams are by aluminium sesquioxide, silicon dioxide, zirconium oxide, 4A zeolite, oxidation
Magnesium, modenite, HZSM-5 zeolite are that 0.1: 2: 1: 0.1: 3: 0.1: 0.01 catalyst constituted joins reaction together in mass ratio
In device, stirring and realize under conditions of 0.05MPa vacuum and 350 DEG C DCTF rectification short steaming residue catalytic pyrolysis in place and
Vacuum distilling, makes chloro-pyridine compounds, fluorine chloro-pyridine compounds and the fluorine being present in DCTF rectification short steaming residue
The polymer conversion formed under the high temperature conditions for pyridine compounds and their for comprising 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol, 2,5,6-
Three chloro-3-trifluoromethyl pyridines, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridines, 2,3,6-tri-chloro-5-
(dichlorofluoromethyl) pyridine, 2,3,6-tri-chloro-5-(difluorochloromethyl) pyridines, 2,3-bis-chloro-5-(dichlorofluoromethyl) pyridine,
Pentachloropyridine, 2,3-bis-chloro-5-(difluorochloromethyl) pyridine is in interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine class
Compound, and the polymer being difficult to crack carrying out with the reaction mass containing DCTF being formed during the short steaming of rectification separates, thus
Obtain containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol；By by sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Ammonium hydrogen carbonate and sodium hydroxide be in mass ratio 1: 0.8: 0.1: 5: 0.4: 0.5 mass percentage concentration that is made into of alkaline assistant constituted be 1%
Solution washing containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol, then to after alkali liquid washing containing 5,6-bis-chloro-3-methylol
The crude oil of pyridine-2-phenol carries out rectification under vacuum successively and collects 140～180 DEG C/0.667～the fraction of 2.67kPa, freezing and crystallizing, true
Empty filtration or centrifugation, it is achieved 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol and other chloro-pyridine compounds and fluorine chlorine in crude oil
For the separation of pyridine compounds and their, and obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product；By by petroleum ether, ether, ring
Hexane, isobutyltrimethylmethane., benzene, toluene and dimethylbenzene are that 100: 10: 0.1: 3: 8: 10: the 10 double solvents washings constituted are passed through in mass ratio
Vacuum filter or be centrifugally separating to obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product, and 0.10MPa vacuum and 30 DEG C
Under the conditions of the solid obtained is dried, finally obtain 5,6-with the yield relative to DCTF rectification short steaming mass of residue 1%
Two chloro-3-hydroxymethylpyridine-2-phenol weight/mass percentage composition are the 5 of 98.7%, 6-bis-chloro-3-hydroxymethylpyridine-2-phenolic product.
Embodiment 3:
1000 grams of DCTF rectification short steaming residues and 10 grams are by aluminium sesquioxide, silicon dioxide, zirconium oxide, 4A zeolite, oxidation
Magnesium, modenite, HZSM-5 zeolite are that 1: 0.2: 1: 0.01: 15: 10: 10 catalyst constituted join reaction together in mass ratio
In device, stirring and realize under conditions of 0.09MPa vacuum and 300 DEG C DCTF rectification short steaming residue catalytic pyrolysis in place and
Vacuum distilling, makes chloro-pyridine compounds, fluorine chloro-pyridine compounds and the fluorine being present in DCTF rectification short steaming residue
The polymer conversion formed under the high temperature conditions for pyridine compounds and their for comprising 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol, 2,5,6-
Three chloro-3-trifluoromethyl pyridines, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridines, 2,3,6-tri-chloro-5-
(dichlorofluoromethyl) pyridine, 2,3,6-tri-chloro-5-(difluorochloromethyl) pyridines, 2,3-bis-chloro-5-(dichlorofluoromethyl) pyridine,
Pentachloropyridine, 2,3-bis-chloro-5-(difluorochloromethyl) pyridine is in interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine class
Compound, and the polymer being difficult to crack carrying out with the reaction mass containing DCTF being formed during the short steaming of rectification separates, thus
Obtain containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol；By by sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Ammonium hydrogen carbonate and sodium hydroxide be in mass ratio 10: 0.01: 10: 5: 4: 10 mass percentage concentration that are made into of alkaline assistants constituted be 5%
Solution washing containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol, then to after alkali liquid washing containing 5,6-bis-chloro-3-methylol
The crude oil of pyridine-2-phenol carries out rectification under vacuum successively and collects 140～180 DEG C/0.667～the fraction of 2.67kPa, freezing and crystallizing, true
Empty filtration or centrifugation, it is achieved 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol and other chloro-pyridine compounds and fluorine chlorine in crude oil
For the separation of pyridine compounds and their, and obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product；By by petroleum ether, ether, ring
Hexane, isobutyltrimethylmethane., benzene, toluene and dimethylbenzene are that 100: 0.02: 30: 50: 4: 0.5: the 10 double solvents washings constituted are logical in mass ratio
Cross that vacuum filters or is centrifugally separating to obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product, and 0.09MPa vacuum and 20 DEG C
Under conditions of the solid obtained is dried, finally obtain 5,6-with the yield relative to DCTF rectification short steaming mass of residue 3%
Two chloro-3-hydroxymethylpyridine-2-phenol weight/mass percentage composition are the 5 of 98%, 6-bis-chloro-3-hydroxymethylpyridine-2-phenolic product.
Embodiment 4:
1000 grams of DCTF rectification short steaming residues and 5 grams are by aluminium sesquioxide, silicon dioxide, zirconium oxide, 4A zeolite, oxidation
Magnesium, modenite, HZSM-5 zeolite are that 30: 60: 0.01: 40: 3: 15: 10 catalyst constituted join reaction together in mass ratio
In device, stirring and realize under conditions of 0.09MPa vacuum and 300 DEG C DCTF rectification short steaming residue catalytic pyrolysis in place and
Vacuum distilling, makes chloro-pyridine compounds, fluorine chloro-pyridine compounds and the fluorine being present in DCTF rectification short steaming residue
The polymer conversion formed under the high temperature conditions for pyridine compounds and their for comprising 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol, 2,5,6-
Three chloro-3-trifluoromethyl pyridines, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridines, 2,3,6-tri-chloro-5-
(dichlorofluoromethyl) pyridine, 2,3,6-tri-chloro-5-(difluorochloromethyl) pyridines, 2,3-bis-chloro-5-(dichlorofluoromethyl) pyridine,
Pentachloropyridine, 2,3-bis-chloro-5-(difluorochloromethyl) pyridine is in interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine class
Compound, and the polymer being difficult to crack carrying out with the reaction mass containing DCTF being formed during the short steaming of rectification separates, thus
Obtain containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol；By by sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Ammonium hydrogen carbonate and sodium hydroxide be in mass ratio 10: 4: 5: 5: 3: 10 mass percentage concentration that are made into of alkaline assistants constituted be 10%
Solution washing contain 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol, then to after alkali liquid washing containing 5,6-bis-chloro-3-methylol pyrrole
The crude oil of pyridine-2-phenol carries out rectification under vacuum successively and collects 140～180 DEG C/0.667～the fraction of 2.67kPa, freezing and crystallizing, vacuum
Filter or centrifugation, it is achieved 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol and other chloro-pyridine compounds and fluorine chloro in crude oil
The separation of pyridine compounds and their, and obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product；By by petroleum ether, ether, hexamethylene
Alkane, isobutyltrimethylmethane., benzene, toluene and dimethylbenzene are that 100: 0.02: 0.01: 50: 4: 0.01: the 5 double solvents washings constituted are logical in mass ratio
Cross that vacuum filters or is centrifugally separating to obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product, and 0.09MPa vacuum and 20 DEG C
Under conditions of the solid obtained is dried, finally obtain with the yield relative to DCTF rectification short steaming mass of residue 0.3%
5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol weight/mass percentage composition are the 5 of 98.5%, 6-bis-chloro-3-hydroxymethylpyridine-2-phenolic product.
Embodiment 5:
1000 grams of DCTF rectification short steaming residues and 3 grams are by aluminium sesquioxide, silicon dioxide, zirconium oxide, 4A zeolite, oxidation
Magnesium, modenite, HZSM-5 zeolite are that 50: 30: 0.1: 37: 5: 18: 9 catalyst constituted join reactor together in mass ratio
In, stirring also realizes DCTF rectification short steaming residue catalytic pyrolysis in place and true under conditions of 0.098MPa vacuum and 260 DEG C
Empty distillation, makes chloro-pyridine compounds, fluorine chloro-pyridine compounds and the fluoro being present in DCTF rectification short steaming residue
The polymer conversion that pyridine compounds and their is formed under the high temperature conditions for comprising 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol, 2,5,6-trichlorines
-3-trifluoromethyl pyridine, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridines, 2,3,6-tri-chloro-5-(two
Chlorine methyl fluoride) pyridine, 2,3,6-tri-chloro-5-(difluorochloromethyl) pyridines, 2,3-bis-chloro-5-(dichlorofluoromethyl) pyridine, pentachloro-
Pyridine, 2,3-bis-chloro-5-(difluorochloromethyl) pyridine is at interior chloro-pyridine micromolecular compound and fluorine chloro-pyridine class chemical combination
Thing, and the polymer being difficult to crack carrying out with the reaction mass containing DCTF being formed during the short steaming of rectification separates, thus obtain
Containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol；By by sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, carbonic acid
Hydrogen ammonium and sodium hydroxide are the aqueous solution that mass percentage concentration is 15% that 9: 8: 7: 5: 8: 10 alkaline assistants constituted are made in mass ratio
Washing containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol, then to after alkali liquid washing containing 5,6-bis-chloro-3-hydroxymethylpyridine-2-
The crude oil of phenol carry out successively rectification under vacuum and collect 140～180 DEG C/0.667～the fraction of 2.67kPa, freezing and crystallizing, vacuum filter
Or centrifugation, it is achieved 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol and other chloro-pyridine compounds and fluorine chloro-pyridine in crude oil
The separation of compounds, and obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product；By by petroleum ether, ether, hexamethylene,
Isobutyltrimethylmethane., benzene, toluene and dimethylbenzene are that 100: 0.02: 0.01: 50: 4: 0.01: 5 double solventss constituted wash by very in mass ratio
Empty filter or be centrifugally separating to obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product, and at 0.09MPa vacuum and the bar of 20 DEG C
Under part, the solid obtained is dried, finally obtains 5 with the yield relative to DCTF rectification short steaming mass of residue 1.3%, 6-bis-
Chloro-3-hydroxymethylpyridine-2-phenol weight/mass percentage composition is 98.5%5,6-bis-chloro-3-hydroxymethylpyridine-2-phenolic product.
Claims (3)
1. one kind utilizes DCTF rectification short steaming residue to prepare 5, the method for 6-bis-chloro-3-hydroxymethylpyridine-2-phenol, it is characterised in that:
Utilize chloro-pyridine compounds, fluorinated pyridine class present in the DCTF rectification short steaming residue produced in DCTF production technology
The polymer that compound, fluorine chloro-pyridine compounds are formed under the high temperature conditions and chloro-pyridine micromolecular compound, fluoro
Pyridines micromolecular compound and fluorine chloro-pyridine micromolecular compound difference on volatility, dissolubility and boiling point, and by
Aluminium sesquioxide, silicon dioxide, zirconium oxide, 4A zeolite, magnesium oxide, modenite, HZSM-5 zeolite be in mass ratio 0.01～
50: 0.01～60: 0.001～10: 0.01～80: 0.001～10: 0.01～30: 0.01～10 catalyst constituted are to chloro-pyridine class
The catalytic degradation function of the polymer that compound, fluorine chloro-pyridine compounds and fluorinated pyridine compounds are formed under the high temperature conditions,
It is catalyzed in place by DCTF rectification short steaming residue under conditions of 0.001MPa～0.101MPa vacuum and 100～400 DEG C and splits
Solve and the means of vacuum distilling, promote chloro-pyridine compounds, the fluorine chloro-pyridine being present in DCTF rectification short steaming residue
The polymer conversion that compounds and fluorinated pyridine compounds are formed under the high temperature conditions for comprising 5,6-bis-chloro-3-hydroxymethylpyridine
-2-phenol, 2,5,6-tri-chloro-3-trifluoromethyl pyridines, 2,3-bis-chloro-5-trichloromethylpyridine, 2,3,4,6-tetra-chloro-5-trifluoromethylpyridines,
2,3,6-tri-chloro-5-(dichlorofluoromethyl) pyridines, 2,3,6-tri-chloro-5-(difluorochloromethyl) pyridines, 2,3-bis-chloro-5-(dichloro fluorine
Methyl) pyridine, Pentachloropyridine, 2,3-bis-chloro-5-(difluorochloromethyl) pyridine at interior chloro-pyridine micromolecular compound and
Fluorine chloro-pyridine compounds, and being polymerized of cracking of being difficult to of carrying out with the reaction mass containing DCTF being formed during the short steaming of rectification
Thing separates, thus obtains containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol；Containing 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol thick
Oil via sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium hydrogen carbonate and sodium hydroxide be in mass ratio 0.01～10: 0.01～
The mass percentage concentration that 8: 0.01～10: 0.01～5: 0.001～8: 0.001～10 alkaline assistants constituted are made into is 0.01～20%
Solution washing, then to after alkali liquid washing containing 5, the crude oil of 6-bis-chloro-3-hydroxymethylpyridine-2-phenol carries out rectification under vacuum successively and receives
Collection 140～180 DEG C/0.667～the fraction of 2.67kPa, freezing and crystallizing, vacuum filtration or centrifugation, it is achieved 5,6-bis-chloro-3-hydroxyls
Picoline-2-phenol separates with other chloro-pyridine compounds in crude oil and fluorine chloro-pyridine compounds, and obtains 5,6-bis-
Chloro-3-hydroxymethylpyridine-2-phenol pyridine crude product；By by petroleum ether, ether, hexamethylene, isobutyltrimethylmethane., benzene, toluene and dimethylbenzene
It is 0.01～100: 0.001～20: 0.001～100: 0.01～50: 0.001～8: 0.001～10: 0.001～10 compositions in mass ratio
Double solvents washing through vacuum filter or be centrifugally separating to obtain 5,6-bis-chloro-3-hydroxymethylpyridine-2-phenol crude product, and
Under conditions of 0.001MPa～0.101MPa vacuum and-10～50 DEG C, the solid obtained is dried, i.e. obtains 5, the chloro-3-of 6-bis-
Hydroxymethylpyridine-2-phenol weight/mass percentage composition is more than the 5 of 95%, 6-bis-chloro-3-hydroxymethylpyridine-2-phenolic product.
One the most according to claim 1 utilizes DCTF rectification short steaming residue to prepare 5,6-bis-chloro-3-hydroxymethylpyridine-2-
The method of phenol, it is characterised in that: by aluminium sesquioxide, silicon dioxide, zirconium oxide, 4A zeolite, magnesium oxide, modenite,
HZSM-5 zeolite be in mass ratio 0.01～50: 0.01～60: 0.001～10: 0.01～80: 0.001～10: 0.01～30: 0.01～
10 catalyst constituted are 0.01～20: 0.01～90 with the mass ratio of DCTF rectification short steaming residue.
One the most according to claim 1 utilizes DCTF rectification short steaming residue to prepare 5,6-bis-chloro-3-hydroxymethylpyridine-2-
The method of phenol, it is characterised in that: obtain 5 with the yield relative to DCTF rectification short steaming mass of residue 0.1～5%, the chloro-3-of 6-bis-
Hydroxymethylpyridine-2-phenol weight/mass percentage composition is more than the 5 of 95%, 6-bis-chloro-3-hydroxymethylpyridine-2-phenolic product.
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| CN105061299A (en) * | 2015-08-12 | 2015-11-18 | 盐城工学院 | Method for preparing 2,3,4,6-tetrachloro-5-trifluoromethyl pyridine by using DCTF (2, 3-dichloro-5-trifluoromethyl pyridine) rectification and short steaming residues |
| CN106902489A (en) * | 2017-04-16 | 2017-06-30 | 内蒙古佳瑞米精细化工有限公司 | A kind of residual processing method of CTC rectifying stills |
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| CN105061299A (en) * | 2015-08-12 | 2015-11-18 | 盐城工学院 | Method for preparing 2,3,4,6-tetrachloro-5-trifluoromethyl pyridine by using DCTF (2, 3-dichloro-5-trifluoromethyl pyridine) rectification and short steaming residues |
| CN105061298A (en) * | 2015-07-29 | 2015-11-18 | 盐城工学院 | Method for preparing 2,3,6-trichloro-5-(dichlorofluoromethyl)pyridine from DCTF rectifying short steaming residues |
| CN105237471A (en) * | 2015-09-11 | 2016-01-13 | 盐城工学院 | Method for preparing pentachloropyridine from DCTF rectifying short steaming residues |
| CN105237470A (en) * | 2015-09-11 | 2016-01-13 | 盐城工学院 | Method for preparing 2,5,6-trichloro-3-tirfluoromethylpyridine from DCTF rectifying short steaming residues |
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| CN105061298A (en) * | 2015-07-29 | 2015-11-18 | 盐城工学院 | Method for preparing 2,3,6-trichloro-5-(dichlorofluoromethyl)pyridine from DCTF rectifying short steaming residues |
| CN105061299A (en) * | 2015-08-12 | 2015-11-18 | 盐城工学院 | Method for preparing 2,3,4,6-tetrachloro-5-trifluoromethyl pyridine by using DCTF (2, 3-dichloro-5-trifluoromethyl pyridine) rectification and short steaming residues |
| CN105237471A (en) * | 2015-09-11 | 2016-01-13 | 盐城工学院 | Method for preparing pentachloropyridine from DCTF rectifying short steaming residues |
| CN105237470A (en) * | 2015-09-11 | 2016-01-13 | 盐城工学院 | Method for preparing 2,5,6-trichloro-3-tirfluoromethylpyridine from DCTF rectifying short steaming residues |
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| CN105061299A (en) * | 2015-08-12 | 2015-11-18 | 盐城工学院 | Method for preparing 2,3,4,6-tetrachloro-5-trifluoromethyl pyridine by using DCTF (2, 3-dichloro-5-trifluoromethyl pyridine) rectification and short steaming residues |
| CN106902489A (en) * | 2017-04-16 | 2017-06-30 | 内蒙古佳瑞米精细化工有限公司 | A kind of residual processing method of CTC rectifying stills |
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