CN103864624A - Simple method for efficiently preparing secondary amine through alkali catalyzed N-alkylation - Google Patents
Simple method for efficiently preparing secondary amine through alkali catalyzed N-alkylation Download PDFInfo
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- CN103864624A CN103864624A CN201410077157.4A CN201410077157A CN103864624A CN 103864624 A CN103864624 A CN 103864624A CN 201410077157 A CN201410077157 A CN 201410077157A CN 103864624 A CN103864624 A CN 103864624A
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Abstract
The invention discloses a simple method of efficiently preparing secondary amine by alkali catalyzed N-alkylation. The method comprises the following step: by taking aryl amine or alkyl amine and aryl alcohol or alkyl alcohol compounds as raw materials, under the condition of no transition metal catalysts and solvents, carrying out N-alkylation reaction by adopting a hot bath reflux method by taking simple alkali as an accelerant to prepare a secondary amine compound. The method is free from any metal catalysts, simple and feasible in reaction manner, single in product selectivity and high in product conversion rate and selectivity in the product of secondary amine. The method is free from any other organic solvents, so that the synthetic cost and the environmental pollution by the organic solvents are lowered. The method has the advantages of greenness, economy, environment-friendliness, safe and simple operation and the like, and has a good application and popularization potential.
Description
Technical field
The present invention relates to a kind of N-alkylation, the method for secondary amine is efficiently prepared in the N-alkylation that is specifically related to a kind of simple base catalysis.
Background technology
Aminated compounds is extensively present in occurring in nature as important biologically active substance, is important organic synthesis raw material and intermediate, is widely used in the fields such as medicine, agricultural chemicals, food and dyestuffs industries.Synthesizing in pharmaceutical chemistry and Synthetic Organic Chemistry field of secondary amine occupies very consequence.The method of preparing organic amine is a lot, and wherein more traditional method is the alkylation reaction of halohydrocarbon and ammonia, primary amine or secondary amine.Although this method technique is simple, halohydrocarbon majority is poisonous, and the hydrogen halide producing in reaction process need to, with a large amount of alkali absorptions, produce the three wastes materials such as a large amount of inorganic salt thus.Another conventional method is from alcohol, forms aldehydes or ketones through dehydrogenation, and the latter and primary amine are condensed into imines, then through H
2catalytic reduction is prepared the three step process of secondary amine.Wherein aldehydes or ketones is to be oxidized by alcohol, and raw materials cost is high, and needs higher H when hydrogenation
2, there is security risk in pressure.
In recent years, the amine taking alcohol as alkylating reagent
n-alkylated reaction start to receive publicity [Adv. Synth. Catal, 2007,349:1555; Science, 2010,329:635; Chem Rev, 2010,110:1611; Chem Rev, 2011,111:1825].The by product of this class reaction is water, and catalytic process has very high Atom economy; Most of alcohol toxicity is very low simultaneously, is conducive to large-scale industrial application.But, due to the Electron Affinities of most of alcohol a little less than, be conventionally difficult to and amine generation electrophilic substitution reaction.Therefore, find a kind of method of effective activation alcohol to become the focus that people pay close attention to, borrow the application of hydrogen strategy to solve well this difficult problem.That is, alcohol is first dehydrogenation under catalyst action, generates corresponding aldehydes or ketones, and the latter and primary amine condensation, dehydration generate imines, then generate corresponding secondary amine or tertiary amine through catalytic hydrogenating reduction.1981, document [J Chem. Soc, Chem. Commun., 1981:611; Tetrahedron Lett., 1981,22:2667] with RhH (PPh
3)
4with RuCl
2(PPh
3)
3title complex is catalyzer, the amine that catalytic alcohol is alkylating reagent under homogeneous phase condition first
n-alkylated reaction generates secondary amine or tertiary amine, but reaction conditions is relatively harsh.Along with going deep into of research, constantly there is the catalyst system of reaction conditions gentleness, wherein also comprise the amine taking alcohol as alkylating reagent
nthe heterogeneous catalytic system of the synthetic high primary amine of-alkylation.In recent years, the amine that the alcohol based on borrowing hydrogen strategy, heterogeneous catalyst is alkylating reagent
n-alkylated reaction has developed into and has had the synthetic secondary amine of application prospect and the green approach of tertiary amine.
But the N-alkylated reaction of reporting in document and patent at present, generally all uses transition metal especially noble metal catalyst and reaction is normally carried out in organic solvent.Therefore, inventing a kind of N-alkylation quick, cheap, eco-friendly nontransition metal catalysis is the objective requirement of current such reaction, will have good application prospect.
Summary of the invention
The object of the invention is to overcome the shortcoming existing in prior art N-alkylation, provide a kind of easy, quick, reaction conditions is gentle, the N-alkylation of wide application range of substrates, environmental friendliness, process economy.The method of secondary amine is efficiently prepared in the N-alkylation that the invention provides a kind of simple base catalysis, and only the promotor using highly basic as reaction promotes N-alkylated reaction to prepare secondary amine.
The present invention be a kind of solvent-free, without the N-alkylation of transition-metal catalyst gentleness.It is characterized in that taking arylamines or alkylamine and aryl alcohol or alkyl alcohol compound as raw material, in without transition-metal catalyst, solvent-free situation, taking alkali-metal carbonate, oxyhydroxide or organic alkali (as potassium tert.-butoxide, sodium methylate etc.) as alkali promotor, the mode that adopts heating bath to reflux is carried out N-alkylated reaction and is prepared a series of secondary amine compounds.
In the present invention, involved reaction can adopt following reaction formula to represent:
R
1and R
2can be straight chained alkyl, cycloalkyl, phenyl, substituted-phenyl, benzyl.
Specific embodiment of the invention scheme is: arylamines or alkylamine and aryl alcohol or alkyl alcohol compound, alkali promotor are joined in round-bottomed flask successively, and the mode that adopts ceramic heater heating bath to reflux, stirs lower reacting by heating; Reaction finish after, centrifugation reaction solution and alkali, reaction solution after GC detection by quantitative through dichloromethane extraction, precipitation, reaction mixture through alkali alumina post column chromatography for separation purify, obtain N-alkylate.
Press such scheme, described arylamines can be that replace or non-substituted, the arylamines replacing comprises PA, o-Nitraniline, Ortho Toluidine, p-Chlorobenzoic acid amide, P-nethoxyaniline, 2,4-xylidine, and non-substituted arylamines comprises the one in aniline, benzylamine; Described alkylamine refers to hexahydroaniline.
Press such scheme, described aryl alcohol comprises phenylcarbinol, p-Hydroxybenzylalcohol, p-methoxybenzyl alcohol, 2 phenylethyl alcohol; Described alkyl alcohol comprises Pentyl alcohol, propyl carbinol, 1-octanol, hexalin.
Press such scheme, described alkali promotor comprises alkali-metal carbonate (sodium carbonate, salt of wormwood), oxyhydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide), organic alkali (potassium tert.-butoxide, sodium methylate)
Press such scheme, the consumption of described alkali is 5～30 % of reaction substrate arylamines or alkylamine.
Press such scheme, the mol ratio of described reaction substrate arylamines and alcohol is 1:10～1:2.
Press such scheme, the mode that described reaction heating can adopt common heating bath to reflux, temperature of reaction is that 120～230 ° of C, reaction times are 2～8 h.
That carbon-nitrogen coupling reaction method provided by the invention has is simple to operate, the reaction times is short, product is simply easy to separate and the shortcoming such as environmental friendliness.Especially in reaction, do not use any solvent, do not use any transition-metal catalyst, only use alkali promotor to promote the carrying out of N-alkylated reaction; Adopt the mode of common heating bath heating, with the reacting phase ratio of the same type of reporting in document, effectively improve the environment friendly of reaction, more conform to the requirement of scientific development, in natural product, medicine and polymer, the high-throughput of organic amide monomer may have broad application prospects aspect preparing.
Embodiment
By several specific embodiments, technical scheme of the present invention is further described below.Following examples do not form limitation of the invention.
Embodiment 1
By 40 mg sodium hydroxide, 4 mmol aniline, 40 mmol phenylcarbinols join in the round-bottomed flask of 25 ml, under ceramic heaters heat temperature to 180 ° C condition, react 6 h.After reaction stops, reaction solution is through centrifugation, and filtrate is carried out gas-chromatography (GC) quantitative analysis on the one hand, is extracted with ethyl acetate on the other hand, filters after washing, saturated common salt washing, anhydrous magnesium sulfate drying, filtrate decompression distillation, purifies through alkali alumina post column chromatography for separation.It is 100 % that GC analyzes aniline transformation efficiency, and the selectivity of product secondary amine (Phenhenzamine) is 98.2 %.
Embodiment 2
By 60 mg lithium hydroxides, 4 mmol benzylamines, 40 mmol p-Hydroxybenzylalcohols join in the round-bottomed flask of 25 ml, under ceramic heaters heat temperature to 200 ° C condition, react 6 h.After reaction stops, reaction solution is through centrifugation, and filtrate is carried out gas-chromatography (GC) quantitative analysis on the one hand, is extracted with ethyl acetate on the other hand, filters after washing, saturated common salt washing, anhydrous magnesium sulfate drying, filtrate decompression distillation, purifies through alkali alumina post column chromatography for separation.It is 86.5 % that GC analyzes aniline transformation efficiency, and the selectivity of product secondary amine is 96.3 %.
Embodiment 3
By 20 mg potassium hydroxide, 4 mmol hexahydroaniline, 20 mmol p-methoxybenzyl alcohol join in the round-bottomed flask of 25 ml, under ceramic heaters heat temperature to 200 ° C condition, react 8 h.After reaction stops, reaction solution is through centrifugation, and filtrate is carried out gas-chromatography (GC) quantitative analysis on the one hand, is extracted with ethyl acetate on the other hand, filters after washing, saturated common salt washing, anhydrous magnesium sulfate drying, filtrate decompression distillation, purifies through alkali alumina post column chromatography for separation.It is 90.1 % that GC analyzes aniline transformation efficiency, and the selectivity of product secondary amine is 86.5 %.
Embodiment 4
By 40 mg sodium carbonate, 4 mmol2-aminopyridine, 40 mmol 2 phenylethyl alcohols join in the round-bottomed flask of 25 ml, under ceramic heaters heat temperature to 220 ° C condition, react 4 h.After reaction stops, reaction solution is through centrifugation, and filtrate is carried out gas-chromatography (GC) quantitative analysis on the one hand, is extracted with ethyl acetate on the other hand, filters after washing, saturated common salt washing, anhydrous magnesium sulfate drying, filtrate decompression distillation, purifies through alkali alumina post column chromatography for separation.It is 92.4 % that GC analyzes aniline transformation efficiency, and the selectivity of product secondary amine is 91.6 %.
Embodiment 5
By 40 mg salt of wormwood, 4 mmol o-Nitranilines, 40 mmol Pentyl alcohols join in the round-bottomed flask of 25 ml, under ceramic heaters heat temperature to 180 ° C condition, react 6 h.After reaction stops, reaction solution is through centrifugation, and filtrate is carried out gas-chromatography (GC) quantitative analysis on the one hand, is extracted with ethyl acetate on the other hand, filters after washing, saturated common salt washing, anhydrous magnesium sulfate drying, filtrate decompression distillation, purifies through alkali alumina post column chromatography for separation.It is 83.8 % that GC analyzes aniline transformation efficiency, and the selectivity of product secondary amine is 88.6 %.
Embodiment 6
By 60 mg potassium tert.-butoxides, 8 mmol Ortho Toluidines, 16 mmol propyl carbinols join in the round-bottomed flask of 25 ml, under ceramic heaters heat temperature to 160 ° C condition, react 2 h.After reaction stops, reaction solution is through centrifugation, and filtrate is carried out gas-chromatography (GC) quantitative analysis on the one hand, is extracted with ethyl acetate on the other hand, filters after washing, saturated common salt washing, anhydrous magnesium sulfate drying, filtrate decompression distillation, purifies through alkali alumina post column chromatography for separation.It is 89.4 % that GC analyzes aniline transformation efficiency, and the selectivity of product secondary amine is 86.5 %.
Embodiment 7
By 40 mg sodium methylates, 4 mmol p-Chlorobenzoic acid amide, 40 mmol1-octanols join in the round-bottomed flask of 25 ml, under ceramic heaters heat temperature to 140 ° C condition, react 6 h.After reaction stops, reaction solution is through centrifugation, and filtrate is carried out gas-chromatography (GC) quantitative analysis on the one hand, is extracted with ethyl acetate on the other hand, filters after washing, saturated common salt washing, anhydrous magnesium sulfate drying, filtrate decompression distillation, purifies through alkali alumina post column chromatography for separation.It is 87.9 % that GC analyzes aniline transformation efficiency, and the selectivity of product secondary amine is 90.1 %.
Embodiment 8
By 40 mg sodium hydroxide, 4 mmol P-nethoxyaniline, 40 mmol hexalin join in the round-bottomed flask of 25 ml, under ceramic heaters heat temperature to 160 ° C condition, react 8 h.After reaction stops, reaction solution is through centrifugation, and filtrate is carried out gas-chromatography (GC) quantitative analysis on the one hand, is extracted with ethyl acetate on the other hand, filters after washing, saturated common salt washing, anhydrous magnesium sulfate drying, filtrate decompression distillation, purifies through alkali alumina post column chromatography for separation.It is 91.2 % that GC analyzes aniline transformation efficiency, and the selectivity of product secondary amine is 100 %.
Embodiment 9
By 40 mg sodium hydroxide, 4 mmol 2,4-xylidine, 40 mmol phenylcarbinols join in the round-bottomed flask of 25 ml, under ceramic heaters heat temperature to 180 ° C condition, react 6 h.After reaction stops, reaction solution is through centrifugation, and filtrate is carried out gas-chromatography (GC) quantitative analysis on the one hand, is extracted with ethyl acetate on the other hand, filters after washing, saturated common salt washing, anhydrous magnesium sulfate drying, filtrate decompression distillation, purifies through alkali alumina post column chromatography for separation.It is 95.8 % that GC analyzes aniline transformation efficiency, and the selectivity of product secondary amine is 94.7 %.
Claims (7)
1. the method for secondary amine is efficiently prepared in the N-alkylation of a simple base catalysis, it is characterized in that: taking arylamines or alkylamine and aryl alcohol or alkyl alcohol compound as raw material, in without transition-metal catalyst, solvent-free situation, taking alkali-metal carbonate, oxyhydroxide or organic alkali (as potassium tert.-butoxide, sodium methylate etc.) as alkali promotor, the mode that adopts heating bath to reflux is carried out N-alkylated reaction and is prepared a series of secondary amine compounds.
2. the method for secondary amine is efficiently prepared in the N-alkylation of a kind of simple base catalysis according to claim 1, it is characterized in that: described arylamines can be that replace or non-substituted, the arylamines replacing comprises PA, o-Nitraniline, Ortho Toluidine, p-Chlorobenzoic acid amide, P-nethoxyaniline, 2,4-xylidine, non-substituted arylamines comprises the one in aniline, benzylamine; Described alkylamine refers to hexahydroaniline.
3. the method for secondary amine is efficiently prepared in the N-alkylation of a kind of simple base catalysis according to claim 1, it is characterized in that: described aryl alcohol comprises phenylcarbinol, p-Hydroxybenzylalcohol, p-methoxybenzyl alcohol, 2 phenylethyl alcohol; Described alkyl alcohol comprises Pentyl alcohol, propyl carbinol, 1-octanol, hexalin.
4. the method for secondary amine is efficiently prepared in the N-alkylation of a kind of simple base catalysis according to claim 1, it is characterized in that: described alkali promotor comprises alkali-metal carbonate (sodium carbonate, salt of wormwood), oxyhydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide), organic alkali (potassium tert.-butoxide, sodium methylate).
5. the method for secondary amine is efficiently prepared in the N-alkylation of a kind of simple base catalysis according to claim 1, it is characterized in that: the consumption of described alkali is 5～30 % of reaction substrate arylamines or alkylamine.
6. the method for secondary amine is efficiently prepared in the N-alkylation of a kind of simple base catalysis according to claim 1, it is characterized in that: the mol ratio of described reaction substrate arylamines and alcohol is 1:10～1:2.
7. the method for secondary amine is efficiently prepared in the N-alkylation of a kind of simple base catalysis according to claim 1, it is characterized in that: the mode that described reaction heating can adopt common heating bath to reflux, temperature of reaction is that 120～230 ° of C, reaction times are 2～8 h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529889A (en) * | 2014-12-02 | 2015-04-22 | 温州大学 | Dehydration C-alkylation method for heterocyclic methyl compound |
| CN107433198A (en) * | 2017-08-15 | 2017-12-05 | 重庆大学 | NMPA gentle Fast back-projection algorithm and Pd@RGO catalyst |
| CN108774137A (en) * | 2018-05-14 | 2018-11-09 | 荆楚理工学院 | A kind of method that double-core manganese complex catalyzes and synthesizes secondary amine compound |
| CN112574097A (en) * | 2020-12-21 | 2021-03-30 | 杭州仟源保灵药业有限公司 | Preparation method of Ebastine and fumarate thereof |
| CN113061091A (en) * | 2021-03-16 | 2021-07-02 | 南京林业大学 | Preparation method of N-alkylated derivative of primary amine compound |
| CN114436851A (en) * | 2022-01-17 | 2022-05-06 | 常州大学 | Preparation method of N, N-dimethylbenzylamine and derivative thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529889A (en) * | 2014-12-02 | 2015-04-22 | 温州大学 | Dehydration C-alkylation method for heterocyclic methyl compound |
| CN104529889B (en) * | 2014-12-02 | 2018-09-04 | 温州大学 | A kind of dehydration C- alkylations of heterocyclic methyl compound |
| CN107433198A (en) * | 2017-08-15 | 2017-12-05 | 重庆大学 | NMPA gentle Fast back-projection algorithm and Pd@RGO catalyst |
| CN107433198B (en) * | 2017-08-15 | 2020-03-03 | 重庆大学 | Mild rapid synthesis of NMPA and Pd @ RGO catalyst |
| CN108774137A (en) * | 2018-05-14 | 2018-11-09 | 荆楚理工学院 | A kind of method that double-core manganese complex catalyzes and synthesizes secondary amine compound |
| CN112574097A (en) * | 2020-12-21 | 2021-03-30 | 杭州仟源保灵药业有限公司 | Preparation method of Ebastine and fumarate thereof |
| CN113061091A (en) * | 2021-03-16 | 2021-07-02 | 南京林业大学 | Preparation method of N-alkylated derivative of primary amine compound |
| CN113061091B (en) * | 2021-03-16 | 2023-12-05 | 南京林业大学 | Preparation method of N-alkylated derivative of primary amine compound |
| CN114436851A (en) * | 2022-01-17 | 2022-05-06 | 常州大学 | Preparation method of N, N-dimethylbenzylamine and derivative thereof |
| CN114436851B (en) * | 2022-01-17 | 2023-08-22 | 常州大学 | Preparation method of N, N-dimethylbenzylamine and derivatives thereof |
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Application publication date: 20140618 |