CN111100019B - N, N-di-N-propyl-2-propoxyethylamine and preparation method and application thereof - Google Patents
N, N-di-N-propyl-2-propoxyethylamine and preparation method and application thereof Download PDFInfo
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- CN111100019B CN111100019B CN202010016673.1A CN202010016673A CN111100019B CN 111100019 B CN111100019 B CN 111100019B CN 202010016673 A CN202010016673 A CN 202010016673A CN 111100019 B CN111100019 B CN 111100019B
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- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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Abstract
N, N-di-N-propyl-2-propoxyethylamine with molecular formula of C 11 H 25 NO, the preparation method comprises the following steps: heating chloroethyl propyl ether serving as a raw material to 100-180 ℃, adding another raw material of di-N-propylamine, keeping the temperature, reacting for 8-20 h, cooling to room temperature, adding an alkali aqueous solution, adjusting the pH to 8-10, collecting an organic layer after layering, and carrying out reduced pressure distillation to obtain a product N, N-di-N-propyl-2-propoxyethylamine. The invention applies N, N-di-N-propyl-2-propoxyethylamine as an auxiliary agent to the synthesis of a pretilachlor key intermediate, and solves the problems of low fluidity of a reaction system and low selectivity and yield of a target product when the intermediate 2, 6-diethyl-N- (2-propoxyethyl) aniline is synthesized.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to N, N-di-N-propyl-2-propoxyethylamine and a preparation method and application thereof.
Background
The prior patent EP0518013 discloses compounds of the general formula and proposes a process for the preparation of some of the compounds.
In the formula: r 1 ＝C 1 -C 10 An alkyl group; r 2 ＝C 1 -C 10 Alkyl radical, R 2 Can be reacted with R 1 The same or different.
This publication describes the preparation of compounds of the above general formula, mainly compounds of formulae (II) to (VII), starting from beta-dialkylaminoethanol and an alkyl halide:
in the prior art, the compound shown as the formula (I) is not reported to a preparation method and an application thereof.
In the N-alkylation monosubstitution reaction of aniline compounds and chlorohydrin compounds, an auxiliary agent is usually required to be added to enable a reaction system to have better fluidity, so that a target product has better selectivity and yield. However, in some N-alkylation mono-substitution reactions, such as the synthesis of 2, 6-diethyl-N- (2-propoxyethyl) aniline, which is a key intermediate of pretilachlor, common auxiliaries are added for reaction, the problem of low fluidity of a reaction system still exists, and the selectivity and yield of a target product are low.
A common production method for synthesizing a key intermediate 2, 6-diethyl-N- (2-propoxyethyl) aniline of pretilachlor is to take 2, 6-diethyl aniline and chloroethyl propyl ether as raw materials and add an acid-binding agent to react under the condition of normal pressure or pressurization. Currently, naOH is generally used as an acid-binding agent in the production of the intermediate, but the problems of low selectivity and yield of a target product exist. Chinese patent CN104478741 discloses the synthesis of 2, 6-diethyl-N- (2-propoxyethyl) aniline as an intermediate by using metal oxides such as magnesium oxide, aluminum oxide, calcium oxide and the like as an acid-binding agent (preferably magnesium oxide), and the result shows that the content of 2, 6-diethyl-N- (2-propoxyethyl) aniline in the feed liquid is only 63% at most. Shichang et al (Liaoning chemical, 2016, 45 (6): 190-195.) reported that the yield of 2, 6-diethyl-N- (2-propoxyethyl) aniline obtained by esterification of ethylene glycol mono-N-propyl ether with p-methylbenzenesulfonyl chloride and condensation reaction with 2, 6-diethylaniline was only 87%.
Therefore, when the 2, 6-diethyl-N- (2-propoxyethyl) aniline, a key intermediate of pretilachlor, is synthesized, the problems of low reaction system fluidity and low selectivity and yield of target products still exist, and a novel auxiliary agent needs to be developed to solve the technical problem.
Disclosure of Invention
In order to overcome the defects of low fluidity of a reaction system and low selectivity and yield of a target product in the prior art, the invention provides N, N-di-N-propyl-2-propoxyethylamine and a preparation method and application thereof, so that the fluidity of the reaction system is improved, and the selectivity and yield of the target product are improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
n, N-di-N-propyl-2-propoxyethylamine has a structural formula shown as a formula (I):
a preparation method of N, N-di-N-propyl-2-propoxyethylamine comprises the steps of heating chloroethyl propyl ether to 100-180 ℃, adding di-N-propylamine, and reacting for 8-20 hours under the condition of heat preservation, wherein the molar ratio of the di-N-propylamine to the chloroethyl propyl ether is 1-4; after the reaction is finished and the temperature is reduced to room temperature, adding an alkali aqueous solution to adjust the pH value to 8-10, collecting an organic layer after layering, and carrying out reduced pressure distillation to obtain the N, N-di-N-propyl-2-propoxyethylamine.
The application of N, N-di-N-propyl-2-propoxyethylamine is carried out by the following reactions:
when the 2, 6-diethyl-N- (2-propoxyethyl) aniline serving as the pretilachlor key intermediate is prepared, the 2, 6-diethyl aniline serving as the raw material and chloroethyl propyl ether are subjected to N-alkylation mono-substitution reaction, and N, N-di-N-propyl-2-propoxyethylamine serving as an auxiliary agent is added, so that the fluidity of a reaction system can be improved, the di-substitution side reaction is inhibited, and the selectivity and the yield of a target product are improved.
Further, in the N-alkylation mono-substitution reaction of 2, 6-diethylaniline and chloroethyl propyl ether, the molar ratio of the raw material 2, 6-diethylaniline to the chloroethyl propyl ether is 1-3, the added auxiliary agent N, N-di-N-propyl-2-propoxyethylamine is 10-100% of the molar weight of the chloroethyl propyl ether, the reaction temperature is controlled at 120-200 ℃, and the reaction time is 5-15 h; after the reaction is finished, adding an alkali aqueous solution to adjust the pH value to 8-10, collecting an organic layer after layering, and rectifying and purifying to obtain the product 2, 6-diethyl-N- (2-propoxyethyl) aniline.
Preferably, the added auxiliary agent N, N-di-N-propyl-2-propoxyethylamine accounts for 50 to 70 percent of the molar weight of the chloroethyl propyl ether.
In the present invention, the term "complete reaction" in the above technical scheme means that the content of chloroethyl propyl ether detected by GC method is less than 1%.
The invention has the beneficial effects that: the invention applies the compound as an auxiliary agent to the synthesis of a pretilachlor key intermediate, and solves the problems of low reaction system fluidity and low selectivity and yield of a target product when the intermediate 2, 6-diethyl-N- (2-propoxyethyl) aniline is synthesized.
Detailed Description
The present invention will be described in more detail with reference to the following embodiments.
Example 1:
n, N-di-N-propyl-2-propoxyethylamine with molecular formula of C 11 H 25 NO, structural formula (I):
the preparation method of the N, N-di-N-propyl-2-propoxyethylamine comprises the following steps:
98.08g (0.8 mol) of chloroethyl propyl ether is added into a 500mL four-neck flask, stirred, and after the temperature is raised to 120 ℃, 161.91g (1.6 mol) of di-n-propylamine is started to be dropwise added, and the reaction is kept for 10 hours after the dropwise addition. Cooling, adding 10% NaOH aqueous solution to adjust the pH value of the reaction solution to 8-10, fully stirring, standing for layering, collecting an organic layer, carrying out reduced pressure distillation, recovering the raw materials of di-N-propylamine and chloroethyl propyl ether, collecting fractions at 126-132 ℃ (-0.01 MPa), and obtaining a product, namely 121.78g of N, N-di-N-propyl-2-propoxyethylamine (colorless liquid), wherein the yield is 81.3%, and the content is 99% by GC detection.
Example 2
The preparation method of the N, N-di-N-propyl-2-propoxyethylamine comprises the following steps:
122.59g (1.0 mol) of chloroethyl propyl ether is added into a 500mL four-neck flask, stirred, and after the temperature is raised to 180 ℃, 101.19g (1.0 mol) of di-n-propylamine is started to be dropwise added, and the reaction is kept for 8 hours after the dropwise addition. Cooling, adding NaOH aqueous solution with the mass fraction of 10% to adjust the pH value of the reaction liquid to 8-10, fully stirring, standing for layering, collecting an organic layer for reduced pressure distillation, recovering raw materials of di-N-propylamine and chloroethyl propyl ether, and collecting fractions at the temperature of 126-132 ℃ (-0.01 MPa) to obtain 96.78g of product N, N-di-N-propyl-2-propoxy ethylamine with the yield of 51.7%, wherein the content is 99% through GC detection.
Example 3
The preparation method of the N, N-di-N-propyl-2-propoxyethylamine comprises the following steps:
122.59g (1.0 mol) of chloroethyl propyl ether is added into a 1000mL four-neck flask, stirred, and after the temperature is raised to 100 ℃, 405.32g (4.0 mol) of di-n-propylamine is started to be dropwise added, and the reaction is kept for 20 hours after the dropwise addition. Cooling, adding 10% NaOH aqueous solution to adjust the pH value of the reaction solution to 8-10, fully stirring, standing for layering, collecting an organic layer, carrying out reduced pressure distillation, recovering the raw materials of di-N-propylamine and chloroethyl propyl ether, collecting fractions at 126-132 ℃ (-0.01 MPa), and obtaining a product, namely 128.32g of N, N-di-N-propyl-2-propoxyethylamine, with the yield of 68.5%, and the content of 99% by GC detection.
Example 4
The invention relates to an application of N, N-di-N-propyl-2-propoxyethylamine, and a novel auxiliary agent prepared by the invention is reacted (the same below).
18.63g (125 mmol) of 2, 6-diethylaniline is added into a 100mL four-neck flask, stirred, after the temperature rises to 200 ℃, 6.13g (50 mmol) of chloroethyl propyl ether is dropwise added, 0.95g (5 mmol) of N, N-di-N-propyl-2-propoxyethylamine is dropwise added, and after the dropwise addition is finished, the reaction is kept for 10 hours. Cooling, adding 10% NaOH aqueous solution to adjust the pH of the reaction solution to 8-10, fully stirring, standing for layering, collecting the organic layer, and rectifying and purifying. The selectivity of the target product of the reaction was 92.9%.
Example 5:
22.35g (150 mmol) of 2, 6-diethylaniline is added into a 100mL four-neck flask, stirred, 18.39g (150 mmol) of chloroethyl propyl ether is dropwise added after the temperature rises to 180 ℃, 8.43g (45 mmol) of N, N-di-N-propyl-2-propoxyethylamine is dropwise added, and after the dropwise addition is finished, the reaction is kept for 5 hours. Cooling, adding 10% NaOH aqueous solution to adjust the pH of the reaction solution to 8-10, fully stirring, standing for layering, collecting the organic layer, and rectifying and purifying. The selectivity of the target product of the reaction was 85.7%.
Example 6:
22.35g (150 mmol) of 2, 6-diethylaniline is added into a 100mL four-neck flask, stirred, 18.39g (150 mmol) of chloroethyl propyl ether is dropwise added after the temperature rises to 160 ℃, 14.05g (75 mmol) of N, N-di-N-propyl-2-propoxyethylamine is dropwise added, and after the dropwise addition is finished, the reaction is kept for 5 hours. Cooling, adding 10% NaOH aqueous solution to adjust the pH of the reaction solution to 8-10, fully stirring, standing for layering, collecting the organic layer, and rectifying and purifying. The selectivity of the target product of the reaction was 95.6%.
Example 7:
18.63g (125 mmol) of 2, 6-diethylaniline is added into a 100mL four-neck flask, stirred, after the temperature rises to 140 ℃, 6.13g (50 mmol) of chloroethyl propyl ether is dropwise added, 6.56g (35 mmol) of N, N-di-N-propyl-2-propoxyethylamine is dropwise added, and after the dropwise addition is finished, the temperature is kept for reaction for 15 hours. Cooling, adding 10% NaOH aqueous solution to adjust the pH of the reaction solution to 8-10, fully stirring, standing for layering, collecting the organic layer, and rectifying and purifying. The selectivity of the target product of the reaction was 97.0%.
Example 8:
18.63g (125 mmol) of 2, 6-diethylaniline is added into a 100mL four-neck flask, stirred, after the temperature rises to 120 ℃, 6.13g (50 mmol) of chloroethyl propyl ether is dropwise added, 8.43g (45 mmol) of N, N-di-N-propyl-2-propoxyethylamine is dropwise added, and after the dropwise addition is finished, the reaction is kept for 15 hours. Cooling, adding 10% NaOH aqueous solution to adjust the pH of the reaction solution to 8-10, fully stirring, standing for layering, collecting the organic layer, and rectifying and purifying. The selectivity of the target product of the reaction is 97.7 percent, and the chloroethyl propyl ether serving as the raw material is not completely reacted.
Example 9:
22.35g (150 mmol) of 2, 6-diethylaniline is added into a 100mL four-neck flask, stirred, after the temperature rises to 160 ℃, 6.13g (50 mmol) of chloroethyl propyl ether is dropwise added, 9.37g (50 mmol) of N, N-di-N-propyl-2-propoxyethylamine is dropwise added, and after the dropwise addition is finished, the reaction is kept for 10 hours. Cooling, adding 10% NaOH aqueous solution to adjust the pH of the reaction solution to 8-10, fully stirring, standing for layering, collecting the organic layer, and rectifying and purifying. The selectivity of the target product of the reaction was 94.7%.
Example 10: the novel auxiliary agent prepared by the invention is used for carrying out amplification reaction.
1492g of raw material 2, 6-diethylaniline is added into a 5L reaction kettle, stirred and heated until the reaction temperature rises to 160 ℃, 490g of chloroethyl propyl ether and 450g of N, N-di-n-propyl-2-propoxyethylamine are added in batches, and the reaction is carried out for 10 hours under the condition of heat preservation. Cooling, adding NaOH aqueous solution to adjust the pH value of the reaction solution to 8-10, fully stirring, standing for layering, collecting an organic layer for rectification and purification, recovering the auxiliary agent N, N-di-N-propyl-2-propoxyethylamine and the raw material 2, 6-diethylaniline, collecting distillate at 172-175 ℃ (-0.01 MPa), and obtaining 893g of the product, namely 2, 6-diethyl-N- (2-propoxyethyl) aniline, wherein the yield is 94.9%, and the content is 99% by GC detection. The reaction selectivity of N, N-di-N-propyl-2-propoxyethylamine as an auxiliary agent is 95.9%, and the fluidity of a reaction system is good.
Example 11: and (3) taking triethylamine as an acid-binding agent to perform amplification reaction as a reference.
1492g of raw material 2, 6-diethylaniline is added into a 5L reaction kettle, stirred and heated until the reaction temperature rises to 160 ℃, 490g of chloroethyl propyl ether and 243g of triethylamine are added in batches, and the mixture is reacted for 10 hours under the condition of heat preservation. Cooling, adding NaOH aqueous solution to adjust the pH value of the reaction solution to 8-10, fully stirring, standing for layering, collecting an organic layer for rectification and purification, recovering acid-binding agent triethylamine and raw material 2, 6-diethylaniline, collecting distillate at 172-175 ℃ (-0.01 MPa), obtaining a product of 827g of 2, 6-diethyl-N- (2-propoxyethyl) aniline with yield of 87.8%, and detecting by GC, wherein the content is 98%. The reaction selectivity of triethylamine as an acid-binding agent is 92.7 percent, and the fluidity of a reaction system is slightly poor.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention, and all variations that may be derived or suggested from the present disclosure are intended to be included within the scope of the present invention.
Claims (3)
1. The application of N, N-di-N-propyl-2-propoxyethylamine is characterized in that the structural formula of the N, N-di-N-propyl-2-propoxyethylamine is shown as the formula (I):
heating chloroethyl propyl ether to 100-180 ℃, adding di-n-propylamine, and reacting for 8-20 h under the condition of heat preservation, wherein the molar ratio of the di-n-propylamine to the chloroethyl propyl ether is 1-4; after the reaction is finished and the temperature is reduced to room temperature, adding an alkali aqueous solution to adjust the pH value to 8-10, collecting an organic layer after layering, and carrying out reduced pressure distillation to obtain N, N-di-N-propyl-2-propoxyethylamine;
participate in the following reactions:
when the 2, 6-diethyl-N- (2-propoxyethyl) aniline serving as the key intermediate of pretilachlor is prepared, the 2, 6-diethyl aniline serving as a raw material and chloroethyl propyl ether are subjected to N-alkylation mono-substitution reaction, and N, N-di-N-propyl-2-propoxyethylamine serving as an auxiliary agent is added, so that the fluidity of a reaction system can be improved, the di-substitution side reaction is inhibited, and the selectivity and the yield of a target product are improved.
2. The application as claimed in claim 1, wherein in the N-alkylation mono-substitution reaction of 2, 6-diethylaniline and chloroethyl propyl ether, the molar ratio of the raw material 2, 6-diethylaniline to the chloroethyl propyl ether is 1-3, the added auxiliary agent N, N-di-N-propyl-2-propoxyethylamine is 10-100% of the molar weight of the chloroethyl propyl ether, the reaction temperature is controlled at 120-200 ℃, and the reaction time is 5-15 h; after the reaction is finished, adding an alkali aqueous solution to adjust the pH value to 8-10, collecting an organic layer after layering, and rectifying and purifying to obtain the product 2, 6-diethyl-N- (2-propoxyethyl) aniline.
3. Use according to claim 2, characterized in that: the amount of the added auxiliary agent N, N-di-N-propyl-2-propoxyethylamine is 50 to 70 percent of the molar weight of the chloroethyl propyl ether.
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|---|---|---|---|---|
| US4183868A (en) * | 1978-04-26 | 1980-01-15 | Ciba-Geigy Corporation | Process for the preparation of 2,6-dialkyl-N-alkylanilines |
| US4324580A (en) * | 1972-06-06 | 1982-04-13 | Ciba-Geigy Corporation | Herbicidal and plant growth inhibiting agent |
| EP0190101A2 (en) * | 1985-01-29 | 1986-08-06 | Ciba-Geigy Ag | Process for the preparation of N-alkyl-anilines |
| EP0518013A2 (en) * | 1991-06-14 | 1992-12-16 | Hüls Aktiengesellschaft | Process for the preparation of 1-alkoxy-2-dialkylaminoethanes |
| CN104478741A (en) * | 2014-11-21 | 2015-04-01 | 山东侨昌化学有限公司 | Method for producing 2, 6-diethyl-N-(2-propoxyethyl)phenylamine serving as pretilachlor intermediate |
| CN105601529A (en) * | 2015-12-19 | 2016-05-25 | 浙江大学 | Pretilachlor synthesis method |
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- 2020-01-08 CN CN202010016673.1A patent/CN111100019B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324580A (en) * | 1972-06-06 | 1982-04-13 | Ciba-Geigy Corporation | Herbicidal and plant growth inhibiting agent |
| US4183868A (en) * | 1978-04-26 | 1980-01-15 | Ciba-Geigy Corporation | Process for the preparation of 2,6-dialkyl-N-alkylanilines |
| EP0190101A2 (en) * | 1985-01-29 | 1986-08-06 | Ciba-Geigy Ag | Process for the preparation of N-alkyl-anilines |
| EP0518013A2 (en) * | 1991-06-14 | 1992-12-16 | Hüls Aktiengesellschaft | Process for the preparation of 1-alkoxy-2-dialkylaminoethanes |
| CN104478741A (en) * | 2014-11-21 | 2015-04-01 | 山东侨昌化学有限公司 | Method for producing 2, 6-diethyl-N-(2-propoxyethyl)phenylamine serving as pretilachlor intermediate |
| CN105601529A (en) * | 2015-12-19 | 2016-05-25 | 浙江大学 | Pretilachlor synthesis method |
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