CN103242189B - Method for catalytic preparation of aromatic amide compound by solid alkali - Google Patents
Method for catalytic preparation of aromatic amide compound by solid alkali Download PDFInfo
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- CN103242189B CN103242189B CN201310184034.6A CN201310184034A CN103242189B CN 103242189 B CN103242189 B CN 103242189B CN 201310184034 A CN201310184034 A CN 201310184034A CN 103242189 B CN103242189 B CN 103242189B
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Abstract
The invention relates to a method for preparing an aromatic amide compound. The method comprises the following steps of: enabling the aromatic amide compound and amine to react under catalysis of a solid alkali catalyst; and adding a promoter to promote reaction, so as to obtain the aromatic amide compound. The method has the outstanding advantages of high productivity, good selectivity and the like. In addition, the method is mild in reaction condition and short in time, and has good industrialized application prospect.
Description
Technical field
The present invention relates to the preparation method of organic chemistry filed amides, relate more specifically to a kind of aromatic aldehyde and amine and under solid base catalyst effect, react the novel method of preparing aromatic amides.
Background technology
Aromatic amides compounds is widely used in biological medicine, organic synthesis and spices, the fields such as dyestuff, the formation of amido linkage is also one of of paramount importance reaction type of organic chemistry filed, and mostly there is reagent costliness in the synthetic method of existing acid amides, the low inferior shortcoming of productive rate, Green Chemistry research institution of American Chemical Society in 2007 proposes that " acid amides is avoided weak (poor) Atom economy reagent in forming " is vitochemical overriding challenge (Top Challenge) thus, thereby make the effective preparation method of novelty who studies amides become the focus that numerous researchers are paid close attention to.
Particularly, for this compounds, there is following synthetic method.
Traditional acid amides synthetic method depends on coupling or condensation reagent is converted into active carboxylicesters by inactive carboxylic acid and then reacts and prepare acid amides with amine; Or adopt acyl chlorides to react to prepare acid amides with amine.These react owing to adopting coupling or condensation reagent to cause product purification difficulty, or adopt acyl chlorides to exist raw material to be difficult to the shortcoming of preserving, response stimulus is strong as raw material, make these methods leave hidden danger in amplificationization is produced.
(" the Direct synthesis of amides from alcohols and amines with liberation of H such as Chidambaram Gunanathan
2",
science, 2007,317,790-792) and a kind of synthetic method of acid amides disclosed.Described method, take alcohol as raw material, is reacted and is prepared amide compound with amine through oxidation under the effect of ruthenium catalyst, has wherein used expensive ruthenium chelating catalyst, does not possess the prospect of suitability for industrialized production, and has been subject to limitation for the improvement of catalyzer thereafter.
Chan Wing-Kei etc. (" amide synthesis and N-terminal a-amino group ligation of peptides in aqueous medium ",
j. Am. Chem. Soc., 2006,128,14796-14797) and a kind of preparation method of acid amides disclosed.Described method is reacted with amine and is prepared acid amides for fragrant and fatty alkynes class under mangano-porphyrin catalyst action under alkalescence-oxidizing condition, has wherein adopted equally expensive catalyzer, and severe reaction conditions and product yield differ greatly, and there is no the prospect of industrialization.
CN102424645A discloses a kind of preparation method of aromatic amides.Described method prepares corresponding aromatic amides with aromatic aldehyde and amine under the effect of mineral alkali (as saleratus) or organic bases (as potassium tert.-butoxide), but the yield of product lower (<50%), poor selectivity.
As can be seen here, how finding one cost is low, yield is high, be suitable for the preparation method of the aromatic amides of suitability for industrialized production, is the emphasis problem of research both at home and abroad at present.
Summary of the invention
For many defects of above-mentioned existence, the inventor, through a large amount of further investigations, is paying after a large amount of creative works, has researched and developed a kind of preparation method of new aromatic amides compounds.Surprisingly, the present invention owing to adopting novel solid base catalyst, carry out suitable and rational processing parameter and select to have obtained beyond thought technique effect.The method of the invention has the plurality of advantages such as reaction yield is high, cost is low, selectivity is good, has good industrial prospect.
Particularly, the invention provides the method for a kind of solid base catalyst catalysis preparation formula (I) compound (being aromatic amides compounds),
Described method comprises: under solid base catalyst exists, formula (II) compound and formula (III) compound react in organic solvent,
Wherein, Ar is for replacing or unsubstituted aryl; Described aryl is phenyl, naphthyl, pyridyl, pyrryl, thienyl or furyl; Described substituting group be halogen, C1-C6 alkyl, C1-C6 alkoxyl group, hydroxyl, nitro or-NR
3r
4; The preferred halogen of described substituting group, methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, hydroxyl, nitro, methoxyl group, oxyethyl group, dimethylamino or diethylin;
R
3, R
4be selected from independently of one another H or C1-C6 alkyl; More preferably H, methyl, ethyl, n-propyl, sec.-propyl or the tertiary butyl;
R
1or R
2identical or different between itself, and be selected from independently of one another H, C1-C6 alkyl, the aryl identical with above-mentioned Ar; Or R
1and R
2form 5-6 unit cyclammonium with N atom, for example, can form Pyrrolidine, hexahydropyridine, imidazolidine, oxazolidine or piperazine.
In described method of the present invention, halogen atom refers to fluorine, chlorine, bromine atoms.
In described method of the present invention, C
1-C
6alkyl refers to the alkyl with 1-6 carbon atom, and it can be straight or branched, for example can be to indefiniteness methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl etc.
In described method of the present invention, C
1-C
6alkoxyl group refers to " C defined above
1-C
6alkyl " group after being connected with O atom.
In described method of the present invention, organic solvent when formula (II) is reacted with (III) is not particularly limited, can be any conventional solvent using in organic synthesis field, for example can be to indefiniteness one or more in benzene, toluene, ethylene dichloride, methylene dichloride, trichloromethane, tetracol phenixin, normal hexane, tetrahydrofuran (THF) (THF), ether, acetonitrile, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol, hexanol etc., preferably tetrahydrofuran (THF), chloroform, toluene, acetonitrile.
In described method of the present invention, described formula (II) and (III) mol ratio of compound are 1:1-5, this scope has comprised any sub-range scope wherein, as 1:1.1-1.9,1:2.1-2.9,1:3.1-3.9,1:4.1-4.9, also comprise any concrete point value wherein, exemplarily for example can be 1:1.5,1:1.6,1:2,1:2.5,1:3,1:3.5,1:4,1:4.5 or 1:5.
In described method of the present invention, the implication of described solid base catalyst refers to the solid alkali being composited by Multimetal oxide, particularly, described solid base catalyst is to be composited by the oxide compound of the oxide compound of the oxide compound of La, Zr, Mg, wherein, with the molar ratio computing of atoms metal, the ratio of Mg, Zr and La is 0.5:1:0.1-0.5, for example can be to indefiniteness 0.5:1:0.1,0.5:1:0.2,0.5:1:0.3,0.5:1:0.4 or 0.5:1:0.5.
In described method of the present invention, the quality of described solid base catalyst is (II) and (III) 1-5% of both quality sums, this scope has comprised any sub-range scope wherein, as 1-4%, 2-3%, also comprise any concrete point value wherein, exemplarily for example can be (II) and 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% of (III) both quality sums.
More preferably, except using above-mentioned solid base catalyst, also can in reaction system, further add promotor, described promotor is polyoxyethylene glycol compounds, for example, can be PEG-400 (molecular weight is 400 g/mol), PEG-600 (molecular weight is 600 g/mol), PEG-800 (molecular weight is 800 g/mol), PEG-1000 (molecular weight is 1000 g/mol) or PEG-2000 (molecular weight is 2000 g/mol) etc.Contriver finds, when on the basis of above-mentioned solid base catalyst, while further adding polyethylene glycols promotor, unexpectedly further to have improved reaction process, for example, shortened the reaction times, improved yield.Wherein in mass, promotor can be 1-4:1 with the ratio of solid base catalyst, as 1:1,1.5:1,2:1,2.5:1,3:1,3.5:1 or 4:1.
In described method of the present invention, reaction times there is no special restriction, for example can determine the suitable reaction times by the residual per-cent of liquid chromatographic detection object product or raw material, it typically is 1-6 hour, is indefiniteness for example 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours.
In described method of the present invention, temperature of reaction is 40-80 ℃, for example can be to indefiniteness 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
In described method of the present invention, the preparation of described solid base catalyst can adopt conventional method for preparing catalyst, as coprecipitation method, pickling process etc.
The present invention is by using solid base catalyst, and preferably further add alkali metal hydroxide, and effectively make formula II and III compound react, obtain aromatic amides, and there is the plurality of advantages such as cost is low, yield is high, selectivity is good, there is good prospects for commercial application and economic benefit.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but these exemplary embodiments not form any type of any restriction to real protection scope of the present invention.
The preparation of preparation example 1:Mg-Zr-La solid base catalyst
Adopt co-precipitation-pickling process to be prepared, as the exemplary preparation method of one, its preparation process is as follows:
(1) at room temperature, by 300 ml concentration be the La (NO of 0.05 mol/L
3)
2the aqueous solution, 300 ml concentration are the ZrOCl of 0.5 mol/L
2aqueous solution stirring and dissolving, controlling bath temperature is 60 ℃, slowly drips in the ammonia soln that concentration is 1 mol/L to mixed solution, form precipitation, regulate pH to 9-10, centrifuge washing, suction filtration, at 130 ℃, calcine 3-5 hour after drying, grind to form powdery for subsequent use.
(2) take Mg (NO
3)
2(being 1:0.5 according to Zr:Mg mol ratio) is made into the aqueous solution, adds in the beaker that above-mentioned dry powder is housed, and steeping fluid liquid level is higher than solid 1 cm left and right, put it in baking oven, constantly be stirred to moisture evaporation, mixture in the pasty state, is dried at 130 ℃, take out and grind, roasting at 600 ℃, makes Mg-Zr-La solid base catalyst, wherein with atoms metal molar ratio computing, Mg:Zr:La=0.5:1:0.1, by its called after catalyzer MZL-1.
According to the method described above, fixing ZrOCl
2consumption and concentration, and by changing La (NO
3)
3concentration, and made respectively with atoms metal molar ratio computing the Mg-La solid base catalyst of Mg:Zr:La=0.5:1:0.2 and 1:0.3, respectively called after catalyzer MZL-2 and MZL-3.
Embodiment 1
In 100 ml flasks, once add 20 ml tetrahydrofuran (THF)s, 10 mmol diethylamine, and 2 mmol p-tolyl aldehydes, be incorporated as the catalyzer MZL-1 of two kinds of reaction raw materials total masses 3% under heated and stirred, stirring reaction 2h at 60 ℃, be cooled to after completion of the reaction room temperature, add deionized water wash, dichloromethane extraction, revolve steaming, cross column purification, vacuum-drying obtains target product N, white solid 0.24 g of N-diethyl-4-methyl benzamide.N, the productive rate of N-diethyl-4-methyl benzamide is 62%.
1H-NMR?(CDCl
3,?300?MHz)?δ：1.35?(t,?6H)，2.34?(s,?3H)，3.99?(m,?4H)，7.39-7.90?(m,?4H)。
MS?m/z：191.12?(M+1,?100)。
Embodiment 2
In 100 ml flasks, once add 30 ml tetrahydrofuran (THF)s, 15 mmol n-Butyl Amine 99s, and 5 mmol2-hydroxyl-3-ethoxy-benzaldehyde, under heated and stirred, be incorporated as the catalyzer MZL-2 of two kinds of reaction raw materials total masses 4.5%, at 65 ℃, stirring reaction 4.5 h, are cooled to room temperature after completion of the reaction, add deionized water wash, dichloromethane extraction, revolve steaming, cross column purification, vacuum-drying obtains white solid 0.79 g of target product N-butyl-2-hydroxy-3-ethoxy benzamide.The productive rate of N-butyl-2-hydroxy-3-ethoxy benzamide is 67%.
1H-NMR?(CDCl
3,?300?MHz)?δ：0.90?(t,?3H)，1.30?(m,?2H)，1.33?(t,?3H)，1.56?(m,?2H),?3.31?(t,?2H),?4.09?(m,?2H),?5.35?(s,?1H),?7.09-7.41?(m,?3H),?8.03?(s,?1H)。
MS?m/z：237.16?(M+1,?100)。
Embodiment 3
In 100 ml flasks, once add 15 ml toluene; 8 mmol Pyrrolidines; and 5 mmol 3-fluorobenzaldehydes, under heated and stirred, be incorporated as the catalyzer MZL-3 of two kinds of reaction raw materials total masses 2%, stirring reaction 4 h at 50 ℃; be cooled to after completion of the reaction room temperature; add deionized water wash, dichloromethane extraction, revolves steaming; cross column purification, vacuum-drying obtains target product N-(3-fluoroformyl) Pyrrolidine 0.59 g.The productive rate of N-(3-fluoroformyl) Pyrrolidine is 61%.
1H-NMR?(CDCl
3,?300?MHz)?δ：1.95?(t,?4H)，3.48?(m,?4H)，7.49-7.8?(m,?4H)。
MS?m/z：193.09?(M+1,?100)。
Embodiment 4
In 100 ml flasks, once add 25 ml chloroforms, 6 mmol N, N-diphenylformamide, and 4 mmol 2 furan carboxyaldehydes, under heated and stirred, be incorporated as the catalyzer MZL-2 of two kinds of reaction raw materials total masses 5%, at 45 ℃, stirring reaction 3 h, are cooled to room temperature after completion of the reaction, add deionized water wash, dichloromethane extraction, revolve steaming, cross column purification, vacuum-drying obtains target product N, N-phenylbenzene-2 furan carboxyaldehyde 0.68 g.N, the productive rate of N-phenylbenzene-2 furan carboxyaldehyde is 65%.
1H-NMR?(CDCl
3,?300?MHz)?δ：6.83?(t,?1H)，7.19-7.23?(m,?3H)，7.43-7.47?(m,?8H)，8.09?(d,?1H)。
MS?m/z：263.09?(M+1,?100)。
Embodiment 5-6
Carried out embodiment 5,6 in the mode of embodiment 1,4 respectively, difference part is to adopt the catalyzer of potassium tert.-butoxide as reaction.Concrete outcome sees the following form 4.
Product yield and the purity of table 1. embodiment 5,6
Embodiment 7-10
Carry out embodiment 7-10 in the mode of embodiment 1-4 respectively, the PEG analog assistant (its kind sees the following form) that it is 1.5:1 that difference part is also to have added with solid alkali mass ratio in reaction system, and shortened the time required while reaching reaction end.Concrete outcome sees the following form 42.
Product yield and the purity of table 2. embodiment 7-10
Embodiment 11-14
Carry out embodiment 11-14 in the mode of embodiment 1-4 respectively, the PEG analog assistant (its kind sees the following form) that it is 4:1 that difference part is also to have added with solid alkali mass ratio in reaction system, and shortened the time required while reaching reaction end.Concrete outcome sees the following form 3.
Product yield and the purity of table 3. embodiment 11-14
As can be seen here:
1, react when solid base catalyst being applied to aromatic aldehyde the reaction type of preparing aromatic amides with amine; especially can be found out by above-mentioned table 1; adopt this reaction of Mg-Zr-La solid base catalyst catalyzed by solid base, product yield, selectivity are all significantly better than potassium tert.-butoxide;
2, can be found out by above-mentioned table 2-3, when add polyoxyethylene glycol compounds in reaction system time, product yield is greatly improved, and has shortened the reaction times.
Therefore, method of the present invention compared with prior art, by the use of solid base catalyst, avoid the use of noble metal catalyst, greatly improve reaction yield, especially, in the time adding PEG compounds, further improved productive rate and shortened the reaction times, obtain beyond thought technique effect, there is certain market outlook and economic benefit for amplification or the suitability for industrialized production of amides.
The purposes that should be appreciated that these embodiment only limits the scope of the invention for the present invention being described but not being intended to.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various changes, modification and/or modification to the present invention, within these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (9)
1. a method for solid base catalyst catalysis preparation formula (I) compound,
Described method comprises: under solid base catalyst exists, formula (II) compound and formula (III) compound react in organic solvent,
Wherein, Ar is for replacing or unsubstituted phenyl or furyl; Described substituting group is halogen, C1-C6 alkyl, C1-C6 alkoxyl group or hydroxyl;
R
1or R
2identical or different between itself, and be selected from independently of one another H, C1-C6 alkyl, phenyl, or R
1and R
2form 5-6 unit cyclammonium with N atom;
Described solid base catalyst is to be composited by the oxide compound of the oxide compound of Zr, La and the oxide compound of Mg;
In described solid base catalyst, with the molar ratio computing of atoms metal, the ratio of Mg, Zr and La is 0.5:1:0.1-0.5.
2. the method for a kind of solid base catalyst catalysis preparation formula (I) compound according to claim 1, is characterized in that: described aryl substituent is halogen, methyl, oxyethyl group; R
1and R
2the 5-6 unit cyclammonium forming with N atom is Pyrrolidine.
3. the method for a kind of solid base catalyst catalysis preparation formula (I) compound according to claim 1, is characterized in that: described formula (II) is 1:1-5 with (III) mol ratio of compound.
4. the method for a kind of solid base catalyst catalysis preparation formula (I) compound according to claim 1, is characterized in that: the quality of described solid base catalyst is (II) and (III) 1-5% of both quality sums.
5. the method for a kind of solid base catalyst catalysis preparation formula (I) compound according to claim 1, is characterized in that: described organic solvent is one or more in benzene, toluene, ethylene dichloride, methylene dichloride, trichloromethane, tetracol phenixin, normal hexane, tetrahydrofuran (THF), ether, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol, hexanol.
6. the method for a kind of solid base catalyst catalysis preparation formula (I) compound according to claim 5, is characterized in that: described organic solvent is tetrahydrofuran (THF), chloroform or toluene.
7. the method for a kind of solid base catalyst catalysis preparation formula (I) compound according to claim 1, is characterized in that: the reaction times is 1-6 hour.
8. the method for a kind of solid base catalyst catalysis preparation formula (I) compound according to claim 1, is characterized in that: temperature of reaction is 40-80 ℃.
9. the method for a kind of solid base catalyst catalysis preparation formula (I) compound according to claim 1, it is characterized in that: in reaction system, further add promotor, described promotor is polyoxyethylene glycol, the molecular weight of described polyoxyethylene glycol is 400g/mol, 1000g/mol or 2000g/mol, in mass, promotor is 1-4:1 with the ratio of solid base catalyst.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987298A (en) * | 2015-07-14 | 2015-10-21 | 朱绍清 | Synthetic method of aryl amide compound |
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| CN101507917A (en) * | 2009-04-02 | 2009-08-19 | 北京化工大学 | Solid base catalyst for synthesizing alkanolamide type compound and preparation method thereof |
| CN101608131A (en) * | 2008-06-20 | 2009-12-23 | 华东理工大学 | A kind of biodiesel oil preparing process of no byproduct glycerol |
| CN102424645A (en) * | 2011-07-29 | 2012-04-25 | 湖南大学 | Method for synthesizing aromatic amide and aromatic methanol |
-
2013
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608131A (en) * | 2008-06-20 | 2009-12-23 | 华东理工大学 | A kind of biodiesel oil preparing process of no byproduct glycerol |
| CN101507917A (en) * | 2009-04-02 | 2009-08-19 | 北京化工大学 | Solid base catalyst for synthesizing alkanolamide type compound and preparation method thereof |
| CN102424645A (en) * | 2011-07-29 | 2012-04-25 | 湖南大学 | Method for synthesizing aromatic amide and aromatic methanol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987298A (en) * | 2015-07-14 | 2015-10-21 | 朱绍清 | Synthetic method of aryl amide compound |
| CN104987298B (en) * | 2015-07-14 | 2016-12-28 | 青岛申达众创技术服务有限公司 | Synthetic method of aryl amide compound |
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