CN110498748B - Application of L-arginine and derivatives thereof in preparing cyclododecanone oxime and method for preparing cyclododecanone oxime - Google Patents
Application of L-arginine and derivatives thereof in preparing cyclododecanone oxime and method for preparing cyclododecanone oxime Download PDFInfo
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- CN110498748B CN110498748B CN201910873345.0A CN201910873345A CN110498748B CN 110498748 B CN110498748 B CN 110498748B CN 201910873345 A CN201910873345 A CN 201910873345A CN 110498748 B CN110498748 B CN 110498748B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Abstract
The invention discloses application of L-arginine and derivatives thereof in preparing cyclododecanone oxime and a method for preparing cyclododecanone oxime. The L-arginine derivative comprises one or more of L-arginine-L-glutamic acid, L-arginine hydrochloride and L-arginine amber salt. The method takes one or more of L-arginine and derivatives thereof as an auxiliary agent, and cyclododecanone reacts with hydroxylamine sulfate to prepare cyclododecanone oxime. The auxiliary agent can control the content of iron ions in a reaction system, inhibit the decomposition of hydroxylamine sulfate, inhibit the generation of cyclododecylamine, improve the reaction selectivity, and is easy to separate and recover.
Description
Technical Field
The invention relates to application of a compound, in particular to application of L-arginine and derivatives thereof in preparing cyclododecanone oxime, and also relates to a method for preparing the cyclododecanone oxime by cyclododecanone.
Background
Cyclododecanone oxime can be rearranged to produce laurolactam, which is a monomer of nylon dodeca. Cyclododecanone is industrially commonly reacted with hydroxylamine sulfate to produce cyclododecanone oxime, and many documents are available on this oximation reaction.
GB1126495A describes a process for obtaining cyclododecanone oxime by oximation using cyclododecanone and hydroxylamine sulfate as a solvent at a pH of 3 to 5 using cumene hexahydroxide, and also reducing the consumption of hydroxylamine sulfate by two-stage countercurrent operation, but it does not mention how to solve the problem of slow reaction rate of the two-phase reaction.
In CN102892752A, a method for preparing cyclododecanone oxime by oximation using cyclododecanone and hydroxylamine sulfate is also described, and how to remove double bond impurities, double bridge impurities and other entrained impurities which may exist in the process, wherein it is mentioned that in order to avoid the volume of the reactor becoming large due to the excessively long reaction time, an additive such as a surfactant should be added to improve the mass transfer rate between oil and water phases to accelerate the reaction speed, but the method is only once carried out, and no specific additive is given, nor is it a patent point.
In CN100390137C, a process is described, but this invention uses a co-ammoximation process for the preparation of ketoximes, which uses a mixture of cyclohexanone and cyclododecanone, and hydrogen peroxide and ammonia water as raw materials, titanium silicalite as a catalyst, hexahydrocumene as a solvent, a quaternary ammonium salt as a co-catalyst, and an alkyl sulfonate as an interphase contact agent to produce a mixture of cyclohexanone and cyclododecanone oxime. The method requires the use of a mixture of cyclohexanone and cyclododecanone as a feedstock, and the proportion of cyclohexanone and cyclododecanone is kept at a relatively high level; in addition, the hydrogen peroxide reaction is used, and the safety and the decomposition consumption per se are also unfavorable for the reaction; in addition, various additives such as a catalyst, a cocatalyst and an interphase contact agent are required, so that the cost is high, the separation difficulty is high, and whether the catalyst can be recycled is not clear.
WO2005016817 discloses hydroxylamine stabilizers for use in hydroxylamine free base manufacturing processes. The stabilizer comprises aminoacetic acid, iminodiacetic acid, tris (2-aminoethyl) amine hexaacetic acid and the like, but the stabilizer is not a two-phase system aiming at a reaction system and has no catalytic effect on the reaction.
CN110015974A discloses that nitrogen-containing heterocyclic compounds such as piperazine, imidazole, pyridine, etc. can be used as pH buffer in oxime exchange reaction, which can improve the stability of organosilicon ether under strong acidic condition, prevent dehydration or hydrogen sulfide reaction and oxime dehydration, and reduce the formation of imine and amide. However, this patent is primarily directed to oxime exchange reaction systems, where the pH buffer mentioned does not have a significant promoting effect on the rate of the oximation reaction and hydroxylamine stability.
CN1235872C discloses that cyclododecanone oxime is prepared by using hydrogen peroxide, ammonia water and cyclododecanone as raw materials, a TS-1 titanium silicalite molecular sieve is used as a catalyst, citric acid is used as a cocatalyst, and alkyl sulfonate is used as an interphase contact agent, wherein the cocatalyst mainly has the function of improving selectivity and conversion rate. This method has the same problems as in CN100390137C described above.
CN102906065B discloses a process for the preparation of ketoximes from ketones and hydroxylamines in a two-phase system of a hydrophobic solvent and water, in the presence of a carboxylic acid/carboxylate. The patent mentions that the addition of carboxylic acid/carboxylate salts can increase the speed of the oximation reaction and reduce the reaction time, but does not address the problems of hydroxylamine stability and reaction by-products.
Therefore, in view of the technical problems of the above patents, an auxiliary and a new process are needed to solve the problems of long reaction time, partial impurities and hydroxylamine stability in the reaction raw materials of the traditional cyclododecanone oximation.
Disclosure of Invention
The invention aims to provide application of L-arginine and derivatives thereof in preparing cyclododecanone oxime. The invention also aims to provide a method for preparing cyclododecanone oxime by using one or more of L-arginine and derivatives thereof as an auxiliary agent. The auxiliary agent can control the content of iron ions in a reaction system, inhibit the decomposition of hydroxylamine sulfate, inhibit the generation of cyclododecylamine, improve the reaction selectivity, and is easy to separate and recover.
In order to solve the technical problems, the following technical scheme is adopted:
the application of L-arginine and derivatives thereof in preparing cyclododecanone oxime.
The structural formula of the L-arginine is shown as
The L-arginine derivative comprises one or more of L-arginine-L-glutamic acid, L-arginine hydrochloride and L-arginine succinate, and the structural formula of the L-arginine derivative is respectively shown as follows:
a process for preparing cyclododecanone oxime comprising the steps of: in the presence of a solvent and one or more of L-arginine and derivatives thereof (hereinafter referred to as an auxiliary agent), cyclododecanone and hydroxylamine sulfate react at a pH of 3-6.5 to prepare cyclododecanone oxime.
In the method of the invention, the content of iron ions in the reaction system is less than or equal to 10ppm, preferably less than or equal to 5ppm, and more preferably less than or equal to 1ppm during the reaction process.
The hydroxylamine sulfate can be pure hydroxylamine sulfate or raschig solution containing hydroxylamine sulfate, preferably raschig solution which mainly contains three components of ammonium sulfate, hydroxylamine sulfate and sulfuric acid and is mainly prepared by a raschig method.
As the solvent of the present invention, alicyclic hydrocarbons having a carbon number of 6 or more such as cyclohexane, ethylcyclohexane, isopropylcyclohexane, diisopropylcyclohexane and the like, aromatic compounds such as benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene, trimethylbenzene, tetramethylbenzene and the like, and long-chain alkanes such as octane, nonane, decane and the like are generally used. Among them, ethylcyclohexane and/or isopropylcyclohexane are preferable, which have advantages that the subsequent oil-water separation step is easy to separate, the loss in the aqueous phase is small and the recovery in the solvent recovery step is easy, and further, the sulfuric acid can be tolerated, and the same solvent can be used in the next rearrangement reaction of concentrated sulfuric acid.
When the solvent is used, the reaction is a two-phase reaction, namely cyclododecanone is in an organic phase, and raschig liquid is in an aqueous phase, so that the reaction rate is limited by the mass transfer rate between an oil phase and a water phase, the reaction time is longer, and the decomposition amount of hydroxylamine is increased.
As a preferred embodiment, a process for producing cyclododecanone oxime, comprising the steps of:
(1) mixing cyclododecanone, a solvent and hydroxylamine sulfate, then adding a molten assistant, then dropwise adding ammonia water, controlling the reaction temperature to be 85-90 ℃ and the pH value to be 4.5-6.5;
(2) after the reaction is finished, adding ammonia water to adjust the pH value to 6.5-7.5, reducing the temperature to 60-70 ℃, separating oil and water phases, filtering and recovering the auxiliary agent.
In the step (1), the auxiliary agent is added in a molten state, so that the auxiliary agent can be mixed and dissolved with the solution more quickly and can exert a better catalytic effect.
In the step (1) of the invention, the auxiliary agent can exert the catalytic and emulsifying effects to the greatest extent, and the reaction liquid forms relatively stable emulsion.
In step (2) of the present invention, separation and recovery of the auxiliary are achieved by filtration.
In the step (1), the molar ratio of cyclododecanone to hydroxylamine sulfate is 0.8: 1-2: 1.
the molar ratio of the solvent to the cyclododecanone is 2: 1-5: 1.
the mass ratio of the auxiliary agent to the cyclododecanone is 0.1: 1-0.5: 1.
the guanidino of the auxiliary agent can increase the electrophilicity of carbonyl of cyclododecanone, is favorable for attack of a nucleophilic reagent and is favorable for generation of oxime.
The hydroxylamine, because of its intermediate valence state, has both oxidative and reductive properties, rendering it unstable and undergoing decomposition to form N under both acidic and basic conditions2、NH3、NOxAnd the like, which brings great risk to the reaction system. This is a problem that those skilled in the art have been trying to overcome. In order to improve the utilization rate of hydroxylamine sulfate as much as possible, the excess of cyclododecanone is required to be kept all the time to fully utilize the hydroxylamine sulfate, and the traditional process usually adopts two-stage countercurrent operation of two reactors to guide unreacted raw materials to the other reactor, thereby increasing the complexity of the process.
Unexpectedly, the adjuvants of the invention are capable of inhibiting the reactant hydroxylamine sulfate itselfDecomposing and improving the utilization rate of the hydroxylamine sulfate. The reason for this analysis may be: trace amounts of metal ion impurities including but not limited to iron ions (Fe) have a significant catalytic effect on hydroxylamine decomposition3+、Fe2+). The addition of the assistant can form a complex with the metal ions to prevent the metal ions from directly contacting with hydroxylamine, and the assistant can be regarded as a polydentate ligand and is easy to form a plurality of chelate rings. Meanwhile, the assistant has a claw-shaped structure as a whole, namely a multi-branched ligand with a certain space effect, so that hydroxylamine and a salt solution thereof can obtain a good stabilizing effect under a high-temperature condition. In addition, both the L-arginine succinate and the L-arginine hydrochloride can form hydroxylamine salt with hydroxylamine, the hydroxylamine is stabilized, and the high electronegativity anion (succinate ion or hydrochloride ion) and the atom of a lone pair electron (N on guanidine group) in the structures of the L-arginine succinate and the L-arginine hydrochloride can further enhance the functions.
For the oximation reaction of the present invention, the major by-product is cyclododecanimine (mainly via cyclododecanone and NH)3Reaction generation), the assistant can inhibit the generation of cyclododecanimine and improve the reaction selectivity. In addition, the high electronegative anion (succinate ion or hydrochloride ion) and the group of lone pair electrons (guanidyl) in the structures of L-arginine succinate and L-arginine hydrochloride can react with NH3Form hydrogen bond with large steric hindrance to block NH3And the side reaction is carried out with cyclododecanone, so that the generation of cyclododecylamine is further inhibited.
In the method, the use of the auxiliary agent reduces the interfacial tension of two phases of reaction liquid of the oximation reaction, shortens the reaction time, and reduces the decomposition rate of the reactant hydroxylamine sulfate to 0.5 to 1.2 percent
Detailed Description
1. Gas chromatography conditions: shimadzu GC 2010; a chromatographic column: DB-5 (30X 0.32X 0.25); column temperature: temperature programming (50 ℃ for 2min, then 5 ℃/min heating rate to 80 ℃, 15 ℃/min heating rate to 300 ℃, and 10min holding); sample inlet temperature: 260 ℃; FID temperature: 300 ℃; n is a radical of2Flow rate: 1 mL/min; h2Flow rate:40 mL/min; shock insulator purging (N)2) Flow rate: 3 mL/min; carrier gas (N)2) Flow rate: 1 mL/min; split-flow sample introduction, split-flow ratio: 50; sample introduction amount: 0.2. mu.L.
2. ICP ion content detection
The instrument model is as follows: thermo Fisher iCAP ICP-MS
Example 1
A1.0L glass stirring kettle reactor is used as an oximation reaction container, the rotating speed of the stirring kettle is maintained at 1000rpm, 450g of Raschig solution (the hydroxylamine sulfate content is 12.5 wt%), 190g of 30 wt% isopropyl cyclohexane solution of cyclododecanone are added in advance, the iron ion content is detected to be 158ppm, then 15g L-arginine-L-glutamic acid is added as an auxiliary agent, ammonia water is dropwise added for 15min at the flow rate of 2.9g/min, the reaction temperature is controlled at 90 ℃, the pH value is controlled at 4.5-6.5 and timing is carried out, the reaction condition is tracked by GC, and the iron ion content in the reaction process is 0.4ppm by ICP analysis.
Calculating the reaction time until the conversion rate of the cyclododecanone reaches more than 99.8 percent and analyzing the utilization rate of reactants. Then adding ammonia water to adjust the pH value to 7.5, reducing the temperature to 65 ℃, separating oil phase and water phase, filtering and recovering the auxiliary agent. According to the analysis results, it was found that the reaction time was 1.5 hours, the decomposition rate of hydroxylamine sulfate in the reactant was 0.7%, and the cyclododecanone imine content was 5.7ppm (based on the total mass of the reaction liquid). The conversion rate of the cyclododecanone is 99.9 percent, and the selectivity of the cyclododecanone oxime is 99.993 percent.
Example 2
This example was conducted in the same manner as in example 1 except that 15g of L-arginine was added as an auxiliary, and it was found from the results of analysis that the reaction time was 4.1 hours, the decomposition rate of hydroxylamine sulfate in the reaction mixture was 1.2%, and the cyclododecanone imine content was 6.5ppm (based on the total mass of the reaction solution). The conversion rate of cyclododecanone is 99.9%, the selectivity of cyclododecanone oxime is 99.992%, and the iron ion content in the reaction process is 0.9 ppm.
Example 3
This example was conducted in the same manner as in example 1 except that 15g of L-arginine succinic acid was used as an auxiliary agent, and it was found from the results of analysis that the reaction time was 2 hours, the decomposition rate of hydroxylamine sulfate in the reaction mixture was 0.5%, and the cyclododecanone imine content was 1.6ppm (based on the total mass of the reaction solution). The conversion rate of the cyclododecanone is 99.9 percent, the selectivity of the cyclododecanone oxime is 99.998 percent, and the content of iron ions in the reaction process is 0.1 ppm.
Example 4
This example was conducted in the same manner as in example 1 except that 15g of L-arginine hydrochloride was used as an auxiliary, and it was found from the results of analysis that the reaction time was 2.3 hours, the decomposition rate of hydroxylamine sulfate in the reaction mixture was 0.5%, and the cyclododecanone imine content was 2.4ppm (based on the total mass of the reaction solution). The conversion rate of the cyclododecanone is 99.9 percent, the selectivity of the cyclododecanone oxime is 99.997 percent, and the content of iron ions in the reaction process is 0.1 ppm.
Comparative example 1
This example is the same as example 1 except that no auxiliary agent was added, and the conditions of this example were the same as example 1, and it was found from the analysis results that the reaction time of this example was 11 hours, the decomposition rate of hydroxylamine sulfate in the reactant was 8.3%, and the cyclododecanone imine content was 413ppm (based on the total mass of the reaction liquid). The conversion rate of cyclododecanone is 99.9%, the selectivity of cyclododecanone oxime is 99.500%, and the iron ion content in the reaction process is 152 ppm.
Comparative example 2
This example was conducted in the same manner as in example 1 except that 15g of glycine was added as an auxiliary, and based on the results of analysis, it was found that the reaction time in this example was 6.4 hours, the decomposition rate of hydroxylamine sulfate in the reaction mixture was 4.4%, and the cyclododecanone imine content was 316ppm (based on the total mass of the reaction solution). The conversion rate of cyclododecanone is 99.9%, the selectivity of cyclododecanone oxime is 99.900%, and the iron ion content in the reaction process is 102 ppm.
Comparative example 3
This example was conducted in the same manner as in example 1 except that 15g of piperazine was added as an auxiliary agent, and based on the results of analysis, it was found that the reaction time in this example was 10.2 hours, the decomposition rate of hydroxylamine sulfate in the reaction mixture was 2.7%, and the cyclododecanone imine content was 227ppm (based on the total mass of the reaction solution). The conversion rate of cyclododecanone is 99.9%, the selectivity of cyclododecanone oxime is 99.950%, and the iron ion content in the reaction process is 50 ppm.
Comparative example 4
This example was conducted in the same manner as in example 1 except that 15g of urotropin was added as an auxiliary, and based on the results of analysis, it was found that the reaction time in this example was 9.6 hours, the decomposition rate of hydroxylamine sulfate in the reaction mixture was 3.5%, and the cyclododecanone imine content was 283ppm (based on the total mass of the reaction solution). The conversion rate of cyclododecanone is 99.9%, the selectivity of cyclododecanone oxime is 99.900%, and the iron ion content in the reaction process is 80 ppm.
Comparative example 5
This example was conducted in the same manner as in example 1 except that 15g of citric acid was added as an auxiliary, and based on the results of analysis, it was found that the reaction time in this example was 4.2 hours, the decomposition rate of hydroxylamine sulfate in the reaction mixture was 7.4%, and the cyclododecanone imine content was 210ppm (based on the total mass of the reaction solution). The conversion rate of cyclododecanone is 99.9%, the selectivity of cyclododecanone oxime is 99.600%, and the iron ion content in the reaction process is 141 ppm.
Finally, it should be noted that the above-mentioned embodiments only illustrate the preferred embodiments of the present invention, and do not limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications can be made by modifying the technical solution of the present invention or equivalent substitutions within the scope of the present invention defined by the claims.
Claims (9)
1. A process for preparing cyclododecanone oxime comprising the steps of: in the presence of a solvent and an auxiliary agent, under the condition that the pH value is 3-6.5, cyclododecanone and hydroxylamine sulfate react to prepare cyclododecanone oxime, wherein the auxiliary agent is selected from one or more of L-arginine and derivatives thereof; the L-arginine derivative is selected from one or more of L-arginine-L-glutamic acid, L-arginine hydrochloride and L-arginine amber salt.
2. The method of claim 1, wherein the iron ion content in the reaction is 10ppm or less.
3. The method of claim 2, wherein the iron ion content in the reaction is less than or equal to 5 ppm.
4. The method of claim 3, wherein the iron ion content in the reaction is less than or equal to 1 ppm.
5. The method according to claim 1, characterized in that it comprises the following steps:
(1) mixing cyclododecanone, a solvent and hydroxylamine sulfate, then adding a molten assistant, then dropwise adding ammonia water, controlling the reaction temperature to be 85-90 ℃, and controlling the pH to be 4.5-6.5;
(2) after the reaction is finished, adding ammonia water to adjust the pH value to 6.5-7.5, reducing the temperature to 60-70 ℃, separating oil and water phases, filtering and recovering the auxiliary agent.
6. The method according to claim 5, wherein in the step (1), the molar ratio of cyclododecanone to hydroxylamine sulfate is 0.8: 1-2: 1.
7. the process of claim 5, wherein the molar ratio of solvent to cyclododecanone is from 2: 1-5: 1.
8. the method according to claim 5, wherein the mass ratio of the auxiliary agent to cyclododecanone is 0.1: 1-0.5: 1.
9. the method according to claim 5, wherein the solvent is selected from cyclohexane, ethylcyclohexane, isopropylcyclohexane, diisopropylcyclohexane, benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene, trimethylbenzene, tetramethylbenzene, octane, nonane, decane.
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