CN101664699B - Catalyzer used for preparing acidamide compound and application thereof - Google Patents
Catalyzer used for preparing acidamide compound and application thereof Download PDFInfo
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Abstract
The present invention relates to a catalyzer used for preparing acidamide compound and application thereof. The catalyzer has the molecular formula [(p-RPhNLi) iPrNCN iPr] 3Ln.3THF.3DME, wherein R is equal to Cl, H; Ln represents rare earth metal which is selected from one of lanthanum, neodymium, samarium, illinium or ytterbium in lanthanide. Due to the use of the catalyzer, aldehyde and amine are catalyzed under the mild condition in the way of high activity to synthesize acidamide. The activity of the catalyzer is higher than that of the several previously reported catalyzers, and therefore, under the condition of reaching the same yield, the use level of the catalyzer is less, and the reaction time is short; meanwhile, the applicable scope of the catalyzer to substrates is wider.
Description
Technical field
The present invention relates to a kind of catalyst for preparing amide compound, be specifically related to the catalyst that a kind of catalysis aldehyde and amine prepare amide compound.
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.
(11) 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.
(12) Marks is published in Org.Lett.2008, 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.
Inventor place seminar successively is published in J.Org.Chem., 2009,74,2575-2577; Advanced Synthesis ﹠amp; Catalysis 2009,351,1363-1370; Organometallics 2009,28, and the article on the 3856-3862 has been reported at anionic aryloxy rare earth/lithium-complex, anionic bridging amidino groups rare earth lithium-complex [Li (DME)
3] [L
2Ln] and three guanidine radicals rare earth compounds can be at the amidation process of room temperature catalysis aldehyde and amine, but these activity of such catalysts all are still waiting to improve, for example [Li (DME)
3] [L
2Ln] catalyst is that productive rate is 80% under the condition of 1mol% at catalyst amount.
Summary of the invention
The object of the invention provides the catalyst that a kind of catalytic amine and aldehyde prepare acid amides.
For achieving the above object, the technical solution used in the present invention is: the molecular formula of described catalyst is: [(p-RPhNLi)
iPrNCN
iPr]
3Ln3THF3DME, wherein, R=Cl, H; Ln represents rare earth metal, is selected from: a kind of in lanthanum, neodymium, samarium, yttrium or the ytterbium.The molecular structural formula of described catalyst is as follows:
In the technique scheme, described catalyst belongs to pairs of anion guanidine radicals rare earth/Li metal complex, contains a rare earth metal, three lithiums in the molecular formula of this catalyst, three pairs of anion guanidine radicals, three oxolanes (THF), three glycol dimethyl ethers (DME).
Prepare the method for above-mentioned catalyst, may further comprise the steps:
In the entire reaction course, with p-RPhNH
2Mole is a;
(1) under the anhydrous and oxygen-free condition, in the inert gas atmosphere, with a p-RPhNH
2Be dissolved among the THF, add a n-BuLi in 0～20 ℃, temperature slowly rises to room temperature reaction, and the reaction time was more than or equal to 1 hour; Add a diisopropyl diimine again, reaction at room temperature, the reaction time was more than or equal to 1 hour; Add three/a LnCl
3The THF slurry, at room temperature the reaction, reacted about 4 days;
(2) vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing is concentrated into clear liquid dried, adds the THF dissolving, adds three parts of n-BuLis in 0～20 ℃ of scope again, and reaction was more than or equal to 2 hours;
(3) vacuum desolventizes THF, adds DME in the residue, heating for dissolving, and the centrifugal precipitation of removing shifts clear liquid to the crystallization bottle, concentrates clear liquid, and the envelope bottle places crystallization under the room temperature, obtains crystal [(p-RPhNLi)
iPrNCN
iPr]
3Ln3THF3DME, wherein, R=Cl, H; Ln represents rare earth metal, is selected from: a kind of in lanthanum, neodymium, samarium, yttrium or the ytterbium.
The present invention protects above-mentioned catalyst to prepare application in the amide compound at catalysis aldehyde and amine simultaneously.
Use the method that above-mentioned catalyst aldehyde and amine prepare amide compound, may further comprise the steps:
(1) under the anhydrous and oxygen-free condition, in the inert gas atmosphere, amine is added in the THF solution of catalyst, at room temperature stir about companion 30min, add aldehyde again, reacted 3 hours;
In the technique scheme, the reaction time during less than 3 hours productive rate can reduce, the reaction time can lose catalyst advantage efficiently greater than 3 hours, so the reaction time is about 3 hours;
(2) remove by filter catalyst, removal of solvent under reduced pressure, column chromatography obtains acid amides;
In the technique scheme, described aldehyde is selected from: a kind of in benzaldehyde, p-tolyl aldehyde, 4-chloro-benzaldehyde, P-methoxybenzal-dehyde, NSC 43794 or the hexahydrobenzaldehyde; Described amine is selected from: a kind of in one-level arylamine, one-level fatty amine, secondary aliphatic amine or the 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 at the catalysis aldehyde and the amine synthesizing amide of high activity under the temperate condition (under the room temperature condition, the reaction time is 3 hours), and do not need to add peroxide;
2. activity of such catalysts of the present invention is more in the past than several activity of such catalysts height of reporting, reaching under the situation of identical yield, catalyst amount can be 1 mole of %, and the reaction time can be 3 hours, to the scope of application broad of substrate, suitable reactant substrate comprises the one-level arylamine, the one-level fatty amine simultaneously, secondary aliphatic amine and secondary cyclammonium: to benzaldehyde and nafoxidine, the reaction of morpholine has very high reactivity; To hexahydrobenzaldehyde and nafoxidine, the reaction of morpholine also has good reactivity.
3. catalyst amount of the present invention is less, can reduce cost, and also helps the purifying of product.
The specific embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME's is synthetic:
In the reaction bulb of handling through dehydration and deoxidation; weighing 1mol parachloroanilinum and dissolve under the argon shield with THF; at 0 ℃ of n-BuLi that adds 1mol with syringe; temperature slowly rises to room temperature; react and got final product in 1 hour; the diisopropyl diimine that adds 1mol again with syringe react and got final product the NdCl of adding 1/3mol in 1 hour
3The THF slurry, reacted about 4 days; Vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, is concentrated into driedly, adds the THF dissolving, at the n-BuLi that adds 3mol, reacts 2 hours under 0 ℃; Vacuum desolventizes THF, adds DME in the residue, heating for dissolving, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, and through concentrating, the envelope bottle places crystallization under the room temperature, obtains blue look crystal [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME.C
63H
108Cl
3Li
3N
9NdO
9，Mr＝1406.99，Monoclinic，space?group?P?21/c，a＝19.072(3)?
b＝12.2723(18)?
c＝35.336(5)?
β＝94.420°，V＝8246(2)?
Z＝4，ρ
calcd＝1.133g·cm
-3，μ(MoKR)＝0.776mm
-1，31830?collected?reflections，15146?crystallographicallyindependent?reflections(Rint＝0.0325)，12987?reflections?with?I＞2σ(I)，R1＝0.0864(I＞2σ(I))，wR2＝0.2490(all?data).Anal.Calc.forC
63H
108Cl
3Li
3N
9O
9Nd：C，53.78；H，7.74；N，8.96；Nd，10.25.Found：C，53.67；H，7.72；N，8.95；Nd，10.21.IR(KBr?pellet)：3074(s)，2974(s)，2926(s)，2869(s)，1636(s)，1609(s)，1585(s)，1546(s)，1499(s)，1485(s)，1365(m)，1165(m)，1091(m)，1007(m)，952(m)，859(m).
Embodiment two: [(p-ClPhNLi)
iPrNCN
iPr]
3Y3THF3DME's is synthetic:
In the reaction bulb of handling through dehydration and deoxidation; weighing 1mol parachloroanilinum and dissolve under the argon shield with THF; at 0 ℃ of n-BuLi that adds 1mol with syringe; temperature slowly rises to room temperature; reacted 1 hour; add the diisopropyl diimine of 1mol again with syringe, reacted 1 hour, add the YCl of 1/3mol
3The THF slurry, reacted 4 days; Vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, is concentrated into driedly, adds the THF dissolving, at the n-BuLi that adds 3mol, reacts 2 hours under 0 ℃; Vacuum desolventizes THF, adds DME in the residue, heating for dissolving, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, and through concentrating, the envelope bottle places crystallization under the room temperature, obtains clear crystal [(p-ClPhNLi)
iPrNCN
iPr]
3Y3THF3DME.C
63H
108Cl
3Li
3N
9YO
9，Mr＝1351.66，Monoclinic，space?group?P?21/c，a＝19.029(3)?
b＝12.0563(19)?
c＝35.222(6)?
β＝94.175(3)°，V＝8059(2)?
Z＝4，ρ
calcd＝1.114g·cm
-3，μ(Mo?KR)＝0.874mm
-1，46446?collected?reflections，14767crystallographically?independent?reflections(Rint＝0.0715)，9914?reflectionswith?I＞2σ(I)，R1＝0.1308(I＞2σ(I))，wR2＝0.3489(all?data).
1H?NMR(400MHz，TDF)：δ＝7.01-6.89(d，6H，m-H-Ph)，6.55-6.46(m，6H，o-H-Ph)，3.66-3.58(m，12H，α-H-THF)，3.41-3.38(m，12H，O-CH
2-)，3.33-3.30(m，6H，H-C(N)Me
2)，3.24(s，18H，O-CH
3)，1.77-1.70(m，4H，β-H，THF)，1.10-0.97(d，36H，CH
3)PPm.
13C?NMR(100MHz，TDF)：δ＝155.7，127.7，123.3，121.2，115.8，71.9，67.4，58.1，45.5，25.6，23.3ppm.Anal.Calc.forC
63H
108Cl
3Li
3N
9O
9Y(1351.66)：C，55.98；H，8.05；N，9.33；Y，6.58.Found：C，55.78；H，7.82；N，8.93；Y，6.56.IR(KBr?pellet)：3074(s)，2973(s)，2926(s)，2872(s)，1630(s)，1600(s)，1585(s)，1542(s)，1500(s)，1484(s)，1359(m)，1163(m)，1090(m)，1012(m)，952(m)，859(m).
Embodiment three: [(PhNLi)
iPrNCN
iPr]
3Nd3THF3DME's is synthetic:
In the reaction bulb of handling through dehydration and deoxidation; dilute with syringe adding 1mol aniline and with THF under the argon shield; at 0 ℃ of n-BuLi that adds 1mol with syringe; temperature slowly rises to room temperature; reacted 1 hour; add the diisopropyl diimine of 1mol again with syringe, reacted 1 hour, add the NdCl of 1/3mol
3The THF slurry, reacted 4 days; Vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, is concentrated into driedly, adds the THF dissolving, at the n-BuLi that adds 3mol, reacts 2 hours under 0 ℃; Vacuum desolventizes THF, adds DME in the residue, heating for dissolving, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, and through concentrating, the envelope bottle places crystallization under the room temperature, obtains blue colored crystal [(PhNLi)
iPrNCN
iPr]
3Nd3THF3DME.Calc.forC
63H
111Li
3N
9O
9Nd(1300.8)：C，58.04；H，8.58；N，9.67；Nd，11.06。Found：C，58.01；H，8.56；N，9.60；Nd，11.05.IR(KBr?pellet)：3030(s)，2906(s)，2871(s)，2771(s)，1645(s)，1598(s)，1577(s)，1525(s)，1495(s)，1483(s)，1385(m)，?1163(m)，1111(m)，1002(m)，949(m)，851(m).
Embodiment four: [(p-ClPhNLi)
iPrNCN
iPr]
3La3THF3DME's is synthetic:
In the reaction bulb of handling through dehydration and deoxidation; weighing 1mol parachloroanilinum and dissolve under the argon shield with THF; at 0 ℃ of n-BuLi that adds 1mol with syringe; temperature slowly rises to room temperature; reacted 1 hour; add the diisopropyl diimine of 1mol again with syringe, reacted 1 hour, add the LaCl of 1/3mol
3The THF slurry, reacted 4 days; Vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, is concentrated into driedly, adds the THF dissolving, at the n-BuLi that adds three times of moles, reacts 2 hours under 0 ℃; Vacuum desolventizes THF, adds DME in the residue, heating for dissolving, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, and through concentrating, the envelope bottle places crystallization under the room temperature, obtains clear crystal [(p-ClPhNLi)
iPrNCN
iPr]
3La3THF3DME.Anal.Calc.for?C
63H
108Cl
3Li
3N
9O
9La：C，53.98；H，7.77；N，8.99；La，9.91.Found：C，53.88；H，7.75；N，8.97；La，9.96.IR(KBr?pellet)：3066(s)，2971(s)，2931(s)，2876(s)，1640(s)，1615(s)，1583(s)，1556(s)，1500(s)，1495(s)，1385(m)，1160(m)，1091(m)，1017(m)，959(m)，864(m).
Embodiment five: [(p-ClPhNLi)
iPrNCN
iPr]
3Sm3THF3DME's is synthetic:
In the reaction bulb of handling through dehydration and deoxidation; weighing 1mol parachloroanilinum and dissolve under the argon shield with THF; at 0 ℃ of n-BuLi that adds 1mol with syringe; temperature slowly rises to room temperature; reacted 1 hour; add the diisopropyl diimine of 1mol again with syringe, reacted 1 hour, add the SmCl of 1/3mol
3The THF slurry, reacted 4 days; Vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, is concentrated into driedly, adds the THF dissolving, at the n-BuLi that adds 3mol, reacts 2 hours under 0 ℃; Vacuum desolventizes THF, adds DME in the residue, heating for dissolving, and the centrifugal precipitation of removing shifts clear liquid in another crystallization bottle, and through concentrating, the envelope bottle places crystallization under the room temperature, obtains clear crystal [(p-ClPhNLi)
iPrNCN
iPr]
3Sm3THF3DME.Anal.Calc.for?C
63H
108Cl
3Li
3N
9O
9Sm：C，53.55；H，7.70；N，8.92；Sm，10.64.Found：C，53.46；H，7.66；N，8.88；Sm，10.57.IR(KBr?pellet)：3059(s)，2977(s)，2944(s)，2856(s)，1632(s)，1606(s)，1575(s)，1567(s)，1498(s)，1482(s)，1382(m)，1143(m)，1081(m)，1034(m)，944(m)，850(m).
Embodiment six: [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME catalysis benzaldehyde becomes acid amides with the N-methylbenzylamine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME (0.01mmol, 0.014g) THF solution, (0.13mL 1mmol), at room temperature stirs 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 C
6H
4CON (CH
3) C
7H
7, 0.203g, productive rate 90%.
Embodiment seven: [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME catalysis benzaldehyde becomes acid amides with aniline
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME (0.01mmol, 0.014g) THF solution, (0.09mL 1mmol), at room temperature stirs 30min then to add aniline 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 C
6H
5CONHC
6H
5, 0.181g, productive rate 92%.
With [Li (DME)
3] [LnL
2] { L=[Me
3SiNC (Ph) N (CH
2)
3NC (Ph) NSiMe
3] be catalyst, and reacting after 3 hours, productive rate has only 80%.
Embodiment eight: [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME 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 [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME (0.01mmol, 0.014g) THF solution, (0.13mL 1mmol), at room temperature stirs 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
70.155g, productive rate 61%.
Embodiment nine: [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME catalysis 4-chloro-benzaldehyde becomes acid amides with aniline
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME (0.01mmol, 0.014g) THF solution, (0.09mL 1mmol), at room temperature stirs 30min then to add aniline with syringe then, add 4-chloro-benzaldehyde (0.42g with weighing 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 p-ClC
6H
4CONHC
6H
5, 0.211g, productive rate 91%.
Embodiment ten: [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME catalysis hexahydrobenzaldehyde becomes acid amides with nafoxidine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add and contain catalyst [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME (0.01mmol, 0.014g) THF solution, add nafoxidine (0.08mL with syringe then, 1mmol), at room temperature stir 30min then, add hexahydrobenzaldehyde (0.36mL with syringe again, 3mmol), react after 3 hours, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/6) obtains acid amides C
6H
11CONC
5H
100.14g, productive rate 72%.
Embodiment 11: [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME catalysis hexahydrobenzaldehyde becomes acid amides with morpholine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add and contain catalyst [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME (0.01mmol, 0.014g) THF solution, add morpholine (0.083mL with syringe then, 1mmol), at room temperature stir 30min then, add hexahydrobenzaldehyde (0.36mL with syringe again, 3mmol), react after 3 hours, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/6) obtains acid amides C
6H
11CONC
4H
8O, 0.161g, productive rate 81%.
Embodiment 12: [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME catalysis hexahydrobenzaldehyde becomes acid amides with aniline
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add and contain catalyst [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME (0.01mmol, 0.014g) THF solution, add aniline (0.09mL with syringe then, 1mmol), at room temperature stir 30min then, add hexahydrobenzaldehyde (0.36mL with syringe again, 3mmol), react after 3 hours, removal of solvent under reduced pressure, column chromatography (EtOAc/ benzinum=1/6) obtains acid amides C
6H
11CONC
6H
5, 0.113g, productive rate 56%.
Embodiment 13: [(p-ClPhNLi)
iPrNCN
iPr]
3Y3THF3DME catalysis benzaldehyde becomes acid amides with aniline
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst [(p-ClPhNLi)
iPrNCN
iPr]
3Y3THF3DME (0.01mmol, 0.0135g) THF solution, (0.10mL 1mmol), at room temperature stirs 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
5CONC
6H
50.160g, productive rate 81%.
Embodiment 14: [(PhNLi)
iPrNCN
iPr]
3Nd3THF3DME catalysis benzaldehyde becomes acid amides with aniline
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst [(PhNLi)
iPrNCN
iPr]
3Nd3THF3DME (0.01mmol, 0.014g) THF solution, (0.09mL 1mmol), at room temperature stirs 30min then to add aniline 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 C
6H
5CONHC
6H
50.171g, productive rate 87%.
Embodiment 15: [(p-ClPhNLi)
iPrNCN
iPr]
3Sm3THF3DME catalysis benzaldehyde becomes acid amides with aniline
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst [(p-ClPhNLi)
iPrNCN
iPr]
3Sm3THF3DME (0.01mmol, 0.0141g) THF solution, (0.09mL 1mmol), at room temperature stirs 30min then to add aniline 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 C
6H
5CONHC
6H
50.162g, productive rate 82%.
Embodiment 16: [(p-ClPhNLi)
iPrNCN
iPr]
3Sm3THF3DME catalysis benzaldehyde becomes acid amides with the N-methylbenzylamine
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst [(p-ClPhNLi)
iPrNCN
iPr]
3Nd3THF3DME (0.01mmol, 0.014g) THF solution, (0.13mL 1mmol), at room temperature stirs 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 C
6H
4CON (CH
3) C
7H
7, 0.204g, productive rate 91%.
Embodiment 17: [(p-ClPhNLi)
iPrNCN
iPr]
3La3THF3DME catalysis benzaldehyde becomes acid amides with aniline
In the reaction bulb of handling through dehydration and deoxidation, under argon shield, add catalyst [(p-ClPhNLi)
iPrNCN
iPr]
3La3THF3DME (0.01mmol, 0.014g) THF solution, (0.09mL 1mmol), at room temperature stirs 30min then to add aniline 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 C
6H
5CONHC
6H
5, 0.177g, productive rate 90%.
Claims (3)
1. a catalyst for preparing acid amides is characterized in that, the molecular formula of described catalyst is: [(p-RPhNLi)
iPrNCN
iPr]
3Ln3THF3DME, wherein, R=Cl, H; Ln represents rare earth metal, is selected from: a kind of in lanthanum, neodymium, samarium, yttrium or the ytterbium; THF is an oxolane, and DME is a glycol dimethyl ether; The molecular structural formula of described catalyst is as follows:
2. the described Preparation of catalysts method of claim 1 is characterized in that, may further comprise the steps:
In the entire reaction course, with p-RPhNH
2Mole is a;
(1) under the anhydrous and oxygen-free condition, in the inert gas atmosphere, with a p-RPhNH
2Be dissolved among the THF, add a n-BuLi in 0～20 ℃, temperature slowly rises to room temperature reaction, and the reaction time was more than or equal to 1 hour; Add a diisopropyl diimine again, reaction at room temperature, the reaction time was more than or equal to 1 hour; Add three/a LnCl
3The THF slurry, at room temperature the reaction, reacted about 4 days;
(2) vacuum desolventizes THF, and residue extracts with toluene, and the centrifugal precipitation of removing is concentrated into clear liquid dried, adds the THF dissolving, adds three parts of n-BuLis in 0～20 ℃ of scope again, and reaction was more than or equal to 2 hours;
(3) vacuum desolventizes THF, adds DME in the residue, heating for dissolving, and the centrifugal precipitation of removing shifts clear liquid to the crystallization bottle, concentrates clear liquid, and the envelope bottle places crystallization under the room temperature, obtains crystal [(p-RPhNLi)
iPrNCN
iPr]
3Ln3THF3DME, wherein, R=Cl, H; Ln represents rare earth metal, is selected from: a kind of in lanthanum, neodymium, samarium, yttrium or the ytterbium; THF is an oxolane, and DME is a glycol dimethyl ether; The molecular structural formula of described catalyst is as follows:
3. the described catalyst of claim 1 prepares application in the amide compound at catalysis aldehyde and amine.
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| CN102295663B (en) * | 2011-05-30 | 2014-12-10 | 苏州大学 | Dianionic guanidine complex of rare earth and lithium and application thereof |
| CN102603656B (en) * | 2012-02-17 | 2014-07-02 | 苏州大学 | Application of bimetallic cationic complex |
| CN102755906A (en) * | 2012-07-17 | 2012-10-31 | 苏州大学 | Application of amino aryloxy rare-earth metal-lithium amide used as catalyst |
| CN103483362B (en) * | 2013-09-04 | 2016-01-20 | 苏州大学 | Amido bridged linkage bis aryloxy rare earth metal guanidine compound and its preparation method and application |
| CN109225335B (en) * | 2018-07-27 | 2021-03-12 | 安徽师范大学 | Rare earth metal catalyst containing non-classical alpha-diimine dicarbanion ligand and preparation method and application thereof |
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| CN1789272A (en) * | 2005-12-13 | 2006-06-21 | 苏州大学 | Akoxy rare earth cluster compound and use thereof |
| CN101318145A (en) * | 2008-07-14 | 2008-12-10 | 苏州大学 | Catalyst for preparing amide compounds, synthesis and application thereof |
| CN101318144A (en) * | 2008-07-14 | 2008-12-10 | 苏州大学 | Catalyst for preparing amide compounds, synthesis and application thereof |
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| CN1789272A (en) * | 2005-12-13 | 2006-06-21 | 苏州大学 | Akoxy rare earth cluster compound and use thereof |
| CN101318145A (en) * | 2008-07-14 | 2008-12-10 | 苏州大学 | Catalyst for preparing amide compounds, synthesis and application thereof |
| CN101318144A (en) * | 2008-07-14 | 2008-12-10 | 苏州大学 | Catalyst for preparing amide compounds, synthesis and application thereof |
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| Hongting Sheng,et. al..Novel Mixed-Metal Alkoxide Clusters of Lanthanide and Sodium: Synthesis and Extremely Active Catalysts for the Polymerization of E-Caprolactone and Trimethylene Carbonate.《Inorg. Chem.》.2007,(第46期),7722-7724. * |
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