CN103739567B - A kind of 2-chloro-5-chloromethyl thiazole crystal formation and preparation method - Google Patents
A kind of 2-chloro-5-chloromethyl thiazole crystal formation and preparation method Download PDFInfo
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- CN103739567B CN103739567B CN201410045781.6A CN201410045781A CN103739567B CN 103739567 B CN103739567 B CN 103739567B CN 201410045781 A CN201410045781 A CN 201410045781A CN 103739567 B CN103739567 B CN 103739567B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D9/00—Crystallisation
- B01D9/02—Crystallisation from solutions
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Abstract
The present invention relates to 2 chlorine 5 5-chloromethyl thiazole crystal formations and preparation method thereof.The X ray powder diffraction of this crystal formation angle of reflection 2 θ about 10.3 °, 14.1 °, 20.6 °, 24.5 °, 30.6 °, have characteristic peak at 31.2 °；Preferably its X ray powder diffraction is as shown in drawings；More preferably its fusing point 29.5～29.7 DEG C.The invention has the advantages that crystal purity is high, preparation method is simple and environmentally-friendly.
Description
Technical field
The present invention relates to a kind of 2-chloro-5-chloromethyl thiazole crystal formation and preparation method, belong to technical field of fine.
Background technology
2-chloro-5-chloromethyl thiazole, English name 2-Chloro-5-chloromethylthiazole, CAS registration number
105827-91-6, molecular weight: 168, fusing point: 29-30 DEG C, structural formula is as shown below
2-chloro-5-chloromethyl thiazole is synthesis Diacloden (thiamethoxam), thiacloprid (clothianidin) etc. the
The necessary intermediate of secondary anabasine insecticide.The mechanism of action of second filial generation anabasine insecticide and first generation anabasine
Insecticide is similar, but it has, and consumption is lower, insecticidal spectrum is wider, safety more advantages of higher, both above and below ground insect is had one
Fixed preventing and treating property, can process stem and leaf, soil, seed again.Low at Residues in Vegetables, environmental pollution is few, to the mankind endanger
Evil is few, is to replace organophosphor, carbamates, the outstanding kind of organochlorine insecticides.Therefore 2-chloro-5-chloromethyl thiazole
Develop the exploitation of efficient, wide spectrum, low toxicity novel agrochemical had important practical significance.
Highly purified 2-chloro-5-chloromethyl thiazole can effectively prevent impurity from participating in side reaction, improves the productivity of end-product,
Reduce the impurity content of end-product, reduce the purification difficulty of end-product；And the high-purity 2-chloro-5-chlorine therefore developing more advantage
Methylthiazol particularly 2-chloro-5-chloromethyl thiazole crystal formation and preparation method thereof is the most necessary.
Summary of the invention
It is an object of the present invention to provide a kind of 2-chloro-5-chloromethyl thiazole crystal formation.
The 2-chloro-5-chloromethyl thiazole crystal formation that the present invention provides, X-ray powder diffraction spectrum is as shown in Figure 1.
A kind of side preparing 2-chloro-5-chloromethyl thiazole crystal formation of the present invention of offer is provided
Method, is with 2-chloro-5-chloromethyl thiazole crude product as raw material, prepares 2-chloro-5-chloromethyl thiazole by crystallization process, including walking as follows
Rapid:
(1) washing: in washing kettle, by 2-chloro-5-chloromethyl thiazole dissolving crude product in solvent, adds water in batches and enters
Row washing, washing organic facies is to pH value=6～7；
(2) absorption is except color: add decolorizing adsorbent in the organic facies that step (1) obtains, and keeps stirring under uniform temperature
Certain time, become light yellow to mother solution color from buff；
(3) filter pressing: transfer the material into filter-pressing cauldron, carries out filter pressing, and the faint yellow organic facies being press-filtered out enters collecting tank, pressure
Filter cake in filter still is transferred to other equipment, and preferably carries out regenerating with recycling；
(4) precipitation: the material in step (3) collecting tank is transferred to precipitation still, is keeping certain pressure and a constant temperature
The precipitation that reduces pressure is carried out in the case of degree；
(5) organic solvent is added: in precipitation still, add organic solvent, stir, keep temperature of charge about 40 DEG C；
(6) crystallizer crystallization, intensification fusing:
Crystallizer is the crystallizer of the crystallization column plate with concave sandwich, including crystallization tower body (1), mother
Liquid charging aperture (2), nitrogen inlet (3), the crystallization column plate (4) of concave sandwich, material outlet (5)；Wherein, mother solution enters
Material mouth (2), nitrogen inlet (3) are positioned at the top of all crystallization column plates (4), and material outlet (5) is positioned at all crystallization column plates (4)
Lower section；Crystallization column plate (4), by female (A) with around female (A) and relative to female (A) upraised portion
Dividing (B) composition, the inside of female (A) is embedded with the first hollow serpentine pipeline (C) of horizontal direction arrangement, can be passed through cold
Matchmaker or heating agent；The inside of bossing (B) is embedded with the second hollow serpentine pipeline (D) of horizontal direction arrangement, can be passed through heat
Matchmaker；Female (A) is placed with vertical direction and penetrates the through hole (E) of female (A).
Material in precipitation still is transferred to have the crystallizer of the crystallization column plate of concave sandwich, material from
Being neutralized bossing (B) outer rim by through hole (E) to flow downward, crystallizing tower plate temperature is relatively low has made solid gradually separate out；Charging
Crystallize column plate after end to start slowly heat up and keep certain time, make to stick to the solvent of plane of crystal and fail crystallization
Partial material is neutralized bossing (B) outer rim drippage by through hole (E) and flows out, by nitrogen inlet (3) from bottom material outlet (5)
It is passed through the nitrogen with certain flow rate, and crystallizing tower plate temperature is warming up to less than fusing point about 1.5-1 DEG C and keeps a period of time,
Sticking to the material of plane of crystal by nitrogen stripping, enter solvent recovery tank, the nitrogen in operating process returns from being arranged on solvent
Outlet above closed cans enters device for absorbing tail gas；Closing nitrogen, the material that column plate is continuously heating in crystallizing tower all melts,
Material enters product collecting tank from crystallized stock outlet (5), obtains highly purified 2-chloro-5-chloromethyl thiazole crystal.
Further preferred as this method, the most heat insulation between described female (A) and bossing (B), excellent
Choosing is embedded with thermal insulating filling (F), and described thermal insulating filling (F) width is 10～30mm.
Further preferred as this method, crystallization column plate (4) the lower section outward flange of described concave sandwich
Also having downward projection of projection, height of projection is 2～15mm.
Further preferred as this method, described female (A) is uniformly placed with vertical direction and penetrates depressed part
Divide the through hole (E) of (A), the pitch of holes 1～50mm of through hole (E), hole diameter 1～10mm.
Further preferred as this method, the inside of described female (A) is embedded with the of horizontal direction arrangement
One hollow serpentine pipeline (C), the first hollow serpentine pipeline (C) mutual spacing 3～20mm, uniformly it is placed with vertical in the middle of spacing
Nogata is to penetrating the through hole (E) of female (A), and hole surrounding has material parcel to be separated by with serpentine pipeline.
Further preferred as this method, the inside of described female (A) is embedded with the of horizontal direction arrangement
One hollow serpentine pipeline (C), can be passed through coolant or heating agent, and refrigerant temperature can be controlled in-15～35 DEG C, and heat medium temperature can control
At 25～130 DEG C；The inside of bossing (B) is embedded with the second hollow serpentine pipeline (D) of horizontal direction arrangement, is passed through heat
Matchmaker's temperature control is at 25～130 DEG C, and the width of described bossing (B) is 10～35mm, relative to female (A) to
The height of upper process is 2～15mm
Further preferred as this method, the crystallization column plate (4) of described concave sandwich is connecting crystallizing tower
The one side of body (1), its bossing (B) can omit.
Preferred as this method, the solvent used in step (1) is dichloromethane, dichloroethanes, chloroform, first
One or more mixed liquors in benzene, ethyl acetate.
Further preferred as this method, the solvent used in step (1) is preferably the one in toluene, dichloroethanes
Or its mixed liquor.
Preferred as this method, in step (2), decolorizing adsorbent is molecular sieve, silica gel, activated carbon, macroporous adsorbent resin
Compositions Deng one or more adsorbents；Decolorizing adsorbent is 1～25:100 with the mass ratio of material；Decolorization adsorption temperature
It it is 10～90 DEG C；Mixing time is 1～6 hour.
Preferred as this method, in step (4), precipitation pressure is-0.05～-0.095bar；Preferably by distilling off solvent
Directly apply mechanically, dissolve 2-chloro-5-chloromethyl thiazole crude product in step (1).
Preferred as this method, in step (5) organic solvent be acetone, dichloromethane, 1,2-dichloroethanes, chloroform,
The compositions of one or more solvents such as methanol, ethanol, ethyl acetate, N,N-dimethylformamide, dimethyl sulfoxide；Organic molten
Agent is 1～50:150 with the mass ratio of material.
Further object is that offer another kind prepares 2-chloro-5-chloromethyl thiazole crystal formation of the present invention
Method, is with 2-chloro-5-chloromethyl thiazole crude product as raw material, prepares 2-chloro-5-chloromethyl thiazole by crystallization process, including as follows
Step:
(1) washing: in washing kettle, by 2-chloro-5-chloromethyl thiazole dissolving crude product in solvent, adds water in batches and enters
Row washing, washing organic facies is to pH value=6～7；
(2) absorption is except color: add decolorizing adsorbent in the organic facies that step (1) obtains, and keeps stirring under uniform temperature
Certain time, become light yellow to mother solution color from buff；
(3) filter pressing: transfer the material into filter-pressing cauldron, carries out filter pressing, and the faint yellow organic facies being press-filtered out enters collecting tank, pressure
Filter cake in filter still is transferred to other equipment, and preferably carries out regenerating with recycling；
(4) precipitation: the material in step (3) collecting tank is transferred to precipitation still, is keeping certain pressure and a constant temperature
The precipitation that reduces pressure is carried out in the case of degree；
(5) organic solvent is added: in precipitation still, add organic solvent, stir, keep temperature of charge about 40 DEG C；
(6) crystallization apparatus crystallization, intensification fusing: the material in precipitation still is transferred to the crystallization apparatus that can overturn, warp
Supercooling crystallizes, then is warming up to the temperature more slightly higher than fusing point and is incubated diaphoresis, overturns crystallization apparatus, makes material be poured onto filtration
Plate, filters；It is warmed up to fusing point again, all solids in melting plant, collect and obtain highly purified 2-chloro-5-chloromethyl thiophene
Azoles crystal.
Preferred as this method, the solvent used in step (1) is dichloromethane, dichloroethanes, chloroform, first
One or more mixed liquors in benzene, ethyl acetate.
Preferred as this method, in step (2), decolorizing adsorbent is molecular sieve, silica gel, activated carbon, macroporous adsorbent resin
Compositions Deng one or more adsorbents；Decolorizing adsorbent is 1～25:100 with the mass ratio of material；Decolorization adsorption temperature
It it is 10～90 DEG C；Mixing time is 1～6 hour.
Preferred as this method, in step (4), precipitation pressure is-0.05～-0.095bar；Precipitation temperature be 40～
100℃；Preferably distilling off solvent is directly applied mechanically, dissolve 2-chloro-5-chloromethyl thiazole crude product in step (1).
Preferred as this method, in step (5) organic solvent be acetone, dichloromethane, 1,2-dichloroethanes, chloroform,
The compositions of one or more solvents such as methanol, ethanol, ethyl acetate, N,N-dimethylformamide, dimethyl sulfoxide；；Organic
Solvent is 1～50:150 with the mass ratio of material.
Preferred as this method, the crystallization apparatus that can overturn used in step (6), enters including kettle (1), mother solution
Material mouth (2), it is arranged in kettle (1) and can be two-part screen plate (3) by kettle (1) vertical separation, be arranged at kettle (1)
The rotating shaft (4) of outside horizontal direction, extend to the internal rotation bar (5) of kettle (1), discharging opening (6) from kettle (1) is outside,
It is characterized in that: mother liquor mouth (2) and rotation bar (5) are positioned at the side of screen plate (3), and discharging opening (6) is positioned at screen plate (3)
Opposite side；Rotate bar (5) vertical with screen plate (3) and can relative to screen plate (3) movement, and rotation bar (5) front end equipped with
It is parallel to the cross bar (7) of screen plate.
Further preferred as this method, connects tumbler in rotating shaft (4), can be by whole kettle (1) to turn
Axle (4) is that rotary shaft rotates 180 °.
Further preferred as this method, rotates the medium position that bar (5) is positioned at the horizontal direction of kettle (1), rotates
Depending on the maximum of bar (5) stretches into the size that distance designs according to kettle (1)；Cross bar (7) is flat-shaped, length according to material number
It is adjusted.
Further preferred as this method, cross bar (7) length preferably 10～30 centimetres, telescopic rotary bar (5)
Maximum stretches into distance and is advisable with distance screen plate (3) 2～5 centimetres.
Further preferred as this method, other parts of kettle (1) bottom are smooth crystalline portion, on kettle (1)
Portion installs and is provided with discharging opening (6) directly over screen plate (3), screen plate (3), and screen plate (3) has certain mesh number, and mesh number is preferred
For: 50～800 mesh, more preferably 350～500 mesh.
Further preferred as this method, kettle (1) is with chuck, and can be passed through between-30～180 DEG C is hot and cold
Medium；The setup of entrances and exits of hot and cold medium is in the adjacent locations of rotating shaft (4).
Further preferred as this method, opens and rotates bar (5), and its rotation is also mobile to screen plate (3), front end equipped with
Upper for screen plate (3) material piled up is bulldozed by the cross bar (7) being parallel to screen plate.
The mechanism that diaphoresis (sweating) acts on is to be maintained by crystal at a temperature of more slightly higher than its fusing point, allows crystals
Low-melting impurities constantly melt and flow out, so that crystal is purified.
2-chloro-5-chloromethyl thiazole crude product of the present invention, can prepare according to preparation method arbitrary in prior art.Example
As sold cyclization route most commonly seen when product synthesizes at present: 2-chlorine allyl isosulfocyanate, under the effect of sulfonic acid chloride, is sent out
Raw annulation, after having reacted, removed under reduced pressure solvent, obtain 2-chloro-5-chloromethyl thiazole crude product (content 78～80%).
It is an advantage of the invention that and obtain 2-chloro-5-chloromethyl thiazole crystal formation, product purity is high, it is possible to effectively prevent impurity from joining
With side reaction, improve the productivity of end-product, reduce the impurity content of end-product, reduce the purification difficulty of end-product.And pass through
Utilize 2-chloro-5-chloromethyl thiazole fusing point low, the characteristic that impurity fusing point is high, prepare highly purified 2-by the method for crystallization chloro-
5-5-chloromethyl thiazole crystal formation, this preparation method is simple, product purity is high, steady quality, separation method are simple, energy consumption is low, the three wastes
Generation amount is little, is a kind of preparation method meeting green chemical industry demand for development.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diagram of the 2-chloro-5-chloromethyl thiazole crystal form samples of the present invention.
Fig. 2 is the knot with concave sandwich that 2-chloro-5-chloromethyl thiazole crystal formation of the present invention uses when preparing
Its structural representation of crystallizer of brilliant column plate.
Fig. 3 is structure schematic top plan view and middle part X-X ' the half-sectional view schematic diagram crystallizing column plate in Fig. 2 crystallizer.
Fig. 4 be the crystallization apparatus that can overturn that uses when preparing of 2-chloro-5-chloromethyl thiazole crystal formation of the present invention its do not turn over
Rotation structure schematic diagram.
Fig. 5 is the schematic diagram after the crystallization apparatus that can the overturn upset 180 ° of Fig. 4.
The element of Fig. 2 and Fig. 3 and reference:
1, crystallization tower body；2, mother liquor mouth；3, nitrogen inlet；4, the crystallization column plate of concave sandwich；5, thing
Material outlet；A, crystallization column plate female；B, around female A and relative to female A bossing upwards, lower section
Outward flange also has downward projection of projection；C, the inside of crystallization column plate female A are embedded with the first of horizontal direction arrangement
Hollow serpentine pipeline；D, the inside of crystallization column plate bossing B are embedded with the second hollow serpentine pipeline that horizontal direction is arranged；
E, vertical direction penetrate the through hole of female A；It is embedded with thermal insulating filling between F, female A and bossing B；
The element of Fig. 4 and Fig. 5 and reference:
1, kettle；2, mother liquor mouth；3, screen plate；4, rotating shaft；5, bar is rotated；6, discharging opening；7, cross bar.
Detailed description of the invention
Below by the detailed description of the invention of embodiment, the foregoing of the present invention is described further, but these are real
Execute example and the present invention is not constituted any restriction.
The preparation of embodiment 1 2-chloro-5-chloromethyl thiazole crystal formation (uses the crystallization column plate of concave sandwich
Crystallizer)
(1) washing: in washing kettle, be dissolved in 150kg toluene in 400kg2-chloro-5-chloromethyl thiazole crude product, point
Batch adds 900kg water and washes, pH value=6～7 of washing organic facies, after washing, separates lower floor's organic facies；
(2) absorption is except color: add 25kg macroporous adsorbent resin in the material that step (1) obtains, and stirs 3 little at 35 DEG C
Time, become light yellow to mother solution color from buff；
(3) filter pressing: the material that step (2) obtains is transferred to filter-pressing cauldron, carries out filter pressing, the faint yellow material being press-filtered out enters
Enter collecting tank；
(4) precipitation: the material in step (3) collecting tank is transferred to precipitation still, at the pressure of-0.08～-0.095bar
Under, toluene distillation is gone out by 65～75 DEG C, obtains toluene and can directly overlap for step (1) as dissolution solvent；
(5) organic solvent is added: addition 45kg ethyl acetate in precipitation still: N,N-dimethylformamide=1:4(volume
Than) organic solvent, stir, keep temperature of charge about 40 DEG C；
(6) crystallizer crystallization, intensification fusing:
Use the crystallizer of the crystallization column plate of concave sandwich, equipment crystallization column plate gradient temperature control: crystallizing tower
Plate bossing B temperature control at 28～30 DEG C, column plate female A temperature control 3～5 DEG C.
By the Material control temperature in precipitation still at 35 DEG C, divide through material from mother liquor mouth 2 with the flow velocity of 50kg/h
Cloth device enters in the crystallization tower body 1 of crystallizer, after adding material；Crystallization column plate 4 starts to be to slowly warm up to 20～23 DEG C, protects
Hold certain time, make lower of fused materials；The nitrogen with certain flow rate it is passed through by nitrogen inlet 3, then by crystallizing tower plate temperature
It is warming up to 28 DEG C, keeps a period of time, stick to the material of plane of crystal by nitrogen stripping, enter solvent recovery tank, operated
Nitrogen in journey enters device for absorbing tail gas from the outlet being arranged on above solvent recovery tank；Closing nitrogen, column plate continues to heat up
To 40～42 DEG C, the material in crystallizing tower all melts, and material enters product collecting tank from material outlet 5, and product is crystal, pure
Degree >=99.5%.
The preparation (using the crystallizer that can overturn) of embodiment 2 2-chloro-5-chloromethyl thiazole crystal formation
(1) washing: in washing kettle, be dissolved in 300kg dichloroethanes in 400kg2-chloro-5-chloromethyl thiazole crude product
In, add 900kg water in batches and wash, pH value=6～7 of washing organic facies, after washing, separate lower floor's organic facies；
(2) absorption is except color: add 50kg activated carbon in the material that step (1) obtains, stirring 3 hours at 40 DEG C, extremely
Mother solution color is become light yellow from buff；
(3) filter pressing: the material that step (2) obtains is transferred to filter-pressing cauldron, carries out filter pressing, the faint yellow material being press-filtered out enters
Enter collecting tank；
(4) precipitation: the material in step (3) collecting tank is transferred to precipitation still, at the pressure of-0.06～-0.07bar
Under, dichloroethanes is distilled out by 50～60 DEG C, obtains dichloroethanes and can directly overlap for step (1) as dissolution solvent；
(5) add organic solvent: in precipitation still add 50kg methanol: dichloromethane=1:1(volume ratio) organic molten
Agent, stirs, and keeps temperature of charge about 40 DEG C.
(6) crystallization apparatus crystallization, intensification fusing: the material in precipitation still is transferred to the still of the crystallization apparatus that can overturn
Body (1), is slowly introducing 5 DEG C of cold water in chuck so that material was cooled to 5～10 DEG C in 3 hours, and crystallization terminates；Chuck delays
Slowly it is passed through 25～32 DEG C of warm water, makes crystallized stock be incubated 2 hours, after insulation terminates, slowly overturn kettle with rotating shaft 4 for rotary shaft
1 to 180 °, making material slowly be poured onto on screen plate 3, open and rotate bar 5, its rotation is the most mobile to screen plate (3), front end
The material being deposited in screen plate 3 surface is bulldozed by cross bar 7, opens vacuum, carries out sucking filtration, and the material that sucking filtration goes out enters impurity and collects
Tank, after sucking filtration terminates for 2 hours；Kettle 1 chuck is passed through 45～50 DEG C of warm water, by all material melts in kettle, collects liquid phase
Enter product collecting tank, obtain highly purified 2-chloro-5-chloromethyl thiazole crystal, purity >=99.7%.
The preparation (using the crystallizer that can overturn) of embodiment 3 2-chloro-5-chloromethyl thiazole crystal formation
(1) washing: in washing kettle, be dissolved in 150kg toluene in 400kg2-chloro-5-chloromethyl thiazole crude product, point
Batch adds 900kg water and washes, pH value=6～7 of washing organic facies, after washing, separates lower floor's organic facies；
(2) absorption is except color: add 30kg activated carbon in the material that step (1) obtains, stirring 3 hours at 45 DEG C, extremely
Mother solution color is become light yellow from buff；
(3) filter pressing: the material that step (2) obtains is transferred to filter-pressing cauldron, carries out filter pressing, the faint yellow material being press-filtered out enters
Enter collecting tank；
(4) precipitation: the material in step (3) collecting tank is transferred to precipitation still, at the pressure of-0.08～-0.095bar
Under, toluene distillation is gone out by 65～75 DEG C, obtains toluene and can directly overlap for step (1) as dissolution solvent；
(5) organic solvent is added: addition 60kg methanol in precipitation still: N,N-dimethylformamide=1.25:1(volume
Than) organic solvent, stir, keep temperature of charge about 40 DEG C.
(6) crystallization apparatus crystallization, intensification fusing: the material in precipitation still is transferred to the still of the crystallization apparatus that can overturn
Body 1, is slowly introducing 5 DEG C of cold water in chuck so that material was cooled to 5～10 DEG C in 3 hours, and crystallization terminates；In chuck slowly
It is passed through 25～32 DEG C of warm water, makes crystallized stock be incubated 2 hours, after insulation terminates, slowly overturn kettle 1 with rotating shaft 4 for rotary shaft
To 180 °, making material slowly be poured onto on screen plate 3, open and rotate bar 5, its rotation is the most mobile to screen plate (3), the horizontal stroke of front end
The material being deposited in screen plate 3 surface is bulldozed by bar 7, opens vacuum, carries out sucking filtration, and the material that sucking filtration goes out enters impurity and collects
Tank, after sucking filtration terminates for 2 hours；Kettle 1 chuck is passed through 45～50 DEG C of warm water, by all material melts in kettle, collects liquid phase
Enter product collecting tank, obtain highly purified 2-chloro-5-chloromethyl thiazole crystal, purity >=99.7%.
The X-ray powder diffraction of experimental example 1 2-chloro-5-chloromethyl thiazole crystal formation measures
The 2-chloro-5-chloromethyl thiazole crystal form samples prepared by above-described embodiment 1 carries out X-ray test, gained X-ray
Powder diffraction spectrum is as it is shown in figure 1, major parameter is listed in table 1.
| d(A) | 8.5654 | 6.26679 | 4.85511 | 4.48521 | 4.29909 | 4.08585 | 3.89743 | 3.62973 | 3.57306 |
| 2θ(°) | 10.319 | 14.121 | 18.258 | 19.778 | 20.644 | 21.734 | 22.798 | 24.505 | 24.9 |
| d(A) | 3.39114 | 3.36096 | 3.23759 | 3.13217 | 2.91894 | 2.86823 | 2.74943 | 2.48754 | 2.28237 |
| 2θ(°) | 26.259 | 26.499 | 27.528 | 28.474 | 30.603 | 31.158 | 32.54 | 36.078 | 39.449 |
Table 1 crystal form samples X-ray powder diffraction spectrum
The 2-chloro-5-chloromethyl thiazole crystal form samples prepared by above-described embodiment 2-3 carries out X-ray test respectively, obtains
X-ray powder diffraction spectrum same for Fig. 1.
The explanation of above example is only intended to help and understands the present invention, make professional and technical personnel in the field be capable of or
Use the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of being made, equivalent
Replacement, improvement etc., should be included within the scope of the present invention.
Claims (4)
1. the method preparing 2-chloro-5-chloromethyl thiazole crystal formation, is with 2-chloro-5-chloromethyl thiazole crude product as raw material, logical
Cross crystallization process and prepare 2-chloro-5-chloromethyl thiazole, it is characterised in that comprise the steps:
(1) washing: in washing kettle, by 2-chloro-5-chloromethyl thiazole dissolving crude product in solvent, adds water in batches and carries out water
Washing, washing organic facies is to pH value=6～7；
(2) absorption is except color: add decolorizing adsorbent in the organic facies that step (1) obtains, and keeps stirring under uniform temperature certain
Time, become light yellow to mother solution color from buff；
(3) filter pressing: transfer the material into filter-pressing cauldron, carries out filter pressing, and the faint yellow organic facies being press-filtered out enters collecting tank, filter-pressing cauldron
In filter cake be transferred to other equipment；
(4) precipitation: the material in step (3) collecting tank is transferred to precipitation still, is keeping certain pressure and uniform temperature
In the case of carry out reduce pressure precipitation；
(5) organic solvent is added: in precipitation still, add organic solvent, stir, keep temperature of charge about 40 DEG C；
(6) crystallizer crystallization, intensification fusing:
Crystallizer is the crystallizer of the crystallization column plate with concave sandwich, enters including crystallization tower body (1), mother solution
Material mouth (2), nitrogen inlet (3), the crystallization column plate (4) of concave sandwich, material outlet (5)；Wherein, mother liquor mouth
(2), nitrogen inlet (3) be positioned at the top of all crystallization column plates (4), material outlet (5) is positioned under all crystallization column plates (4)
Side；Crystallization column plate (4), raises up part by female (A) with around female (A) and relative to female (A)
(B) composition, the inside of female (A) is embedded with the first hollow serpentine pipeline (C) of horizontal direction arrangement, can be passed through coolant
Or heating agent；The inside of bossing (B) is embedded with the second hollow serpentine pipeline (D) of horizontal direction arrangement, can be passed through heating agent；
Female (A) is placed with vertical direction and penetrates the through hole (E) of female (A)；
Material in precipitation still is transferred to the crystallizer with the crystallization column plate of concave sandwich, and material is from by leading to
Hole (E) neutralizes bossing (B) outer rim and flows downward, and crystallizing tower plate temperature is relatively low has made solid gradually separate out；Charging terminates
Rear crystallization column plate starts slowly heat up and keep certain time, makes to stick to the solvent of plane of crystal and fails the part of crystallization
Material is neutralized bossing (B) outer rim drippage by through hole (E) and flows out from bottom material outlet (5), nitrogen inlet (3) be passed through
There is the nitrogen of certain flow rate, and crystallizing tower plate temperature is warming up to less than fusing point 1.5-1 DEG C and keeps a period of time, stick to
The material of plane of crystal, by nitrogen stripping, enters solvent recovery tank, and the nitrogen in operating process is from being arranged on solvent recovery tank
The outlet of side enters device for absorbing tail gas；Close nitrogen, the material that column plate is continuously heating in crystallizing tower all melts, material from
Crystallized stock outlet (5) enters product collecting tank, obtains highly purified 2-chloro-5-chloromethyl thiazole crystal；
Thermal insulating filling (F), described thermal insulating filling (F) width it is embedded with between described female (A) and bossing (B)
10～30mm；
Described female (A) is uniformly placed with vertical direction and penetrates the through hole (E) of female (A), between the hole of through hole (E)
Away from 1～50mm, hole diameter 1～10mm；
The width of described bossing (B) is 10～35mm, relative to female (A) height upwardly be 2～
15mm；
In step (2), decolorization adsorption temperature is 10～90 DEG C；Mixing time is 1～6 hour；
In step (4), precipitation pressure is-0.05～-0.095bar；Precipitation temperature is 40～100 DEG C.
A kind of method preparing 2-chloro-5-chloromethyl thiazole crystal formation the most according to claim 1, it is characterised in that step
(1) solvent used in is one or more mixing in dichloromethane, dichloroethanes, chloroform, toluene, ethyl acetate
Liquid.
A kind of method preparing 2-chloro-5-chloromethyl thiazole crystal formation the most according to claim 1, it is characterised in that step
(2) in, decolorizing adsorbent is molecular sieve, silica gel, activated carbon, the compositions of one or more adsorbents of macroporous adsorbent resin；De-
Color adsorbent is 1～25:100 with the mass ratio of material.
A kind of method preparing 2-chloro-5-chloromethyl thiazole crystal formation the most according to claim 1, it is characterised in that step
(5) during in, organic solvent is methanol, ethyl acetate, N,N-dimethylformamide, compositions and the volume ratio of two kinds are 1:5～5:
1。
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| CN105037424A (en) * | 2015-08-15 | 2015-11-11 | 湖州旭龙生物化学有限公司 | Chlorpyrifos refining method |
| CN112480023A (en) * | 2020-12-09 | 2021-03-12 | 怀仁市普惠生物科技有限公司 | Method for synthesizing dichloro pentachloromethyl thiazole |
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| CN1055964A (en) * | 1990-04-27 | 1991-11-06 | 日本钢管株式会社 | Make the equipment of silicon single-crystal |
| CN1430613A (en) * | 2000-05-23 | 2003-07-16 | 辛根塔参与股份公司 | Method for producing 2-chloro-5-chloromethyl-1,3-thiazole |
| CN1446204A (en) * | 2000-08-10 | 2003-10-01 | 拜尔农作物科学股份公司 | Method for purifying 2-chloro-5-chloromethyl thiazole |
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| CN1055964A (en) * | 1990-04-27 | 1991-11-06 | 日本钢管株式会社 | Make the equipment of silicon single-crystal |
| CN1430613A (en) * | 2000-05-23 | 2003-07-16 | 辛根塔参与股份公司 | Method for producing 2-chloro-5-chloromethyl-1,3-thiazole |
| CN1446204A (en) * | 2000-08-10 | 2003-10-01 | 拜尔农作物科学股份公司 | Method for purifying 2-chloro-5-chloromethyl thiazole |
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