CN106432138B - A kind of synthetic method of unsaturated acyl amine compound - Google Patents
A kind of synthetic method of unsaturated acyl amine compound Download PDFInfo
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
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Abstract
The present invention relates to a kind of synthetic method of unsaturated acyl amine compound shown in lower formula (III), the method includes：In organic solvent, lower formula (I) compound and formula (II) compound are reacted in the presence of bimetallic catalyst, oxidant, alkali and auxiliary agent, it is post-treated after reaction, to obtain the formula (III) compoundWherein, R H, C1‑C6Alkyl or halogen；R1、R2It is each independently selected from C1‑C6Alkyl or R1、R2With nafoxidine ring or hexahydropyridine ring are formed together with the N connected；X is halogen.This method provides completely new synthetic method for such compound by specific reaction substrate and unique catalystic converter system to obtain purpose product with high yield, has extensive prospects for commercial application.
Description
Technical field
The present invention relates to a kind of synthetic methods of amides compound, relate more particularly to a kind of unsaturated acyl amine chemical combination
The synthetic method of object, belongs to organic chemical synthesis technical field.
Background technology
Amides compound can be widely used among all kinds of organic chemical reactions, such as nucleophilic addition, cycloaddition, freedom
Base reaction etc., while they are also the important synthesis material of multiple biological activities molecule and high molecular material.
And for unsaturated acyl amine compound, since except amide groups, there is also unsaturated bonds, therefore its
Applicability is more extensive in organic synthesis, and more subsequent reactions can occur.Therefore, unsaturated acyl amine compound is studied
Synthetic method is very necessary.
Up to the present, have disclosed or apply in the prior art the synthesis side of a variety of unsaturated acyl amine compounds
Method, such as：
(" the Nickel-Catalyzed Synthesis of Acrylami des such as Kristin D.Schleiher
From r-Olefins and Isocyanates ", Organic Letters, 2007,9,875-878) a kind of nickel is reported to urge
The alkene of change reacts the method for preparing acrylamide compound with isocyanate compound, and reaction equation is as follows：
(" the Organic Iodide ided Carbonylation of Terminal such as Sigeru Torii
Acetylenes wih Palladium Catalyst ", Chemistry Letters, 1991,1673-1676) report one
The synthetic method of the acrylamide of kind palladium chtalyst, organic iodine reagent auxiliary, reaction equation are as follows：
In addition to these approaches, it is further related to using corresponding olefin(e) acid, alkene for synthesizing the conventional method of unsaturated amides
The convenient sources such as acid esters and alkene nitrile.
However, these existing methods but there is substrate source not enough extensively, reaction yield is not high enough, uses corrosivity
Or the problems such as expensive reagent.In view of these drawbacks, the present invention proposes a kind of synthetic method of unsaturated acyl amine compound,
This method uses unique combined reaction catalyst system and catalyzing by specific reaction substrate, to obtain purpose with high yield
Product has extensive prospects for commercial application.
Invention content
In order to overcome many defects as indicated above, present inventor has performed in-depth studies and exploration, are paying
After enough creative works, so as to complete the present invention.
Specifically, technical scheme of the present invention and content are related to unsaturated acyl amine chemical combination shown in a kind of lower formula (III)
The synthetic method of object, the method includes：In organic solvent, lower formula (I) compound and formula (II) compound are urged in bimetallic
It is reacted in the presence of agent, oxidant, alkali and auxiliary agent, it is post-treated after reaction, change to obtain the formula (III)
Object is closed,
Wherein, R H, C1-C6Alkyl or halogen；
R1、R2It is each independently selected from C1-C6Alkyl or R1、R2With nafoxidine ring or six are formed together with the N connected
Pyridinium hydroxide ring；
X is halogen.
Wherein, the C1-C6The meaning of alkyl refers to the linear or branched alkyl group for having 1-6 carbon atom, in non-limiting manner
It may be, for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, n-pentyl, isopentyl or just
Hexyl etc.；The halogen is halogen, may be, for example, F, Cl, Br or I etc..
Wherein, the bimetallic catalyst is molar ratio 1:1 two (triphenylphosphine) cyclopentadienyl group ruthenic chlorides and acetyl
Acetone iron (Fe (acac)3) mixture.
Wherein, the oxidant is tert-butyl hydroperoxide (TBHP), t-butyl peroxybenzoate, potassium peroxydisulfate, peroxide
Change appointing in di-t-butyl (DTBP), bis- chloro- 5,6- dicyanos -1,4- benzoquinones (DDQ) of 2,3- or 2- iodosobenzoic acids (IBX)
Meaning is a kind of, most preferably 2- iodosobenzoic acids (IBX).
Wherein, the alkali is in NaOH, cesium carbonate, potassium tert-butoxide, diethanol amine, KOH or tetramethylethylenediamine (TMEDA)
Any one, most preferably tetramethylethylenediamine (TMEDA).
Wherein, the auxiliary agent is 2,2 '-bipyridyls or 5,5 '-dimethyl -2,2 '-bipyridyls, preferably 5,5 '-diformazans
Base -2,2 '-bipyridyl.
Wherein, the organic solvent is benzene, toluene, n,N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), second
Any one in nitrile, N-Methyl pyrrolidone (NMP) or Isosorbide-5-Nitrae-dioxane or arbitrary a variety of mixture, preferably volume
Than 1:The mixture of 2 dimethyl sulfoxide (DMSO) (DMSO) and acetonitrile.
The dosage of the organic solvent is not particularly limited, if enable to reaction that can fully carry out, and conveniently
Post-processing.Therefore, those skilled in the art can select suitable dosage, this is the experimental ability and water that it should have
It is flat.
Wherein, the mole dosage ratio of formula (I) compound and formula (II) compound can be 1:1.4-2 may be, for example, 1:
1.4,1:1.6,1:1.8 or 1:2.
Wherein, formula (I) compound and bimetallic catalyst are (with two (triphenylphosphine) cyclopentadienyl group ruthenic chlorides and second
Acyl acetone iron (Fe (acac)3) the sum of the two dosage meter) mole dosage ratio can be 1:0.1-0.2 may be, for example, 1:0.1,
1:0.15 or 1:0.2.
Wherein, the mole dosage ratio of formula (I) compound and oxidant can be 1:1.6-2.5 may be, for example, 1:1.6,
1:2 or 1:2.5.
Wherein, the mole dosage ratio of formula (I) compound and alkali can be 1:1-2 may be, for example, 1:1,1:1.5 or 1:2.
Wherein, the mole dosage ratio of formula (I) compound and auxiliary agent can be 1:0.1-0.2 may be, for example, 1:0.1,1:
0.15 or 1:0.2.
Wherein, reaction temperature is 70-100 DEG C, may be, for example, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C.
Wherein, the reaction time can be 6-9 hours, may be, for example, 6 hours, 7 hours, 8 hours or 9 hours.
Wherein, after reaction post-processing is specific as follows：After reaction, it filters, adjusts filtrate pH value to neutrality, and
It is fully washed 2-3 times with deionized water, merges organic phase, anhydrous magnesium sulfate drying is concentrated under reduced pressure, and residue crosses silicagel column color
Spectrum, with volume ratio 1:2 chloroform is rinsed with petroleum ether mixtures, is collected eluent, is evaporated under reduced pressure again, and purpose production is obtained
Object.
Wherein, the reaction mass and/or reagent used in the method for the present invention is known substance, can be by prior art system
It is standby to obtain and/or buy use, it is no longer described in detail herein.
In conclusion the present invention provides a kind of synthetic method of unsaturated acyl amine compound, this method passes through specific
Reaction substrate and unique catalystic converter system provided for such compound to high yield obtain purpose product
Completely new synthetic method has extensive prospects for commercial application.
Specific implementation mode
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not constitutes any type of any restriction to the real protection scope of the present invention, more non-to incite somebody to action
Protection scope of the present invention is confined to this.
Embodiment 1
At room temperature, to appropriate organic solvent (for volume ratio 1:The mixture of 2 dimethyl sulfoxide (DMSO) (DMSO) and acetonitrile) in,
Formula (I) compound, the upper formula (II) compounds of 140mmol, 20mmol bimetallic catalysts are (for 10mmol bis- on addition 100mmol
(triphenylphosphine) cyclopentadienyl group ruthenic chloride and 10mmol ferric acetyl acetonades (Fe (acac)3) mixture), 160mmol oxidation
Agent 2- iodosobenzoic acids (IBX), 200mmol alkali tetramethylethylenediamine (TMEDA) and 10mmol auxiliary agents 5,5 '-dimethyl -2,
2 '-bipyridyls, then stirring is warming up to 70 DEG C, and is stirred to react at such a temperature 9 hours；
After reaction, it filters, adjusts filtrate pH value to neutrality, deionized water is used in combination fully to wash 2-3 times, merge organic
Phase, anhydrous magnesium sulfate drying, is concentrated under reduced pressure, residue crosses silica gel column chromatography, with volume ratio 1:2 chloroform and petroleum ether mixtures
It is rinsed, collects eluent, be evaporated under reduced pressure again, obtain formula (III) purpose product, yield 96.7%.
1H NMR(CDCl3,300MHz):δ7.44-7.38(m,2H),7.07-7.01(m,2H),5.67(s,1H),5.32
(s,1H),3.78-3.58(m,2H),3.42-3.22(m,2H),1.70-1.56(m,4H),1.45-1.35(m,2H)。
Embodiment 2
At room temperature, to appropriate organic solvent (for volume ratio 1:The mixture of 2 dimethyl sulfoxide (DMSO) (DMSO) and acetonitrile) in,
Formula (I) compound, the upper formula (II) compounds of 200mmol, 10mmol bimetallic catalysts are (for 5mmol bis- on addition 100mmol
(triphenylphosphine) cyclopentadienyl group ruthenic chloride and 5mmol ferric acetyl acetonades (Fe (acac)3) mixture), 250mmol oxidants
2- iodosobenzoic acids (IBX), 100mmol alkali tetramethylethylenediamine (TMEDA) and 20mmol auxiliary agents 5,5 '-dimethyl -2,2 ' -
Bipyridyl, then stirring is warming up to 100 DEG C, and is stirred to react at such a temperature 6 hours；
After reaction, it filters, adjusts filtrate pH value to neutrality, deionized water is used in combination fully to wash 2-3 times, merge organic
Phase, anhydrous magnesium sulfate drying, is concentrated under reduced pressure, residue crosses silica gel column chromatography, with volume ratio 1:2 chloroform and petroleum ether mixtures
It is rinsed, collects eluent, be evaporated under reduced pressure again, obtain formula (III) purpose product, yield 96.3%.
1H NMR(CDCl3,300MHz):δ7.44-7.41(m,2H),7.38-7.29(m,3H),5.72(s,1H),5.42
(s, 1H), 3.63 (t, J=6.8Hz, 2H), 3.25 (t, J=6.8Hz, 2H), 1.92-1.86 (m, 2H), 1.85-1.78 (m,
2H)。
Embodiment 3
For reaction equation with embodiment 1, specific reaction process is as follows：
At room temperature, to appropriate organic solvent (for volume ratio 1:The mixture of 2 dimethyl sulfoxide (DMSO) (DMSO) and acetonitrile) in,
Formula (I) compound, the upper formula (II) compounds of 170mmol, 15mmol bimetallic catalysts are (for 7.5mmol bis- on addition 100mmol
(triphenylphosphine) cyclopentadienyl group ruthenic chloride and 7.5mmol ferric acetyl acetonades (Fe (acac)3) mixture), 205mmol oxidation
Agent 2- iodosobenzoic acids (IBX), 150mmol alkali tetramethylethylenediamine (TMEDA) and 15mmol auxiliary agents 5,5 '-dimethyl -2,
2 '-bipyridyls, then stirring is warming up to 80 DEG C, and is stirred to react at such a temperature 7 hours；
After reaction, it filters, adjusts filtrate pH value to neutrality, deionized water is used in combination fully to wash 2-3 times, merge organic
Phase, anhydrous magnesium sulfate drying, is concentrated under reduced pressure, residue crosses silica gel column chromatography, with volume ratio 1:2 chloroform and petroleum ether mixtures
It is rinsed, collects eluent, be evaporated under reduced pressure again, obtain formula (III) purpose product, yield 96.2%.
Characterize data is the same as embodiment 1.
Embodiment 4
For reaction equation with embodiment 2, specific reaction process is as follows：
At room temperature, to appropriate organic solvent (for volume ratio 1:The mixture of 2 dimethyl sulfoxide (DMSO) (DMSO) and acetonitrile) in,
Formula (I) compound, the upper formula (II) compounds of 150mmol, 18mmol bimetallic catalysts are (for 9mmol bis- on addition 100mmol
(triphenylphosphine) cyclopentadienyl group ruthenic chloride and 9mmol ferric acetyl acetonades (Fe (acac)3) mixture), 230mmol oxidants
2- iodosobenzoic acids (IBX), 120mmol alkali tetramethylethylenediamine (TMEDA) and 18mmol auxiliary agents 5,5 '-dimethyl -2,2 ' -
Bipyridyl, then stirring is warming up to 90 DEG C, and is stirred to react at such a temperature 8 hours；
After reaction, it filters, adjusts filtrate pH value to neutrality, deionized water is used in combination fully to wash 2-3 times, merge organic
Phase, anhydrous magnesium sulfate drying, is concentrated under reduced pressure, residue crosses silica gel column chromatography, with volume ratio 1:2 chloroform and petroleum ether mixtures
It is rinsed, collects eluent, be evaporated under reduced pressure again, obtain formula (III) purpose product, yield 96.9%.
Characterize data is the same as embodiment 2.
Comparative example
At room temperature, to appropriate organic solvent (for volume ratio 1:The mixture of 2 dimethyl sulfoxide (DMSO) (DMSO) and acetonitrile) in,
Formula (I) compound, the upper formula (II) compounds of 170mmol, 15mmol bimetallic catalysts are (for 7.5mmol bis- on addition 100mmol
(triphenylphosphine) cyclopentadienyl group ruthenic chloride and 7.5mmol ferric acetyl acetonades (Fe (acac)3) mixture), 200mmol oxidation
Agent 2- iodosobenzoic acids (IBX), 150mmol alkali tetramethylethylenediamine (TMEDA) and 15mmol auxiliary agents 5,5 '-dimethyl -2,
2 '-bipyridyls, then stirring is warming up to 85 DEG C, and is stirred to react at such a temperature 8 hours；
After reaction, it filters, adjusts filtrate pH value to neutrality, deionized water is used in combination fully to wash 2-3 times, merge organic
Phase, anhydrous magnesium sulfate drying, is concentrated under reduced pressure, residue crosses silica gel column chromatography, with volume ratio 1:2 chloroform and petroleum ether mixtures
It is rinsed, collects eluent, be evaporated under reduced pressure again, obtain formula (III) purpose product (t-Bu is tertiary butyl), yield is
75.4%.
1H NMR(CDCl3,500MHz):δ 7.367 (s, 4H), 5.66 (s, 1H), 5.25 (s, 1H), 3.53 (q, J=
7.0Hz, 2H), 3.27 (q, J=7.0Hz, 2H), 1.32 (s, 9H), 1.24 (t, J=7.1Hz, 3H), 1.05 (t, J=7.0Hz,
3H)。
It can be seen that as the R in formula (II) compound1、R2With the N that is connect it is not cyclic when, cause corresponding product to produce
It is significantly reduced when rate is relative to cyclization, this should be due to having led to the cloud density on N when not cyclic and cyclization
Difference, so cause formula (II) compound activity be passivated and caused by.
There are the fact that significant decrease, inventor to find when accelerating agent further is added into reaction system for yield,
Products collection efficiency at this time can be significantly improved, which is disclosed in another application, is no longer described in detail herein.
Embodiment 5-12
Catalyst is replaced with to the two (triphen of one-component of the total dosage of original two kinds of components by the mixture of two kinds of components
Base phosphine) cyclopentadienyl group ruthenic chloride, other operation all sames, so that repetition embodiment 1-4, obtains embodiment 5-8 successively.
Catalyst is replaced with to the one-component levulinic of the total dosage of original two kinds of components by the mixture of two kinds of components
Ketone iron (Fe (acac)3), other operation all sames obtain embodiment 9-12 successively to repeat embodiment 1-4.
As a result it see the table below 1.
Table 1
It can be seen that when using any type one-component, products collection efficiency is caused to have significant decrease, especially only
When using ferric acetyl acetonade, yield is drastically reduced to 27.1-29.6%.And the data of 1-4 are as it can be seen that when using two in conjunction with the embodiments
When the mixture of person is as catalyst, can play each other it is significant mutually promote and improvement, it is excellent to achieve
Products collection efficiency.
Embodiment 13-32
Oxidant IBX is replaced with to the tert-butyl hydroperoxide (TBHP) of same amount, other operation all sames, to weight
Multiple embodiment 1-4, obtains embodiment 13-16 successively.
Oxidant IBX is replaced with to the t-butyl peroxybenzoate of same amount, other operation all sames are real to repeat
A 1-4 is applied, obtains embodiment 17-20 successively.
Oxidant IBX is replaced with to the potassium peroxydisulfate of same amount, other operation all sames, so that embodiment 1-4 is repeated,
Embodiment 21-24 is obtained successively.
Oxidant IBX is replaced with to the di-t-butyl peroxide (DTBP) of same amount, other operation all sames, to weight
Multiple embodiment 1-4, obtains embodiment 25-28 successively.
Oxidant IBX is replaced with to the 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) of same amount, other operations
All same obtains embodiment 29-32 successively to repeat embodiment 1-4.
As a result 2 be see the table below.
Table 2
It can be seen that in all oxidants, IBX has the effect of best, and other oxidants have to a certain degree
Reduction, especially potassium peroxydisulfate reduce it is the most apparent.
Embodiment 33-52
Alkali TMEDA is replaced with to the NaOH of same amount, other operation all sames obtain successively to repeat embodiment 1-4
To embodiment 33-36.
Alkali TMEDA is replaced with to the cesium carbonate of same amount, other operation all sames, to repeat embodiment 1-4, successively
Obtain embodiment 37-40.
Alkali TMEDA is replaced with to the potassium tert-butoxide of same amount, other operation all sames, so that embodiment 1-4 is repeated, according to
It is secondary to obtain embodiment 41-44.
Alkali TMEDA is replaced with to the diethanol amine of same amount, other operation all sames, so that embodiment 1-4 is repeated, according to
It is secondary to obtain embodiment 45-48.
Alkali TMEDA is replaced with to the KOH of same amount, other operation all sames obtain successively to repeat embodiment 1-4
To embodiment 49-52.
As a result 3 be see the table below.
Table 3
It can be seen that the type selection of alkali has a significant impact final yield, highly basic NaOH, KOH and potassium tert-butoxide
Yield it is relatively lower, and TMEDA can then obtain best effect.
Embodiment 53-60
By 5,5 '-dimethyl -2 of auxiliary agent, 2 '-bipyridyls replace with the 2 of same amount, and 2 '-bipyridyls, other operations are homogeneously
Together, to repeat embodiment 1-4, embodiment 53-56 is obtained successively.
Except being added without 5,5 '-dimethyl -2 of auxiliary agent, outside 2 '-bipyridyls, other operation all sames, to repeat embodiment 1-
4, embodiment 57-60 is obtained successively.
As a result 4 be see the table below.
Table 4
It can be seen that when without using auxiliary agent, products collection efficiency has significant decrease.Although and be all bipyridyl, 5,5 '-two
2,2 '-bipyridyl of methyl-will be significantly better than 2,2 '-bipyridyls, this proves minor alteration of the auxiliary agent in structure, can all cause not
Predictable influence.
Embodiment 61-67
Admixture solvent is replaced using following single solvent, to which embodiment 1-4 be repeated, solvent for use repeats in fact
It applies example and yield see the table below 5.
Table 5
It can be seen that when using single solvent, yield has significant decrease, especially NMP.And works as and use DMSO and second
When the mixture of nitrile, the excellent yield of embodiment 1-4 can be obtained.
In conclusion the present invention provides a kind of synthetic method of unsaturated acyl amine compound, this method passes through specific
Reaction substrate and unique catalystic converter system provided for such compound to high yield obtain purpose product
Completely new synthetic method has extensive prospects for commercial application.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limitation protection model of the invention
It encloses.In addition, it should also be understood that, after reading the technical contents of the present invention, those skilled in the art can make the present invention each
Kind change, modification and/or variation, all these equivalent forms equally fall within and are protected defined by the application the appended claims
Within the scope of shield.
Claims (6)
1. the synthetic method of unsaturated acyl amine compound shown in a kind of lower formula (III), the method includes：In organic solvent
In, lower formula (I) compound and formula (II) compound are reacted in the presence of bimetallic catalyst, oxidant, alkali and auxiliary agent,
It is post-treated after reaction, to obtain the formula (III) compound,
Wherein, R H, C1-C6Alkyl or halogen；
R1、R2It is each independently selected from C1-C6Alkyl or R1、R2With nafoxidine ring or hexahydro pyrrole are formed together with the N connected
Phenazine ring；
X is halogen；
The bimetallic catalyst is molar ratio 1:1 two (triphenylphosphine) cyclopentadienyl group ruthenic chlorides and ferric acetyl acetonade it is mixed
Close object；
The oxidant is 2- iodosobenzoic acids；
The alkali is tetramethylethylenediamine；
The auxiliary agent is 5,5 '-dimethyl -2,2 '-bipyridyl；
The organic solvent is volume ratio 1:2 dimethyl sulfoxide (DMSO) and the mixture of acetonitrile.
2. synthetic method as described in claim 1, it is characterised in that：Formula (I) compound is rubbed with formula (II) compound
Your amount ratio is 1:1.4-2.
3. synthetic method as described in claim 1, it is characterised in that：Formula (I) compound and bimetallic catalyst rub
Your amount ratio is 1:0.1-0.2.
4. synthetic method as described in claim 1, it is characterised in that：The mole dosage of formula (I) compound and oxidant
Than being 1:1.6-2.5.
5. synthetic method as described in claim 1, it is characterised in that：The mole dosage ratio of formula (I) compound and alkali is
1:1-2。
6. synthetic method as described in any one in claim 1-5, it is characterised in that：Formula (I) compound and auxiliary agent rub
Your amount ratio is 1:0.1-0.2.
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| Tapas Kumar Achar and Prasenjit Mal.Radical-Induced Metal and Solvent-Free Cross-Coupling Using TBAI−TBHP: Oxidative Amidation of Aldehydes and Alcohols with N‑Chloramines via C−H Activation.《J. Org. Chem.》.2015,第80卷第666−672页. * |
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