CN101696170B - Method for synthesizing N-ethyl cyclohexylamine - Google Patents
Method for synthesizing N-ethyl cyclohexylamine Download PDFInfo
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- CN101696170B CN101696170B CN200910153233A CN200910153233A CN101696170B CN 101696170 B CN101696170 B CN 101696170B CN 200910153233 A CN200910153233 A CN 200910153233A CN 200910153233 A CN200910153233 A CN 200910153233A CN 101696170 B CN101696170 B CN 101696170B
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- ethyl cyclohexylamine
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Abstract
The invention discloses a method for synthesizing N-ethyl cyclohexylamine. The N-ethyl cyclohexylamine is prepared by taking a normal pressure fixed bed reactor as a reaction device, and putting gamma-Al2O3 serving as a catalyst in the normal pressure fixed bed reactor; using a mixture of cyclohexylamine and diethyl ether as a raw material in a mole ratio of the diethyl ether to the cyclohexylamine of 1-5:1; gasifying the raw material after the raw material is put in the reactor, then performing reaction under an atmosphere of taking an inert gas as a carrier under the action of the gamma-Al2O3 at a normal pressure, wherein the reaction temperature is between 200 and 350 DEG C, the reaction volume space velocity v is 0.1-0.6/h, and the volume space velocity is h-1; and after the reaction is finished, condensing and separating the obtained reaction product. The N-ethyl cyclohexylamine synthesized by the method has the characteristics of low cost, high yield and high selectivity.
Description
Technical field
The present invention relates to the atmospheric fixed bed reactors synthesis of a kind of compound method of organic cpds, particularly organic pesticide, medicine intermediate-N-ethyl cyclohexylamine.
Background technology
Aliphatic amide and verivate thereof are one type of important chemical material and medicine intermediate; Secondary aliphatic amine; Molecular structure is RNHR ', wherein when R and R ' are aliphatic alkyl inequality or cycloalkyl group, and the midbody that can be used as epoxy hardener or produce as the plant-growth protective material.The N-ethyl cyclohexylamine that this paper relates to promptly belongs to a kind of secondary aliphatic amine.At present, be that starting raw material prepares the existing following report of N-ethyl cyclohexylamine with the hexahydroaniline:
1) be raw material (Journal of Organic Chemistry, 64 (3), 803-806, with acetonitrile and hexahydroaniline; 1999), react through 5%Pd/C and ammonium formiate catalysis, product is N, N-diethyl cyclohexylamine and N-ethyl cyclohexylamine.
Mild condition is at room temperature carried out in this law reaction.But selectivity of product relatively poor (86/14), material toxicity is bigger simultaneously, and catalyzer costs an arm and a leg, and yield lowly is merely 38%.
2), with the reaction of hexahydroaniline and benzoyl hydroperoxide, obtain N-ethyl cyclohexylamine (Journal of Organic Chemistry, 64 (3), 803-806 with the triethyl-boron reaction again after at first generating the benzoyloxy hexahydroaniline; 1999).
It is high by 70.52% that this law has a yield, and product is single, the advantage that selectivity is high.But in two steps of reactions step, operate complicated; The reaction raw materials cost is expensive, is not suitable for industrial applications.
3), adopt monochloroethane (Journal of Chemical Research, Synopses, (10), 346-7; N-alkylating reagent such as 1988).
This method has the reaction preference height usually, the yield advantages of higher; But because the material toxicity that adopts is bigger, do not meet the requirement of modern Green Chemistry, the muriate that produces in the reaction process simultaneously can produce corrosion and other serious environmental pollution problem to equipment.
Summary of the invention
The technical problem that the present invention will solve provides the compound method of the N-ethyl cyclohexylamine that a kind of cost is low, yield is high, selectivity is high and process step is succinct.
In order to solve the problems of the technologies described above, the present invention provides a kind of compound method of N-ethyl cyclohexylamine: as reaction unit, the γ-Al as catalyzer is set in atmospheric fixed bed reactor drum with atmospheric fixed bed reactor drum
2O
3As raw material, the mol ratio of ether and hexahydroaniline is 1～5: 1 with the mixture of hexahydroaniline and ether; Raw material gets into back gasification in the reactor drum, is being under the atmosphere of carrier gas, at γ-Al with the rare gas element then
2O
3Effect under under normal pressure, react, temperature of reaction is 200～350 ℃, the volume space velocity v of reaction is 0.1-0.6/h; Volume space velocity
h
-1After above-mentioned reaction finishes, the reaction product of gained through condensation with separate, the N-ethyl cyclohexylamine.
Improvement as the compound method of N-ethyl cyclohexylamine of the present invention: the flow of rare gas element is 30～80L/h.
Further improvement as the compound method of N-ethyl cyclohexylamine of the present invention: rare gas element is N
2
Further improvement as the compound method of N-ethyl cyclohexylamine of the present invention: atmospheric fixed bed reactor drum is the stainless steel reaction pipe of internal diameter Φ=20mm, total length l=600mm, in establish γ-Al of 100ml
2O
3
Adopt the compound method of N-ethyl cyclohexylamine of the present invention; The gained reaction product is the mixture of N-ethyl cyclohexylamine and unreacted hexahydroaniline and ether; With obtaining the different fractions product after the above-mentioned reaction product process normal pressure simple distillation separation; Be the pure article (165 ℃) and the unreacted hexahydroaniline (can be used for recycled, 134.5 ℃) of N-ethyl cyclohexylamine.The N-ethyl cyclohexylamine of gained is accurate through the GC-MS qualitative framework.
The compound method of N-ethyl cyclohexylamine of the present invention as raw material, avoids the use of the very big ethylization reagent of toxicity (like ethyl sulfate etc.) with the mixture of hexahydroaniline and ether on raw material, therefore have the characteristics of environmental protection; The present invention reacts under normal pressure, and reaction conditions is gentle, has avoided the use of pressure-resistant equipment, has reduced production cost, has therefore that the equipment serialization is good, characteristics of easy handling and realization industrial sectorization.The present invention is with wide material sources and cheap commercially available γ-Al
2O
3Be catalysts, can further reduce production costs.Product of the present invention is merely the N-ethyl cyclohexylamine, and no diethyl cyclohexylamine generates; Therefore has the high advantage of selectivity.
Adopt the N-ethyl cyclohexylamine of the inventive method gained, carry out test analysis through gas chromatograph GC, the purity of N-ethyl cyclohexylamine >=99%.
Description of drawings
Do further explain below in conjunction with the accompanying drawing specific embodiments of the invention.
Fig. 1 is the annexation synoptic diagram of production equipment of the present invention.
Embodiment
Fig. 1 has provided a kind of device that is used for synthetic N-ethyl cyclohexylamine, comprises the carrier gas inlet 10 that under meter is housed, syringe 1, the atmospheric fixed bed reactor drum 3 that raw material (mixture of hexahydroaniline and ether) sample introduction is used; Atmospheric fixed bed reactor drum 3 is a stainless steel reaction pipe, its internal diameter Φ=20mm, total length l=600mm.Atmospheric fixed bed reactor drum 3 outer setting well heaters 9 (for example being process furnace), well heater 9 is used to regulate the temperature of reaction in the atmospheric fixed bed reactor drum 3; Carrier gas inlet 10 is connected with the top of atmospheric fixed bed reactor drum 3 respectively with syringe 1; In atmospheric fixed bed reactor drum 3, be provided with temperature measuring equipment 2.Interlude 5 at atmospheric fixed bed reactor drum 3 inner chambers is provided with the γ-Al as catalyzer
2O
3, in the upper end of interlude 5 filler 4 is set, filler 6 down is set in the lower end of interlude 5, below following filler 6, condensing works 7 is set, the bottom of atmospheric fixed bed reactor drum 3 is provided with outlet 8.
In this device, interlude 5 effective working lengths are about 400mm, effective volume is 110～120ml, general in interlude 5 catalyzer of filling 100ml.
During actual the use, the raw material that hexahydroaniline and ether are formed gets in the atmospheric fixed bed reactor drum 3 from syringe 1, N
2Get in the atmospheric fixed bed reactor drum 3 from carrier gas inlet 10; Raw material after the gasification is with N
2Under the atmosphere for carrier gas, through under the effect of catalyzer, reacting in the last filler 4 back entering interludes 5; The mixed gas of reaction gained is condensed into liquid through the device 7 that is condensed behind the following filler 6, flows out from exporting 8 at last.
The compound method of the N-ethyl cyclohexylamine of following examples 1～embodiment 6 all utilizes said apparatus to carry out.
Embodiment 1: a kind of N-ethyl cyclohexylamine compound method:
1, with the commercially available γ-Al of 100ml
2O
3Fill in the interlude 5 in the atmospheric fixed bed reactor drum 3, open carrier gas inlet 10 and condensing works 7, control N
2After flow velocity was 30L/h, heater 9 heated up and controls in the atmospheric fixed bed reactor drum 3 temperature-stables in 300 ℃; The raw material of 1: 1 hexahydroaniline of mol ratio and ether mixing back formation is placed syringe 1, and the top of frequent press fit bed bioreactor 3 is with N
2The atmospheric fixed bed reactor drum 3 of common entering carries out the N-ethylation reaction, and the raw material after the gasification is with 0.3/h
-1Air speed get into the γ-Al in the interlude 5
2O
3React; Reaction product is collected with liquid form through after the condensation of condensing works 7; Can obtain the different fractions product after separating through normal pressure simple distillation, i.e. pure article of N-ethyl cyclohexylamine (through gas chromatographic analysis content more than 99%) and unreacted hexahydroaniline.
The appearance that gets collection is carried out gas chromatographic analysis, and the hexahydroaniline transformation efficiency is 78%, and product is merely the N-ethyl cyclohexylamine, and no diethyl cyclohexylamine generates.
The hexahydroaniline that reclaims is used for recycled, and in hexahydroaniline, the yield of product N-ethyl cyclohexylamine is 69%.
Change flow rate of carrier gas, hexahydroaniline and ether mole proportioning among the embodiment 1, temperature of reaction, raw material volume space velocity, all the other steps obtain embodiment 2～embodiment 6 respectively with embodiment 1.The experimental result of gained is as shown in table 1:
Table 1 synthesizes instance
| Sequence number | Ether: hexahydroaniline (mol ratio) | Temperature of reaction (℃) | Flow rate of carrier gas (L/h) | Air speed (h -1) | Hexahydroaniline transformation efficiency % | N-ethyl cyclohexylamine yield % |
| |
1.5 | 200 | 40 | 0.1 | 65 | 67 |
| |
2 | 250 | 50 | 0.4 | 78 | 74 |
| |
3 | 300 | 80 | 0.2 | 87 | 80 |
| |
4 | 300 | 70 | 0.5 | 75 | 69 |
| Embodiment 6 | 5 | 350 | 60 | 0.6 | 83 | 77 |
At last, it is also to be noted that what more than enumerate only is several specific exampless of the present invention.Obviously, the invention is not restricted to above instance, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. the compound method of a N-ethyl cyclohexylamine is characterized in that: as reaction unit, the γ-Al as catalyzer is set in atmospheric fixed bed reactor drum with atmospheric fixed bed reactor drum
2O
3As raw material, the mol ratio of said ether and hexahydroaniline is 1～5: 1 with the mixture of hexahydroaniline and ether; Raw material gets into back gasification in the reactor drum, is being under the atmosphere of carrier gas, at γ-Al with the rare gas element then
2O
3Effect under under normal pressure, react, temperature of reaction is 200～350 ℃, the volume space velocity v of reaction is 0.1-0.6/h; Said volume space velocity
h
-1After above-mentioned reaction finishes, the reaction product of gained through condensation with separate, the N-ethyl cyclohexylamine.
2. the compound method of N-ethyl cyclohexylamine according to claim 1 is characterized in that: the flow of said rare gas element is 30～80L/h.
3. the compound method of N-ethyl cyclohexylamine according to claim 1 and 2 is characterized in that: said rare gas element is N
2
4. the compound method of N-ethyl cyclohexylamine according to claim 3 is characterized in that: said atmospheric fixed bed reactor drum is the stainless steel reaction pipe of internal diameter Φ=20mm, total length l=600mm, in establish γ-Al of 100ml
2O
3
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| CN200910153233A CN101696170B (en) | 2009-10-29 | 2009-10-29 | Method for synthesizing N-ethyl cyclohexylamine |
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| CN101696170B true CN101696170B (en) | 2012-09-19 |
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| CN103435494B (en) * | 2013-07-30 | 2016-02-03 | 苏州环科新材料有限公司 | The preparation method of N-ethyl cyclohexylamine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005239594A (en) * | 2004-02-25 | 2005-09-08 | Nagoya Industrial Science Research Inst | Method for alkylating aliphatic amine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005239594A (en) * | 2004-02-25 | 2005-09-08 | Nagoya Industrial Science Research Inst | Method for alkylating aliphatic amine |
Non-Patent Citations (2)
| Title |
|---|
| Nacario, Ruel, et al..Reductive monoalkylation of aromatic and aliphatic nitro compounds and the corresponding amines with nitriles.《Org. Lett.》.2005,第7卷(第3期),471-474. * |
| O. Phanstiel, et al..Synthesis of secondary amines via N-(benzoyloxy)amines and organoboranes.《J. Org. Chem.》.1999,第64卷(第3期),803-806. * |
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