CN110354777B - Method for preparing cis-para-substituted cyclohexylamino nitrile maleate by using reaction device of ultrasonic-assisted crystallization - Google Patents
Method for preparing cis-para-substituted cyclohexylamino nitrile maleate by using reaction device of ultrasonic-assisted crystallization Download PDFInfo
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- CN110354777B CN110354777B CN201910698616.3A CN201910698616A CN110354777B CN 110354777 B CN110354777 B CN 110354777B CN 201910698616 A CN201910698616 A CN 201910698616A CN 110354777 B CN110354777 B CN 110354777B
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 15
- -1 cyclohexylamino Chemical class 0.000 title claims abstract description 12
- 238000002425 crystallisation Methods 0.000 title claims abstract description 10
- 230000008025 crystallization Effects 0.000 title claims abstract description 10
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 29
- 239000011976 maleic acid Substances 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 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
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000005931 Spirotetramat Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CLSVJBIHYWPGQY-GGYDESQDSA-N spirotetramat Chemical compound CCOC(=O)OC1=C(C=2C(=CC=C(C)C=2)C)C(=O)N[C@@]11CC[C@H](OC)CC1 CLSVJBIHYWPGQY-GGYDESQDSA-N 0.000 description 2
- 125000006725 C1-C10 alkenyl group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000005133 alkynyloxy group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 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
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- 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 invention relates to a reaction device for ultrasonic-assisted crystallization and application thereof, which comprises a kettle body, a kettle cover, a stirrer, a hollow baffle plate arranged on the inner wall of the kettle body, and an ultrasonic generator arranged in the hollow baffle plate. The invention also relates to the use of the above-described reaction apparatus for preparing cis-para-substituted cyclohexylamino nitrile maleate, and a method for preparing cis-para-substituted cyclohexylamino nitrile maleate using the apparatus.
Description
Technical Field
The invention relates to a reaction device for ultrasonic-assisted crystallization, application thereof and a preparation method using the device.
Background
The maleic acid can separate para-substituted cyclohexanecarbazide compound with good selectivity, and the cis-form salt compound obtained after salifying and separating is an important intermediate for preparing spirotetramat.
However, since maleic acid is a solid and has low solubility in the reaction solvent, the solubility of cis-para-substituted cyclohexylamino nitrile maleate obtained by salifying is also low, and the phenomenon that cis-form salt is deposited on the surface of free maleic acid and wraps the free maleic acid can occur, so that the salifying of the wrapped free maleic acid is blocked, and finally, the non-salified free maleic acid pollutes the product, and the purity and quality of the product are affected.
Disclosure of Invention
In view of the above, the present invention aims to provide a reaction apparatus for ultrasonic-assisted crystallization.
The invention relates to the following specific steps:
(1) A reaction device for ultrasonic-assisted crystallization comprises a kettle body, a kettle cover, a stirrer, a hollow baffle plate arranged on the inner wall of the kettle body and an ultrasonic generator arranged in the hollow baffle plate.
(2) The reaction device described in the above (1), the stirrer is preferably an axial-flow paddle stirrer, and the number of preferable blades is three or two, i.e. three blades are arranged at the bottom of the stirring paddle, and two blades are arranged at the middle of the stirring paddle.
(3) The reaction apparatus according to the above (1) or (2), wherein the number of hollow baffles is 2 or more, preferably 2 to 4, more preferably 4.
(4) The reaction apparatus according to any one of the above (1) to (3), wherein a jacket is provided outside the vessel body.
(5) The reaction apparatus according to any one of the above (1) to (4), wherein a discharge port is provided at the bottom of the vessel.
(6) The reaction device according to any one of the above (1) to (5), wherein a pressure gauge is provided above the kettle body, and an explosion-proof valve is provided on a communication pipe between the pressure gauge and the inner cavity of the kettle body.
(7) The reaction apparatus according to any one of the above (1) to (6), wherein a thermocouple type temperature sensor is provided on one side of the tank body.
(8) The reaction device according to any one of the above (1) to (7), wherein a frequency converter is provided on the motor.
(9) The reaction apparatus according to any one of the above (1) to (8), wherein bases are provided on both sides below the tank body.
(10) The reaction apparatus according to any one of the above (1) to (9), wherein the tank cover is connected to the upper side of the tank body by a flange.
(11) The use of the reaction apparatus as described in any one of the above (1) to (11) for producing a cis-para-substituted cyclohexylaminonitrile maleate represented by the following formula (I):
in the formula (I), R 1 Is C 1 -C 10 Alkyl or alkyloxy, C 1 -C 10 Alkenyl or alkenyloxy, C 1 -C 10 Alkynyl or alkynyloxy, C 1 -C 10 Cycloalkyl or cycloalkyloxy, C containing 1-2 heteroatoms selected from O and N 1 -C 10 Heterocycloalkyl or heterocycloalkyloxy; preferably the above-mentioned groups having 1 to 6 carbon atoms, more preferably C 1-6 Alkyl or alkyloxy, C 1-6 Cycloalkyl or cycloalkyloxy, C containing 1-2 heteroatoms selected from O and N 1-6 Heterocyclyl or heterocycloalkyloxy, more preferably C 1-6 Alkyl or alkyloxy, particularly preferably methyl or methoxy. HX is maleic acid.
(12) A process for producing a cis-para-substituted cyclohexylaminonitrile maleate represented by the above formula (I), wherein the reaction apparatus as defined in any of the above items (1) to (10) is used.
(13) The method of the above (12), which comprises: an organic solvent solution of a cis/trans para-substituted cyclohexylaminonitrile compound corresponding to the above formula (I) and 0.3 to 0.55 mol times, preferably 0.3 to 0.5 mol times, of maleic acid are added to the above reaction apparatus, stirred and sonicated, and then cis-para-substituted cyclohexylaminonitrile maleate represented by the above formula (I) is separated by filtration or the like.
(14) The method according to the above (12) or (13), wherein the temperature in the reaction apparatus is maintained at 5 to 40 ℃, preferably 20 to 30 ℃, more preferably 25 to 30 ℃ while stirring and ultrasonic treatment.
(15) The method of any one of the above (12) to (14), wherein the time of stirring and ultrasonic treatment is 1 to 10 hours, preferably 2 to 8 hours, more preferably 3 to 6 hours.
(16) The method according to any one of the above (12) to (15), wherein the ultrasonic power of the reaction device is set to 0.1 to 0.8W/liter.
(17) The method according to any one of the above (12) to (16), wherein the organic solvent is an anhydrous organic solvent or a low-moisture organic solvent having a moisture content of 1% or less, preferably toluene or xylene.
Drawings
FIG. 1 is a schematic view of an example of a reaction apparatus for ultrasonic-assisted crystallization according to the present application.
Reference numerals illustrate:
1-jacket; 2-a kettle body; 3-an ultrasonic generator; 4-a hollow baffle; 5-kettle cover; 6-manhole; 7-a thermo-well; 8-wiring holes of the ultrasonic generator; 9-a stirrer; 10-a discharge port 11-a jacket liquid inlet; 12-jacket liquid outlet.
Detailed Description
In the reaction device, the hollow baffle plate is arranged on the inner wall of the kettle body, and the ultrasonic generator is arranged in the baffle plate, so that the reaction device has simple structure and reasonable design.
The baffle plate is arranged in the reaction device, so that the shearing performance of the stirrer can be improved, and particularly in a solid-liquid mixed suspension system, the particles can be fine and uniform.
In addition, the baffle is hollow structure, through setting up supersonic generator in it, gives the baffle additional ultrasonic function, the cleanness of reation kettle of being convenient for.
In addition to the above advantages, when the reaction apparatus of the present invention is used for selectively separating the cis-substituted cyclohexanecarbazide maleate salt by salifying the para-substituted cyclohexanecarbazide compound with maleic acid, the phenomenon that the maleate solid after salifying is deposited on the surface of the undissolved free maleic acid solid particles and encapsulates the maleic acid, thereby preventing the internal maleic acid from further salifying, thereby enabling the salifying reaction to be more sufficient and further reducing the pollution of the free maleic acid in the final product.
In a preferred embodiment, 2 to 4 baffles, more preferably 4 baffles, are provided in the reaction vessel. An ultrasonic generator is arranged in each baffle. The ultrasonic intensity can be controlled by controlling the on-off of each ultrasonic generator or adjusting the output power thereof.
The ultrasonic intensity can be adjusted according to the quantity of materials and other factors, and the ultrasonic power is preferably 0.1-0.8W/L.
Preferably, the ultrasonic generator is connected with a control part arranged outside the kettle body through a wiring hole on the kettle body.
In a more preferred embodiment, a jacket may be provided outside the tank body, and a cooling medium or the like may be circulated in the jacket as needed.
In other preferred embodiments, the stirrer adopts an axial-flow paddle stirrer, the number of blades is three or two, namely, three blades are arranged at the bottom of the stirring paddle, and two blades are arranged at the middle of the stirring paddle, so that stirring is more sufficient.
The above-described reaction apparatus of the present invention is not limited to the above-described maleate salt production, but can be applied to other reactions involving a crystallization step as well.
A preferred example of the reaction apparatus of the present invention is shown in FIG. 1, but the scope of the present invention is not limited to these examples, and any changes or modifications that do not depart from the gist of the present invention are intended to be within the scope of the present invention.
The starting compound used in the production process of the present invention, that is, the cis/trans para-substituted cyclohexylaminonitrile compound corresponding to the above formula (I), can be synthesized by a known method disclosed in, for example, chinese patent document CN103270020 a.
The time for stirring and ultrasonic treatment is usually 1 to 10 hours, preferably 2 to 8 hours, more preferably 3 to 6 hours.
The temperature in the reaction apparatus is maintained at 5 to 40 ℃, preferably 20 to 30 ℃, more preferably 25 to 30 ℃ during stirring and ultrasonic treatment.
The organic solvent used in the production method of the present invention is preferably an anhydrous organic solvent or a low-moisture organic solvent having a moisture content of 1% or less, more preferably toluene or xylene, from the viewpoint of obtaining a product having higher stability.
The amount of maleic acid is preferably 0.3 to 0.55 mol times, more preferably 0.3 to 0.5 mol times, relative to the cis/trans para-substituted cyclohexylamino nitrile compound.
After stirring and sonication, the cis-para-substituted cyclohexylaminonitrile maleate is isolated by filtration or the like.
Examples
Example 1
1200kg of toluene solution of p-methoxycyclohexylamino nitrile (total 3000 kg) with a cis/trans ratio of 55:45 and 362kg of maleic acid (0.4 times by mole) were added to the reaction vessel shown in FIG. 1, the temperature was maintained at 25 to 30℃after the addition, the ultrasonic vibration was carried out for 3 hours while stirring at an ultrasonic power of 0.5W/liter, and then the reaction mixture was taken out from the discharge port at the bottom of the vessel, filtered, rinsed with an appropriate amount of toluene, and dried to obtain white cis-p-methoxycyclohexylamino nitrile maleate (800 kg, cis/inverse ratio: 98.7:1.3).
The obtained product is measured by a gas-phase internal standard method with paraxylene as an internal standard under the following conditions, and the amount of maleic acid combined with the cyanamide is calculated according to the content, and the amount of maleic acid combined with the cyanamide is subtracted from the maleic acid feeding amount, so that the amount of the coated free maleic acid is obtained.
Gas phase conditions FID detector
Sample inlet: 245 ℃ detector: 250 DEG C
Programming temperature: the initial temperature is kept at 60 ℃ for 0min, the temperature is raised to 110 ℃ at 11.5 ℃/min, the temperature is kept for 2.5min, the temperature is raised to 200 ℃ at 11.5 ℃/min, and the temperature is kept for 1min.
Split ratio: 10:1 sample injection amount: 0.2ul, flow: 8.0ml/min
Chromatographic column: SE-54 medium polarity column 30m×0.53mm
The result of the measurement in this example was that the amount of the encapsulated free maleic acid was 5.1% of the total amount of maleic acid charged.
20g of the obtained cis-p-methoxycyclohexylaminonitrile maleate was stored in a sample cell having a temperature of 25 to 30℃and a humidity of 40 to 45%, and the decomposition rate was 0.29% as measured on day 7.
Comparative example 1
1200kg of toluene solution of p-methoxycyclohexylaminonitrile (total 3000 kg) and 362kg of maleic acid (0.4 times by mole) in a cis/trans ratio of 55:45 were added to a conventional reaction vessel without an ultrasonic generator, the temperature was maintained at 25 to 30℃after the addition, the reaction vessel was stirred for 12 hours, and the precipitated maleate was filtered, rinsed with an appropriate amount of toluene and dried to give white cis-p-methoxycyclohexylaminonitrile maleate (770 kg, cis/trans ratio: 92.1:7.9).
The amount of the coated free maleic acid was 10.1% based on the total amount of maleic acid charged as measured in the same manner as in example 1, and the decomposition rate of the resulting cis-p-methoxycyclohexylaminonitrile maleate was 0.43% at day 7.
As is apparent from the results of the above examples and comparative examples, the reaction vessel with an ultrasonic generator of the present invention can promote faster and more sufficient salt formation of free maleic acid with p-methoxycyclohexylamino nitrile, save a lot of time, and reduce pollution of free maleic acid in the product, which is extremely advantageous for industrial mass production, as compared with conventional reaction vessels.
Industrial applicability
The reaction device can well solve the problem of free maleic acid encapsulation in the synthesis process of cis-p-methoxyl cyclohexyl amino nitrile maleate which is an important intermediate of spirotetramat, can also be used in other reactions with similar problems, and is a novel reaction device which is very useful in industry.
Claims (10)
1. A process for the preparation of cis-para substituted cyclohexylaminonitrile maleate of formula (I) wherein the following reaction apparatus for ultrasound-assisted crystallization is used:
in the formula (I) of the present invention,
R 1 is C 1 -C 10 Alkyl or alkyloxy groups of (a); HX is maleic acid;
the reaction device for ultrasonic-assisted crystallization comprises a kettle body, a kettle cover, a stirrer, a hollow baffle plate arranged on the inner wall of the kettle body and an ultrasonic generator arranged in the hollow baffle plate.
2. The process according to claim 1, wherein R 1 Is methyl or methoxy.
3. The production method according to claim 1 or 2, wherein the stirrer is an axial-flow paddle stirrer.
4. The production method according to claim 1 or 2, wherein the number of hollow baffles is 2 to 4.
5. The production method according to claim 1 or 2, wherein a jacket is provided outside the tank body.
6. The production method according to claim 1 or 2, comprising: adding an organic solvent solution of cis/trans para-substituted cyclohexylamino nitrile compound corresponding to the above formula (I) and 0.3-0.55 mol times of maleic acid into the reaction device, stirring and ultrasonic treatment, and separating to obtain cis-para-substituted cyclohexylamino nitrile maleate shown in the above formula (I).
7. The process according to claim 6, wherein the organic solvent is an anhydrous organic solvent or a low-moisture organic solvent having a moisture content of 1% or less.
8. The production method according to claim 7, wherein the organic solvent is toluene or xylene.
9. The preparation method according to claim 6, wherein the time of stirring and ultrasonic treatment is 2 to 8 hours.
10. The process according to claim 6, wherein the temperature in the reaction apparatus is maintained at 5 to 40℃while stirring and ultrasonic treatment, and the ultrasonic power of the reaction apparatus is set at 0.1 to 0.8W/liter.
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| Application Number | Priority Date | Filing Date | Title |
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| 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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| 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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