CN110354777A - Reaction unit of a kind of ultrasonic wave added crystallization and application thereof and preparation method using the device - Google Patents
Reaction unit of a kind of ultrasonic wave added crystallization and application thereof and preparation method using the device Download PDFInfo
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- CN110354777A CN110354777A CN201910698616.3A CN201910698616A CN110354777A CN 110354777 A CN110354777 A CN 110354777A CN 201910698616 A CN201910698616 A CN 201910698616A CN 110354777 A CN110354777 A CN 110354777A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 48
- 238000002425 crystallisation Methods 0.000 title claims abstract description 9
- 230000008025 crystallization Effects 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 44
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 44
- -1 Cyclohexylamino Chemical group 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000002825 nitriles Chemical class 0.000 claims abstract description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 25
- 239000011976 maleic acid Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 241000883990 Flabellum Species 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 4
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 3
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 3
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 3
- 125000006725 C1-C10 alkenyl group Chemical group 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- SBUXRMKDJWEXRL-ROUUACIJSA-N cis-body Chemical compound O=C([C@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ROUUACIJSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001245 hexylamino group Chemical group [H]N([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of reaction units and application thereof of ultrasonic wave added crystallization comprising autoclave body, kettle cover, blender, the hollow weir being arranged on the inner wall of kettle and the excusing from death wave producer being built in the hollow weir.The invention further relates to the purposes that above-mentioned reaction unit is used to prepare the Cyclohexylamino nitrile maleate that cis--contraposition replaces, and the method for preparing the Cyclohexylamino nitrile maleate that cis--contraposition replaces using the device.
Description
Technical field
The present invention relates to reaction unit of a kind of ultrasonic wave added crystallization and application thereof and use the preparation side of the device
Method.
Background technique
Maleic acid can align the Cyclohexylamino nitrile compound replaced with good Selective Separation, resulting after separating at salt
Cis- body salt compound is the important intermediate for preparing spiral shell worm ethyl ester.
But since maleic acid is solid, solubility is small in reaction dissolvent, replaces at the resulting cis--contraposition of salt
The solubility of Cyclohexylamino nitrile maleate is also very low, it may occur that cis- body mineralization is in free Malaysia acid surfaces and is wrapped
The phenomenon that wrapping up in causes the free maleic acid wrapped up to be obstructed at salt, finally does not influence to produce at the free maleic acid pollution products of salt
The purity and quality of product.
Summary of the invention
In view of problem above, the present invention is intended to provide a kind of reaction unit of ultrasonic wave added crystallization.
Present invention relates particularly to:
(1) a kind of reaction unit of ultrasonic wave added crystallization comprising autoclave body, kettle cover, blender, setting are in the autoclave body
Hollow weir on wall and the excusing from death wave producer being built in the hollow weir.
(2) reaction unit described in above-mentioned (1), the blender preferably use the dasher of axial-flow type, preferably leaf
Piece quantity is two on lower three, i.e., agitating paddle bottom is three pieces flabellum, is two panels flabellum in the middle part of agitating paddle.
(3) reaction unit described in above-mentioned (1) or (2), wherein the hollow weir is 2 or more, preferably 2 to 4
It is a, more preferably 4.
(4) reaction unit described in any one of above-mentioned (1) to (3), wherein being equipped with collet on the outside of the autoclave body.
(5) reaction unit described in any one of above-mentioned (1) to (4), wherein the autoclave body bottom is equipped with discharge port.
(6) reaction unit described in any one of above-mentioned (1) to (5), wherein pressure gauge is equipped with above the autoclave body, it should
Pressure gauge and the connecting pipeline of the autoclave body inner cavity are equipped with explosion-proof valve.
(7) reaction unit described in any one of above-mentioned (1) to (6), wherein the autoclave body side is equipped with thermojunction type
Temperature sensor.
(8) reaction unit described in any one of above-mentioned (1) to (7) is equipped with frequency converter on motor.
(9) reaction unit described in any one of above-mentioned (1) to (8), wherein two sides are equipped with pedestal below the autoclave body.
(10) reaction unit described in any one of above-mentioned (1) to (9), wherein the kettle cover passes through flange and the kettle
Connection above body.
(11) reaction unit described in any one of above-mentioned (1) to (11) is used to prepare right along following formula-shown in lower formula (I)
The purposes for the Cyclohexylamino nitrile maleate that position replaces:
In formula (I), R1It is C1-C10Alkyl or alkyl oxy, C1-C10Alkenyl or alkenyl oxygroup, C1-C10Alkynyl or
Alkynyl oxygroup, C1-C10Naphthenic base or cycloalkyl oxy, contain the heteroatomic C that 1-2 is selected from O and N1-C10Heterocyclylalkyl or
Heterocyclylalkyl oxygroup；Preferably above-mentioned group of the carbon atom number for 1-6, more preferably C1-6Alkyl or alkyl oxy, C1-6Cycloalkanes
Base or cycloalkyl oxy contain the 1-2 heteroatomic C selected from O and N1-6Heterocyclylalkyl or Heterocyclylalkyl oxygroup, it is further excellent
Choosing is C1-6Alkyl or alkyl oxy, particularly preferably methyl or methoxy.HX is maleic acid.
(12) preparation method for the Cyclohexylamino nitrile maleate that cis- shown in formula (I) on-contraposition replaces, wherein using
Reaction unit described in any one of above-mentioned (1) to (10).
(13) method described in above-mentioned (12), this method comprises: being added into above-mentioned reaction unit corresponding with upper formula (I)
The organic solvent solution for the Cyclohexylamino nitrile compound that the contraposition of cis/trans formula replaces and 0.3~0.55 mole times, preferably 0.3~
0.5 mole times of maleic acid, is stirred and ultrasonic, then passes through cis- shown in the isolated upper formula (I)s of modes such as filtering-contraposition
Substituted Cyclohexylamino nitrile maleate.
(14) method described in above-mentioned (12) or (13), wherein stir and maintain the temperature in above-mentioned reaction unit when ultrasonic
Degree is at 5~40 DEG C, preferably at 20~30 DEG C, more preferably at 25~30 DEG C.
(15) method described in any one of above-mentioned (12) to (14), wherein the time of stirring and ultrasound is 1~10 small
When, preferably 2~8 hours, more preferable 3~6 hours.
(16) method described in any one of above-mentioned (12) to (15), wherein the ultrasonic power of above-mentioned reaction unit is set
For 0.1~0.8 watt/liter.
(17) method described in any one of above-mentioned (12) to (16), wherein the organic solvent is anhydrous organic solvent
Or the low moisture organic solvent of moisture content≤1%, preferably toluene or dimethylbenzene.
Detailed description of the invention
Fig. 1 is the schematic diagram of an example of the reaction unit of the application ultrasonic wave added crystallization.
Description of symbols:
1- collet；2- autoclave body；3- supersonic generator；4- hollow weir；5- kettle cover；6- manhole；7- thermometer wrap；8- is super
The wiring hole of sonic generator；9- blender；10- discharge port 11- collet liquid inlet；12- collet liquid outlet.
Specific embodiment
In reaction unit of the invention, by the way that hollow weir is arranged on inner wall of kettle, and excusing from death is set in the baffle
Wave producer makes reaction unit simple structure and reasonable design.
Baffle is arranged in reaction unit can be improved the cutting performance of blender, the especially body in solid-liquid mix suspending
In system, particle can be made thin and uniform.
In addition, baffle is hollow structure, by the way that excusing from death wave producer is being arranged inside, baffle additional ultrasound function is given, just
In the cleaning of reaction kettle.
In addition to the above advantage, reaction unit of the invention is used for the Cyclohexylamino nitrile compound by replacing contraposition
When carrying out Selective Separation at salt with maleic acid and obtaining cis- substituted Cyclohexylamino nitrile maleate, pass through the interfacial effect of ultrasound
Maleate solid after salt can be reduced into is in the free maleic acid solid particles surface deposition not dissolved and by maleic acid
Package, to prevent internal maleic acid further at salt the phenomenon that, thus make salt-forming reaction more abundant, and then reduce final product
In free Malaysia acid pollution.
In a preferred embodiment, 2~4 baffles are set in reaction kettle, 4 baffles are more preferably set.Each baffle
Inside it is designed with excusing from death wave producer.It can be controlled by controlling the on-off of each excusing from death wave producer or adjusting its output power
Ultrasound intensity.
Ultrasound intensity can how much equal because usually adjusting according to material, and preferably ultrasonic power is 0.1~0.8 watt/liter.
Preferably, supersonic generator is connect by the wiring hole on autoclave body with the control unit being arranged in outside autoclave body.
In preferred embodiment, collet can be set on the outside of autoclave body, can be passed through in collet as needed
Recyclable cooling medium etc..
In other preferred embodiments, blender uses the dasher of axial-flow type, and blade quantity is on lower three
Two, i.e. agitating paddle bottom is three pieces flabellum, is two panels flabellum in the middle part of agitating paddle, keeps stirring more abundant.
Above-mentioned reaction unit of the invention is not limited only in above-described maleate preparation, can be applied equally to
It is related in other reactions of crystallisation step.
The preferred embodiment of reaction unit of the present invention is as shown in Fig. 1, but the scope of the invention is not limited to these examples, it is any not
The change or modification for being detached from spirit of the scope of the present invention are each fallen in the scope of the invention.
Raw material compound used in preparation method of the present invention, cis/trans formula contraposition i.e. corresponding with upper formula (I) replace
Cyclohexylamino nitrile compound can be synthesized for example, by known method disclosed in Chinese patent literature CN103270020A.
It stirs and the time of ultrasound is usually 1~10 hour, preferably 2~8 hours, more preferable 3~6 hours.
Temperature when stirring and is ultrasonic in reaction unit maintains 5~40 DEG C, preferably at 20~30 DEG C, more preferably 25
~30 DEG C.
From the aspect of obtaining the higher product of stability, organic solvent used in preparation method of the present invention is preferably anhydrous
The low moisture organic solvent of organic solvent or moisture content≤1%, more preferably toluene or dimethylbenzene.
Relative to the Cyclohexylamino nitrile compound that the contraposition of cis/trans formula replaces, the amount of maleic acid is preferably that 0.3-0.55 rubs
That times, more preferably 0.3-0.5 moles times.
After stirring and being ultrasonic, the Cyclohexylamino nitrile maleate that cis--contraposition replaces is separated by modes such as filterings.
Embodiment
Embodiment 1
1200kg cis/trans are added into reaction kettle shown in FIG. 1 than being 55:45 to methoxycyclohexyl amino nitrile
Toluene solution (total 3000kg) and 362kg maleic acid (0.4 mole times), maintain temperature at 25~30 DEG C after adding, side stirring
Side ultrasonic vibration 3 hours, ultrasonic power was 0.5 watt/liter, then takes out reaction mixture from the discharge port in bottom portion, is filtered, and was used
Q. s. toluene elution, it is dry, obtain it is white it is cis--to methoxycyclohexyl amino nitrile maleate (800kg, cis/trans ratio: 98.7:
1.3)。
Products therefrom is measured into cyanamide Malaysia as internal standard compound by gas phase internal standard method, using paraxylene under the following conditions
The content of hydrochlorate, the amount of the maleic acid in conjunction with cyanamide is converted by the content, and maleic acid inventory subtracts and cyanamide knot
The amount of the maleic acid of conjunction is the free maleic acid amount wrapped up.
Gas phase condition: fid detector
Injection port: 245 DEG C of detectors: 250 DEG C
Temperature programming: 60 DEG C of holding 0min of initial temperature are warming up to 110 DEG C with 11.5 DEG C/min, 2.5min are kept, with 11.5
DEG C/min is warming up to 200 DEG C, keep 1min.
Split ratio: 10:1 sample volume: 0.2ul, flow: 8.0ml/min
Chromatographic column: SE-54 middle polarity chromatographic column 30m × 0.53mm
The measurement result of the present embodiment is that the free maleic acid wrapped up accounts for maleic acid and feeds intake the 5.1% of total amount.
By it is resulting it is cis- -25~30 DEG C, humidity 40- are placed in methoxycyclohexyl amino nitrile maleate 20g
It is saved in 45% sample room, it is 0.29% that its resolution ratio was measured at the 7th day.
Comparative example 1
1200kg cis/trans are added into the common response kettle without excusing from death wave producer than being 55:45 to methoxy
The toluene solution (total 3000kg) and 362kg maleic acid (0.4 mole times) of butylcyclohexyl amino nitrile, maintain temperature 25 after adding
It~30 DEG C, stirs 12 hours, then the maleate of precipitating is filtered, is eluted with q. s. toluene, it is dry, it obtains white cis--right
Methoxycyclohexyl amino nitrile maleate (770kg, cis/trans ratio: 92.1:7.9).
It it is measured in the same method the free maleic acid wrapped up with embodiment 1 accounts for maleic acid and feed intake the 10.1% of total amount, it is resulting suitable
Formula-is 0.43% in the 7th day resolution ratio to methoxycyclohexyl amino nitrile maleate.
By above-described embodiment with the result of comparative example it is found that comparing with conventional reaction kettle, the present invention is with excusing from death wave hair
The reaction kettle of raw device can promote free maleic acid with to methoxycyclohexyl amino nitrile faster, more fully at salt, save big
The time of amount, and the free Malaysia acid pollution in product is reduced, this is extremely advantageous to industrialization large-scale production.
Industrial applicibility
Reaction unit of the invention can well solve as spiral shell worm ethyl ester important intermediate it is cis--to methoxy basic ring
Free maleic acid in hexylamino nitrile maleate synthesis process wraps up problem, equally can be used for that there are its of similar problems
It is industrial highly useful novel reaction device during it is reacted.
Claims (10)
1. a kind of reaction unit of ultrasonic wave added crystallization comprising autoclave body, kettle cover, blender, setting are on the inner wall of kettle
Hollow weir and the excusing from death wave producer that is built in the hollow weir.
2. reaction unit described in claim 1, the blender uses the dasher of axial-flow type, and preferably blade quantity is
Two on lower three, i.e., agitating paddle bottom is three pieces flabellum, is two panels flabellum in the middle part of agitating paddle.
3. reaction unit of any of claims 1 or 2, wherein the hollow weir is 2 or more, it is preferably 2 to 4, more excellent
It is selected as 4.
4. reaction unit described in any one of claims 1 to 3, wherein collet is equipped on the outside of the autoclave body,
It preferably further is equipped with discharge port in the autoclave body bottom,
Pressure gauge is equipped with more preferably above the autoclave body, the connecting pipeline of the pressure gauge and the autoclave body inner cavity is equipped with explosion-proof
Valve,
It further preferably is equipped with thermocouple temperature sensor in the autoclave body side,
It still more preferably is equipped with frequency converter on motor,
Two sides are equipped with pedestal still more preferably below the autoclave body,
The still more preferably described kettle cover above flange and the autoclave body by connecting.
Replace 5. reaction unit described in any one of Claims 1-4 is used to prepare cis- shown in lower formula (I)-contraposition
The purposes of Cyclohexylamino nitrile maleate,
In formula (I),
R1It is C1-C10Alkyl or alkyl oxy, C1-C10Alkenyl or alkenyl oxygroup, C1-C10Alkynyl or alkynyl oxygroup, C1-
C10Naphthenic base or cycloalkyl oxy, contain the heteroatomic C that 1-2 is selected from O and N1-C10Heterocyclylalkyl or Heterocyclylalkyl oxygen
Base；Preferably above-mentioned group of the carbon atom number for 1-6, more preferably C1-6Alkyl or alkyl oxy, C1-6Naphthenic base or naphthenic base
Oxygroup, the heteroatomic C that O and N is selected from containing 1-21-6Heterocyclylalkyl or Heterocyclylalkyl oxygroup, are further preferred that C1-6Alkyl
Or alkyl oxy, particularly preferably methyl or methoxy；
HX is maleic acid.
The preparation method for the Cyclohexylamino nitrile maleate that cis- shown in formula (I) on 6.-contraposition replaces, wherein being wanted using right
Reaction unit described in asking any one of 1 to 4.
7. method of claim 6, this method comprises: being added into above-mentioned reaction unit corresponding with upper formula (I) cis/trans
The organic solvent solution for the Cyclohexylamino nitrile compound that formula contraposition replaces and 0.3~0.55 mole times, preferably 0.3~0.5 are rubbed
You times maleic acid, stir and ultrasound, then pass through filtering etc. it is cis- shown in the isolated upper formula (I) of modes-contraposition replaces
Cyclohexylamino nitrile maleate.
8. method of claim 7, wherein the organic solvent is the low water of anhydrous organic solvent or moisture content≤1%
Divide organic solvent, preferably toluene or dimethylbenzene.
9. method described in any one of claim 6 to 8, wherein the time of stirring and ultrasound is 1~10 hour, preferably 2
~8 hours, more preferable 3~6 hours.
10. method described in any one of claim 6 to 9, wherein the temperature in reaction unit maintains when stirring and ultrasound
At 5~40 DEG C, preferably at 20~30 DEG C, more preferably at 25~30 DEG C；
The ultrasonic power of the further preferred reaction unit is set as 0.1~0.8 watt/liter.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910698616.3A CN110354777B (en) | 2019-07-31 | 2019-07-31 | Method for preparing cis-para-substituted cyclohexylamino nitrile maleate by using reaction device of ultrasonic-assisted crystallization |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910698616.3A CN110354777B (en) | 2019-07-31 | 2019-07-31 | Method for preparing cis-para-substituted cyclohexylamino nitrile maleate by using reaction device of ultrasonic-assisted crystallization |
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| CN110354777B CN110354777B (en) | 2024-03-12 |
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