CN101318144B - Catalyst for preparing amide compounds, synthesis and application thereof - Google Patents
Catalyst for preparing amide compounds, synthesis and application thereof Download PDFInfo
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- CN101318144B CN101318144B CN200810023102XA CN200810023102A CN101318144B CN 101318144 B CN101318144 B CN 101318144B CN 200810023102X A CN200810023102X A CN 200810023102XA CN 200810023102 A CN200810023102 A CN 200810023102A CN 101318144 B CN101318144 B CN 101318144B
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- acid amides
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Abstract
The invention discloses a catalyst used for preparing an amide compound. The molecular formula of the catalyst is Ln (OC(CH3)3)10(OH)Na8, wherein, Ln is a rear earth metal, chosen from one of the lanthanides of lanthanum, praseodymium, neodymium, europium, samarium, yttrium and ytterbium. The synthetic method is as follows: a tetrahydrofuran solution of LnCl3 is firstly added; a tetrahydrofuran solution of t-butoxy sodium and sodium hydroxide are added according to the quantity ratio of LnCl3 and t-butoxy sodium and sodium hydroxide of 1:10:1 to react for 4 days, the solvent is removed, the remainder is extracted by toluene and the precipitation is removed by centrifugation; the clear liquid is transferred into another crystallization bottle; the needed crystal is obtained after concentration, tube sealing and freezing. When the catalyst of the invention is used for catalyzing amine and aldehyde to synthesize amide, the catalyst has the advantages of mild reaction condition, wide range of suitable substrate, short reaction time and little dosage, and so on.
Description
Technical field
The present invention relates to a kind of alkoxy rare-earth alkali metal cluster compound, be specifically related to a kind of catalyst that is used for the prepared in reaction amide compound of catalytic amine and aldehyde synthesizing amide.
Background technology
The formation reaction of amido link is one of most important reaction in the Synthetic Organic Chemistry, and this is that it extensively is present in polymer, natural products and the medicine because aromatic amides or fatty acid amide are the functional groups that a class has significant application value.
In the prior art, the method for preparing acid amides has following several:
(1) Humphrey, J.M. wait the people to be published in Chem.ReV.1997,97, the article of 2243-2266, the article that Larock, R.C. are published on the ComprehensiVe Organic Transformation discloses the most frequently used synthetic method of preparation acid amides: the carboxylic acid derivates of amine and activation reacts in the presence of oxidant.
(2) Beller, M. wait the people to be published in C.D.J.Mol.Catal.A:Chem.1995,104,17 article, Ali, B.E. be published in J.Appl.Organomet.Chem.2003,17,921 article, Knapton, D.J. be published in Org.Lett.2004,6,687 article, Uenoyama, Y. be published in Angew.Chem., Int.Ed.2005,44,1075 article etc. discloses a kind of method of synthesizing amide: under late transition metal catalyst catalysis, alkene, alkynes and the halogenated hydrocarbons carbonylation synthesizing amide in the presence of amine.
(3) Ramalingan, C. and Park, Y.-T. is published in J.Org.Chem.2007, and it is catalyst with the mercury salt that the article on 72,4536 discloses a kind of, from the reaction of ketoxime through the Beckmann rearrangement synthesizing amide.
(4) Sharghi, H. and Sarvari.M.H. are published in Tetrahedron 2002,58, and 10323. article also has and is reported in wet Al
2O
3Under the effect, aldehyde and hydroxylamine hydrochloride and mesyl chloride are 100 ℃ of reactions.
(5) Tillack, A. wait the people to be published in J.Org.Chem.2001, the article of 523-528, Naota, T. and Murahashi, S. be published in Synlett 1991, the article of 693-694, Tamaru, people such as Y. are published in Synthesis 1983,474-476, and Nakagawa, people such as K are published in Chem.Commun.1966, and the article on the 17-18. has reported that from the direct oxidation amination of aldehyde be the industrial most economical synthetic method that raw material should get, late transition metal palladium, ruthenium and rhodium and nickel compound can be used as catalyst this reaction of catalysis in the presence of oxidant.
(6) Yoo, W.-J. and Li, C.-J. is published in J.Am.Chem.Soc.2006, and 128, the amidation process of cuprous iodide catalysis primary amine in the presence of oxidant reported in the article on the 13064-13065.
(7) Kekeli Ekoue-Kovi and Christian Wolf are published in Org.Lett.2007, and the article on 9,3429 has been reported does not have metallic compound to exist down, utilize TBHP catalysis aldehyde and amine to generate the reaction of acid amides.
(8) Vora, H.U. and Rovis, T. be published in J.Am.Chem.Soc.2007,129, the article of 13796-13797 and Bode, J.W. and Sohn, S.S. is published in J.Am.Chem.Soc.2007,129, the amidation process of N-heterocyclic carbine as catalyst aldehyde and amine reported in the article of 13798-13799.
(9) Shie, J.-J. and Fang, J.-M. is published in J.Org.Chem.2003, and 68,1158 article has reported that aldehyde generates the method for acid amides at room temperature reaction under iodine and hydrogen peroxide effect.
(10) nearest; Gunanathan; C. wait the people to be published in Science 2007, the article of 790-792 report is with the ruthenium catalyst that contains the dinitrogen heterocycle carbine direct acylation reaction of catalytic alcohol and amine in the backflow toluene solution, and aldehyde reacts as an intermediate participation oxidative amination in this reaction.
Above these catalytic reactions all need harsh reaction condition to comprise that needs add peroxide, highly basic, heat or light.
Ishihara, K. and Yano, T. is published in Org.Lett.2004,6, the article of 1983-1986 has been reported with the diisopropyl aniline lithium and has been made the method for catalyst by Cannizzaro reaction synthesizing amide, Zhang, and people such as L are published in J.Org.Chem., 2006,71, the article of 3149-3153 shows that rare earth-iron-boron also can be used as catalyst, this reaction of catalysis, generate acid amides, but the amido lithium of this reaction needed metering.
Marks is published in Org.Lett.2008 recently, and 10, the article of 317-319 has been reported: rare earth aminate Ln[N (SiMe
3)
2]
3(Ln=La, Sm Y) can be at the amidation process of room temperature catalysis aldehyde and amine.This system does not need oxidant applying and highly basic, the reaction condition gentleness, but this catalyst consumption is bigger, and the reaction time is longer.And this catalyst is not high to the reaction yield of aldehyde and secondary cyclammonium.
Summary of the invention
The object of the invention provides the new catalyst that a kind of catalytic amine and aldehyde prepare acid amides, to obtain higher catalytic activity, shortens reaction time and catalyst amount, and is applicable to wideer substrate scope.
For achieving the above object, the technical solution used in the present invention is: a kind of catalyst that is used to prepare amide compound, and its molecular formula is as follows:
Ln[OC (CH
3)
3]
10(OH) Na
8, wherein Ln represents rare earth metal, is selected from a kind of in lanthanum in the lanthanide series, praseodymium, neodymium, europium, samarium, yttrium, the ytterbium.
Catalyst in the technique scheme belongs to alkoxy rare-earth alkali metal cluster compound, contains a rare earth metal, ten tert-butoxy parts in the molecular formula of this catalyst, a hydroxyl, eight sodium.
Above-mentioned alkoxy rare-earth alkali metal cluster compound Ln[OC (CH
3)
3]
10(OH) Na
8Synthetic specifically may further comprise the steps:
(1) in the reaction bulb of handling through dehydration and deoxidation, adds LnCl with syringe under the argon shield
3THF solution, press the ratio LnCl of amount of substance then
3: Na[OC (CH
3)
3]: NaOH=1: 10: 1, at room temperature add Na[OC (CH with syringe
3)
3] THF solution and NaOH, reacted 4 days;
(2) vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, and after concentrated, tube sealing is put into refrigerator, in 5 ℃ freezing, obtain Ln[OC (CH
3)
3]
10(OH) Na
8Crystal.Ln represents rare earth metal: a kind of in lanthanum, praseodymium, neodymium, europium, samarium, yttrium, the ytterbium.
As not needing to obtain Ln[OC (CH
3)
3]
10(OH) Na
8Crystal, concentrate can be added hexane just can be with Ln[OC (CH
3)
3]
10(OH) Na
8Be precipitated out.
Above-mentioned alkoxy rare-earth alkali metal cluster compound Ln[OC (CH
3)
3]
10(OH) Na
8The step of the amidation process of catalysis aldehyde and amine is:
(1) in the reaction bulb of handling through dehydration and deoxidation, under argon shield, adds catalyst Ln[OC (CH
3)
3]
10(OH) Na
8THF solution, add amine with syringe then, at room temperature stir companion 30min, add aldehyde with syringe again, reacted 3 hours;
(2) remove by filter catalyst, removal of solvent under reduced pressure, column chromatography obtains acid amides;
The reactant substrate that above-mentioned catalytic reaction is suitable for comprises the one-level arylamine, one-level fatty amine, secondary aliphatic amine and secondary cyclammonium.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. because the use of this catalyst, can be under temperate condition highly active catalysis aldehyde and amine synthesizing amide, and do not need to add peroxide;
2. activity of such catalysts of the present invention is than the Ln[N (SiMe of report
3)
2]
3Height is reaching under the situation of identical yield, and catalyst amount can be 1 mole of %, and the reaction time can shorten to 3 hours, simultaneously to the scope of application broad of substrate: to benzaldehyde and nafoxidine, the reaction of piperidines has very high reactivity.
3. catalyst amount of the present invention is less, helps the purifying of product.
The specific embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: Nd[OC (CH
3)
3]
10(OH) Na
8Synthetic:
In the reaction bulb of handling through dehydration and deoxidation, add an amount of NdCl with syringe under the argon shield
3THF solution, at room temperature add Na[OC (CH in 1: 10 ratio then with syringe
3)
3] THF solution, add again and add again and NdCl
3Equimolar NaOH reacted 4 days, and vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, after concentrating, and tube sealing, it is freezing to put into refrigerator (5 ℃), obtains Nd[OC (CH
3)
3]
10(OH) Na
8Blue colored crystal.
Embodiment two: Sm[OC (CH
3)
3]
10(OH) Na
8Synthetic:
In the reaction bulb of handling through dehydration and deoxidation, add an amount of SmCl with syringe under the argon shield
3THF solution, at room temperature add Na[OC (CH in 1: 10 ratio then with syringe
3)
3] THF solution, add again and SmCl
3Equimolar NaOH reacted 4 days, and vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, after concentrating, and tube sealing, it is freezing to put into refrigerator (5 ℃), obtains Sm[OC (CH
3)
3]
10(OH) Na
8Clear crystal.
Embodiment three: Yb[OC (CH
3)
3]
10(OH) Na
8Synthetic:
In the reaction bulb of handling through dehydration and deoxidation, add an amount of YbCl with syringe under the argon shield
3THF solution, at room temperature add Na[OC (CH in 1: 10 ratio then with syringe
3)
3] THF solution, add again and YbCl
3Equimolar NaOH reacted 4 days, and vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, after concentrating, and tube sealing, it is freezing to put into refrigerator (5 ℃), obtains Yb[OC (CH
3)
3]
10(OH) Na
8Clear crystal.
Embodiment four: Nd[OC (CH
3)
3]
10(OH) Na
8The catalysis benzaldehyde becomes acid amides with the N-methylbenzylamine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst n d[OC (CH
3)
3]
10(OH) Na
8(0.01mmol, 0.011g) THF solution, (0.13ml 1mmol), at room temperature stirs companion 30min then to add the N-methylbenzylamine with syringe then, add benzaldehyde (0.3ml with syringe again, 3mmol), react after 3 hours, with sand core funnel elimination catalyst, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/7) obtains acid amides FC
6H
4CON (CH
3) C
7H
70.189g, productive rate 84%.
Embodiment five: Nd[OC (CH
3)
3]
10(OH) Na
8The catalysis 4-Fluorobenzaldehyde becomes acid amides with the N-methylbenzylamine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst n d[OC (CH
3)
3]
10(OH) Na
8(0.01mmol, 0.0108g) THF solution, (0.13ml 1mmol), at room temperature stirs companion 30min then to add the N-methylbenzylamine with syringe then, add 4-Fluorobenzaldehyde (0.32ml with syringe again, 3mmol), react after 3 hours, with sand core funnel elimination catalyst, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/7) obtains acid amides FC
6H
4CON (CH
3) C
7H
70.241g, productive rate 99%.
Embodiment six: Nd[OC (CH
3)
3]
10(OH) Na
8The catalysis P-methoxybenzal-dehyde becomes acid amides with the N-methylbenzylamine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst n d[OC (CH
3)
3]
10(OH) Na
8(0.01mmol, 0.0108g) THF solution, (0.13ml 1mmol), at room temperature stirs companion 30min then to add the N-methylbenzylamine with syringe then, add P-methoxybenzal-dehyde (0.36ml with syringe again, 3mmol), react after 3 hours, with sand core funnel elimination catalyst, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/7) obtains acid amides CH
3OC
6H
4CON (CH
3) C
7H
70.179g, productive rate 70%.
Embodiment seven: Sm[OC (CH
3)
3]
10(OH) Na
8The catalysis benzaldehyde becomes acid amides with nafoxidine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add and contain catalyst S m[OC (CH
3)
3]
10(OH) Na
8THF solution (0.005mmol), then with syringe add nafoxidine (0.08ml, 1mmol), at room temperature stir then companion 30min, again with syringe add benzaldehyde (0.3ml, 3mmol), react after 3 hours, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/3) obtains acid amides C
6H
5CONC
4H
80.131g, productive rate 75%.
Embodiment eight: Yb[OC (CH
3)
3]
10(OH) Na
8The catalysis benzaldehyde becomes acid amides with nafoxidine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add and contain catalyst Yb[OC (CH
3)
3]
10(OH) Na
8THF solution (0.005mmol), then with syringe add nafoxidine (0.08ml, 1mmol), at room temperature stir then companion 30min, again with syringe add benzaldehyde (0.3ml, 3mmol), react after 3 hours, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/3) obtains acid amides C
6H
5CONC
4H
80.105g, productive rate 60%.
Embodiment nine: Nd[OC (CH
3)
3]
10(OH) Na
8The catalysis benzaldehyde becomes acid amides with aniline
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst n d[OC (CH
3)
3]
10(OH) Na
8(0.01mol, 0.0108g) THF solution, (0.10ml 1mmol), at room temperature stirs companion 30min then to add aniline with syringe then, add benzaldehyde (0.30ml with syringe again, 3mmol), react after 3 hours, with sand core funnel elimination catalyst, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/7) obtains acid amides C
6H
5CONHC
6H
50.158g, productive rate 80%.
Embodiment ten: Nd[OC (CH
3)
3]
10(OH) Na
8The catalysis benzaldehyde becomes acid amides with aniline
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst n d[OC (CH
3)
3]
10(OH) Na
8(0.03mmol, 0.0324g) THF solution, (0.11ml 1mmol), at room temperature stirs companion 30min then to add benzylamine with syringe then, add benzaldehyde (0.30ml with syringe again, 3mmol), react after 3 hours, with sand core funnel elimination catalyst, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/7) obtains acid amides C
6H
5CONHCH
2C
6H
50.169g, productive rate 80%.
Embodiment 11: Nd[OC (CH
3)
3]
10(OH) Na
8The catalysis benzaldehyde becomes acid amides with nafoxidine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst n d (O
tBu)
10(OH) Na
8(0.01mmol, 0.011g) THF solution, (0.08ml 1mmol), at room temperature stirs companion 30min then to add nafoxidine with syringe then, add benzaldehyde (0.3ml with syringe again, 3mmol), react after 3 hours, with sand core funnel elimination catalyst, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/3) obtains acid amides C
6H
5CONC
4H
80.163g, productive rate 93%.
In contrast, with Ln[N (SiMe
3)
2]
3Be catalyst, react after 24 hours that productive rate has only 38%
Embodiment 12: Nd[OC (CH
3)
3]
10(OH) Na
8The catalysis benzaldehyde becomes acid amides with hexahydropyridine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst n d[OC (CH
3)
3]
10(OH) Na
8(0.01mmol, 0.011g) THF solution, (0.10ml 1mmol), at room temperature stirs companion 30min then to add hexahydropyridine with syringe then, add benzaldehyde (0.3ml with syringe again, 3mmol), react after 3 hours, with sand core funnel elimination catalyst, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/10) obtains acid amides C
6H
5CONC
6H10 0.176g, productive rate 93%.
Claims (1)
1. the application of catalyst in the reaction of catalytic amine and aldehyde synthesizing amide, the molecular formula of described catalyst is as follows:
Ln[OC (CH
3)
3]
10(OH) Na
8, wherein Ln represents rare earth metal, is selected from a kind of in lanthanum in the lanthanide series, praseodymium, neodymium, europium, samarium, the ytterbium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810023102XA CN101318144B (en) | 2008-07-14 | 2008-07-14 | Catalyst for preparing amide compounds, synthesis and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810023102XA CN101318144B (en) | 2008-07-14 | 2008-07-14 | Catalyst for preparing amide compounds, synthesis and application thereof |
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| Publication Number | Publication Date |
|---|---|
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| CN101318144B true CN101318144B (en) | 2010-09-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101664699B (en) * | 2009-09-14 | 2011-08-10 | 苏州大学 | Catalyzer used for preparing acidamide compound and application thereof |
| CN107915653B (en) * | 2017-12-04 | 2020-02-14 | 苏州大学 | Method for preparing amide by catalyzing ester and amine to react |
| CN111620921B (en) * | 2020-05-25 | 2023-06-13 | 上海药明康德新药开发有限公司 | Method for preparing On-DNA amide compound by oxidative amidation in construction of DNA coding compound library |
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2008
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Non-Patent Citations (3)
| Title |
|---|
| Hongting Sheng, et al,.Novel mixed-metal alkoxide clusters of lanthanideandsodium:synthesis and extremely active catalysts forthepolymerization of ε-caprolactone and trimethylenecarbonate,.Inorg.Chem.,46.2007,467723. * |
| SungYong Seo,et al,.Mild Amidation of AldehydeswithAminesMediatedbyLanthanide Catalysts.ORGANIC LETTERS,10, 2.2008,10,(2),317-319. * |
| William J.Evans,et al,.Synthetic and structural studies of nonametallic tert-butoxidemixed-metal complexes ofyttrium,europium,andsodium:X-raycrystal structures of a newclass of LnNa8(OR)10X complexes(Ln=Y,Eu;R=CMe3;X=Cl,OH).J.Am.Chem.Soc,115.1993,1154120. * |
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