CN106083636A - A kind of synthetic method of arylamides - Google Patents
A kind of synthetic method of arylamides Download PDFInfo
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- CN106083636A CN106083636A CN201610460471.XA CN201610460471A CN106083636A CN 106083636 A CN106083636 A CN 106083636A CN 201610460471 A CN201610460471 A CN 201610460471A CN 106083636 A CN106083636 A CN 106083636A
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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Abstract
The present invention relates to the synthetic method of arylamides shown in a kind of lower formula (III), described method includes: in organic solvent, in the presence of catalyst, oxidant and auxiliary agent, lower formula (I) compound and lower formula (II) compound react, after reaction terminates, post-treated, thus obtain described formula (III) compoundWherein, R is selected from H, C1‑C6Alkyl, C1‑C6Alkoxyl, cyano group or halogen.Described method uses suitable reaction substrate, by catalyst, oxidant and the comprehensive synergism of auxiliary agent, such that it is able to high yield obtains purpose product, is advantageous to industrialized production, and application prospect is extensive.
Description
Technical field
The present invention relates to the synthetic method of a kind of aminated compounds, relate more particularly to a kind of arylamides
Synthetic method, belongs to organic chemical synthesis field.
Background technology
Amido link is the important linker that many has in bioactive peptide molecule, natural product and drug molecule
Group, it can also be used for the conversion of multiple chemical structure.Therefore, developing the synthetic method about amido link or amides compound will
It is a most necessary and meaningful job.
According at present, prior art has been developed for use various different initiation material in order to synthesizing amide key
Method.Such as:
(" the Alkyne Carbonylation by Radicals:Tin-such as Yoshitaka Uenoyama
RadicalCatalyzed Synthesis of a-Methylene Amides from 1-Alkynes,Carbon
Monoxide, and Amines ", Angew.Chem.Int.Ed., 2005,44,1075-1078) report one with acetylenic
Compound is raw material, the method building amide compound by carbonylation, and its reaction equation is as follows:
Lin Yong-Shou etc. (" A Novel Approach for the One-Pot Preparat ion of α-
Amino Amides by Pd-Catalyzed Double Carbohydroaminati-on”,Angew.Chem.Int.Ed.,
2001,40,779-781) reporting the synthetic method of the amides compound of a kind of palladium chtalyst, its reaction equation is as follows:
But, these methods existing often also exist that complex process, yield be not ideal enough or the substrate scope of application relatively
Narrow, and affected the drawbacks such as bigger by substituting group position, electronic effect, it can not fully meet present age organic chemical industry, medicine
The common requirements in the fields such as synthesis.
Based on this respect consider, the invention provides the synthetic method of a kind of arylamides, this kind of method
Using aryl alcohol compounds is initiation material, with phenylhydrazine as aminating agent, by the collaborative of catalyst, oxidant and auxiliary agent with
Mutually promote effect, thus define efficient catalystic converter system, purpose product can be obtained with high yield, be advantageous to work
The production of industry, application prospect is extensive.
Summary of the invention
In order to overcome many defects as indicated above, present inventor has performed in-depth study and exploration, paying
After enough creative works, thus complete the present invention.
Specifically, technical scheme and content relate to arylamides shown in formula (III) under one
Synthetic method, described method includes: in organic solvent, in the presence of catalyst, oxidant and auxiliary agent, lower formula (I) chemical combination
Thing and lower formula (II) compound react, after reaction terminates, post-treated, thus obtain described formula (III) compound,
Wherein, R is selected from H, C1-C6Alkyl, C1-C6Alkoxyl, cyano group or halogen.
In the described synthetic method of the present invention, described C1-C6The implication of alkyl refers to the straight chain with 1-6 carbon atom
Or branched alkyl, can be the most such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, uncle
Butyl, n-pentyl, isopentyl or n-hexyl etc..
In the described synthetic method of the present invention, described C1-C6Alkoxyl then refers to " C defined above1-C6Alkyl " and O
Group after atom is connected, such as methoxyl group, ethyoxyl, positive propoxy, n-butoxy.
In the described synthetic method of the present invention, described halogen is fluorine, chlorine, bromine or iodine atom.
In the described synthetic method of the present invention, described catalyst is two (tricyclohexyl phosphine) Nickel dichloride. (NiCl2
(PCy3)2), appointing in double (diphenylphosphine propane) Nickel Chloride of [1,1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride or 1,3-
Meaning one, most preferably [1,1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride.
In the described synthetic method of the present invention, described oxidant is tert-butyl hydroperoxide (TBHP), peroxidating two uncle
Any one in butyl (DTBP), dilauroyl peroxide, 2-iodosobenzoic acid (IBX) or t-butyl peroxybenzoate,
Most preferably 2-iodosobenzoic acid (IBX).
In the described synthetic method of the present invention, described auxiliary agent is silver trifluoroacetate or silver acetate, most preferably trifluoro second
Acid silver.
In the described synthetic method of the present invention, described organic solvent is the polyethylene glycol 200 (PEG-of volume ratio 1:2
200) with the mixture of DMF (N,N-dimethylformamide).
Wherein, the consumption of described organic solvent does not has strict restriction, and those skilled in the art can be according to practical situation
Suitably selecting and determine, such as its consumption size, to facilitate reaction to carry out and post processing, is no longer carried out at this in detail
Thin description.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of formula (II) compound:
1.5-2.5, such as, can be 1:1.5,1:2 or 1:2.5.
In the described synthetic method of the present invention, described formula (I) compound is 1:0.1-0.2 with the mol ratio of catalyst,
Can be such as 1:0.1,1:0.15 or 1:0.2.
In the described synthetic method of the present invention, described formula (I) compound is 1:1.2-1.6 with the mol ratio of oxidant,
Can be such as 1:1.2,1:1.4 or 1:1.6.
In the described synthetic method of the present invention, described formula (I) compound is 1:0.2-0.3 with the mol ratio of auxiliary agent, example
As being 1:0.2,1:0.25 or 1:0.3.
In the described synthetic method of the present invention, reaction temperature is 70-90 DEG C, such as, can be 70 DEG C, 80 DEG C or 90 DEG C.
In the described synthetic method of the present invention, the response time is 8-12 hour, such as, can be 8 hours, 10 hours or 12
Hour.
In the described synthetic method of the present invention, the post processing that reaction terminates is specific as follows: after reaction terminates, mixed to reaction
Compound adds saturated aqueous sodium thiosulfate, fully vibrates, be extracted with ethyl acetate 2-3 time, merge organic facies, anhydrous sulfur
Acid magnesium is dried, and concentrating under reduced pressure, residue is crossed 300-400 mesh silica gel column chromatography, thus obtained described formula (III) compound.
In sum, the invention provides the synthetic method of a kind of arylamides, this kind of method uses properly
Reaction substrate, by catalyst, oxidant and the comprehensive synergism of auxiliary agent, such that it is able to high yield obtains purpose product,
Being advantageous to industrialized production, application prospect is extensive.
Detailed description of the invention
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, and not the real protection scope to the present invention constitutes any type of any restriction, more non-general
Protection scope of the present invention is confined to this.
Embodiment 1
At room temperature, to appropriate organic solvent (polyethylene glycol 200 and DMF (N, the N-dimethyl formyl for volume ratio 1:2
Amine) mixture) in, add formula (I) compound on 100mmol, 150mmol upper formula (II) compound, 10mmol catalyst [1,
1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride, 120mmol oxidant 2-iodosobenzoic acid (IBX) and 20mmol auxiliary agent three
Fluoroethanoic acid silver, then heats to 70 DEG C, and stirring reaction 12 hours at such a temperature；
After reaction terminates, in reactant mixture, add saturated aqueous sodium thiosulfate, fully vibrate, use ethyl acetate
Extracting 2-3 time, merge organic facies, anhydrous magnesium sulfate is dried, concentrating under reduced pressure, and residue crosses 300-400 mesh silica gel column chromatography, thus
Obtaining upper formula (III) compound, productivity is 96.6%.
1H NMR(CDCl3, 400MHz): δ 7.48 (d, J=7.6Hz, 1H), 7.36 (t, J=7.5Hz, 1H), 7.25-
7.16(m,2H),5.94(s,2H),2.52(s,3H)。
13C NMR(101MHz,CDCl3):δ172.43,136.34,135.22,131.21,130.27,126.98,
125.77,19.95。
Embodiment 2
At room temperature, to appropriate organic solvent (polyethylene glycol 200 and DMF (N, the N-dimethyl formyl for volume ratio 1:2
Amine) mixture) in, add formula (I) compound on 100mmol, 200mmol upper formula (II) compound, 15mmol catalyst [1,
1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride, 140mmol oxidant 2-iodosobenzoic acid (IBX) and 25mmol auxiliary agent three
Fluoroethanoic acid silver, then heats to 80 DEG C, and stirring reaction 10 hours at such a temperature；
After reaction terminates, in reactant mixture, add saturated aqueous sodium thiosulfate, fully vibrate, use ethyl acetate
Extracting 2-3 time, merge organic facies, anhydrous magnesium sulfate is dried, concentrating under reduced pressure, and residue crosses 300-400 mesh silica gel column chromatography, thus
Obtaining upper formula (III) compound, productivity is 96.4%.
1H NMR(CDCl3, 400MHz): δ 7.82 (d, J=8.8Hz, 2H), 6.94 (d, J=8.8Hz, 2H), 6.25 (s,
2H), 4.12 (q, J=7.0Hz, 2H), 1.46 (t, J=7.0Hz, 3H).
13C NMR(101MHz,d6-DMSO):δ167.94,161.32,129.83,126.81,114.24,63.71,
15.03。
Embodiment 3
At room temperature, to appropriate organic solvent (polyethylene glycol 200 and DMF (N, the N-dimethyl formyl for volume ratio 1:2
Amine) mixture) in, add formula (I) compound on 100mmol, 250mmol upper formula (II) compound, 20mmol catalyst [1,
1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride, 160mmol oxidant 2-iodosobenzoic acid (IBX) and 30mmol auxiliary agent three
Fluoroethanoic acid silver, then heats to 90 DEG C, and stirring reaction 8 hours at such a temperature；
After reaction terminates, in reactant mixture, add saturated aqueous sodium thiosulfate, fully vibrate, use ethyl acetate
Extracting 2-3 time, merge organic facies, anhydrous magnesium sulfate is dried, concentrating under reduced pressure, and residue crosses 300-400 mesh silica gel column chromatography, thus
Obtaining upper formula (III) compound, productivity is 96.9%.
1H NMR(CDCl3, 400MHz): δ 7.78 (d, J=8.5Hz, 2H), 7.43 (d, J=8.5Hz, 2H), 6.04 (s,
2H)。
13C NMR(101MHz,d6-DMSO):δ167.31,136.53,133.49,129.86,128.77。
Embodiment 4
At room temperature, to appropriate organic solvent (polyethylene glycol 200 and DMF (N, the N-dimethyl formyl for volume ratio 1:2
Amine) mixture) in, add formula (I) compound on 100mmol, 180mmol upper formula (II) compound, 18mmol catalyst [1,
1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride, 130mmol oxidant 2-iodosobenzoic acid (IBX) and 22mmol auxiliary agent three
Fluoroethanoic acid silver, then heats to 8 DEG C, and stirring reaction 9 hours at such a temperature；
After reaction terminates, in reactant mixture, add saturated aqueous sodium thiosulfate, fully vibrate, use ethyl acetate
Extracting 2-3 time, merge organic facies, anhydrous magnesium sulfate is dried, concentrating under reduced pressure, and residue crosses 300-400 mesh silica gel column chromatography, thus
Obtaining upper formula (III) compound, productivity is 96.2%.
1H NMR(CDCl3, 400MHz): δ 8.24 (s, 1H), 8.02 (dd, J=31.4,8.3Hz, 4H), 7.71 (s, 1H).
13C NMR(101MHz,d6-DMSO):δ166.93,138.75,132.86,128.74,118.85,114.11。
Embodiment 5-12
Embodiment 5-8: except catalyst [1,1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride is replaced with two (three hexamethylenes
Base phosphine) Nickel dichloride. (NiCl2(PCy3)2) outward, other operation is the most constant, thus repeats to implement embodiment 1-4, sequentially obtains reality
Execute example 5-8.
Embodiment 9-12: except catalyst [1,1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride being replaced with 1,3-double (two
Phenylphosphine propane) outside Nickel Chloride, other operation is the most constant, thus repeats to implement embodiment 1-4, sequentially obtains embodiment 9-
12。
Result see table 1.
Table 1
As can be seen here, [1,1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride has a best catalytic effect, and other
Catalyst all causes productivity to be significantly reduced.
Embodiment 13-28
Embodiment 13-16: in addition to oxidant IBX is replaced with tert-butyl hydroperoxide (TBHP), other operation is the most constant,
Thus repeat to implement embodiment 1-4, sequentially obtain embodiment 13-16.
Embodiment 17-20: in addition to oxidant IBX is replaced with di-t-butyl peroxide (DTBP), other operation is the most constant,
Thus repeat to implement embodiment 1-4, sequentially obtain embodiment 17-20.
Embodiment 21-24: in addition to oxidant IBX is replaced with dilauroyl peroxide, other operation is the most constant, thus weight
Implement embodiment 1-4 again, sequentially obtain embodiment 21-24.
Embodiment 25-28: in addition to oxidant IBX is replaced with t-butyl peroxybenzoate, other operation is the most constant, thus
Repeat to implement embodiment 1-4, sequentially obtain embodiment 25-28.
Result see table 2.
Table 2
As can be seen here, in all of oxidant, IBX can obtain best technique effect, and other oxidant all causes
Productivity is less than with the products collection efficiency of a certain degree of reduction, especially dilauroyl peroxide and t-butyl peroxybenzoate
90%.
Embodiment 29-36
Embodiment 29-32: in addition to auxiliary agent silver trifluoroacetate is replaced with silver acetate, other operation is the most constant, thus repeats
Implement embodiment 1-4, sequentially obtain embodiment 29-32.
Embodiment 33-36: in addition to being omitted by auxiliary agent silver trifluoroacetate, other operation is the most constant, thus repeats to implement
Embodiment 1-4, sequentially obtains embodiment 33-36.
Result see table 3.
Table 3
As can be seen here, although similar with silver trifluoroacetate height, but the products collection efficiency of silver acetate has significantly reduction.
And it was unexpectedly determined that when not using any auxiliary agent, acquired products collection efficiency is but very nearly the same with the productivity of silver acetate, this
Demonstrate when using silver acetate, do not play the promotion in any front and improve effect, but silver trifluoroacetate has significantly
Improvement result.
Embodiment 37-44
Embodiment 37-40: in addition to organic solvent is replaced with one-component PEG-200, other operation is the most constant, thus weight
Implement embodiment 1-4 again, sequentially obtain embodiment 37-40.
Embodiment 41-44: in addition to organic solvent is replaced with one-component DMF, other operation is the most constant, thus repeats reality
Execute embodiment 1-4, sequentially obtain embodiment 41-44.
Result see table 4.
Table 4
As can be seen here, when using any single solvent component, productivity is all caused to be significantly reduced, especially
DMF.But it is surprising that when using the mixture of PEG-200 Yu DMF of volume ratio 1:2 as organic solvent, but can
Obtaining the products collection efficiency of up to 96%, this proves that the kind of solvent selects to interfere significantly on reaction process and end product equally
Productivity.
In sum, the invention provides the synthetic method of a kind of arylamides, this kind of method uses properly
Reaction substrate, by catalyst, oxidant and the comprehensive synergism of auxiliary agent, such that it is able to high yield obtains purpose product,
Being advantageous to industrialized production, application prospect is extensive.
Should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit the protection model of the present invention
Enclose.Additionally, it will also be appreciated that after the technology contents having read the present invention, the present invention can be made respectively by those skilled in the art
Planting change, amendment and/or modification, all these equivalent form of value falls within the guarantor that the application appended claims is limited equally
Within the scope of protecting.
Claims (10)
1. a synthetic method for arylamides shown in lower formula (III), described method includes: in organic solvent,
In the presence of catalyst, oxidant and auxiliary agent, lower formula (I) compound and lower formula (II) compound react, after reaction terminates,
Post-treated, thus obtain described formula (III) compound,
Wherein, R is selected from H, C1-C6Alkyl, C1-C6Alkoxyl, cyano group or halogen.
2. synthetic method as claimed in claim 1, it is characterised in that: described catalyst is two (tricyclohexyl phosphine) Nickel dichloride.
(NiCl2(PCy3)2), double (diphenylphosphine propane) Nickel Chloride of [1,1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride or 1,3-
In any one, most preferably [1,1 '-bis-(diphenylphosphine) ferrocene] Nickel Chloride.
3. synthetic method as claimed in claim 1 or 2, it is characterised in that: described oxidant is tert-butyl hydroperoxide
(TBHP), di-t-butyl peroxide (DTBP), dilauroyl peroxide, 2-iodosobenzoic acid (IBX) or benzoyl hydroperoxide uncle
Any one in butyl ester, most preferably 2-iodosobenzoic acid (IBX).
4. the synthetic method as described in any one of claim 1-3, it is characterised in that: described auxiliary agent is silver trifluoroacetate or acetic acid
Silver, most preferably silver trifluoroacetate.
5. the synthetic method as described in any one of claim 1-4, it is characterised in that: described organic solvent is volume ratio 1:2
Polyethylene glycol 200 (PEG-200) and the mixture of DMF (N,N-dimethylformamide).
6. the synthetic method as described in any one of claim 1-5, it is characterised in that: described formula (I) compound is changed with formula (II)
The mol ratio of compound is 1:1.5-2.5.
7. the synthetic method as described in any one of claim 1-6, it is characterised in that: described formula (I) compound and catalyst
Mol ratio is 1:0.1-0.2.
8. the synthetic method as described in any one of claim 1-7, it is characterised in that: described formula (I) compound and oxidant
Mol ratio is 1:1.2-1.6.
9. the synthetic method as described in any one of claim 1-8, it is characterised in that: described formula (I) compound rubs with auxiliary agent
That ratio is 1:0.2-0.3.
10. the synthetic method as described in any one of claim 1-9, it is characterised in that: reaction temperature is 70-90 DEG C；During reaction
Between be 8-12 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107652202A (en) * | 2017-10-17 | 2018-02-02 | 孙冉 | A kind of synthetic method of benzamide compound |
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| CN1569820A (en) * | 2004-04-26 | 2005-01-26 | 南京大学 | Process for synthesis of L-glutamine |
| CN105669491A (en) * | 2016-03-14 | 2016-06-15 | 苏州大学 | Acidylation method of amine |
Non-Patent Citations (2)
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| ROSTAM ALI MOLLA ETAL: "An aerobic oxidative synthesis of aryl nitriles and primary aryl amides from benzylic alcohols", 《NEW J. CHEM.》 * |
| RYOSUKE OHMURA ETAL: "Metal-free one-pot oxidative conversion of benzylic alcohols and benzylic halides into aromatic amides with molecular iodine in aq ammonia, and hydrogen peroxide", 《TETRAHEDRON LETTERS》 * |
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| CN107652202A (en) * | 2017-10-17 | 2018-02-02 | 孙冉 | A kind of synthetic method of benzamide compound |
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