CN115353486A - Method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine - Google Patents
Method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine Download PDFInfo
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- -1 heteroaromatic amine Chemical class 0.000 title claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000001408 amides Chemical class 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000004440 column chromatography Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 5
- 238000012544 monitoring process Methods 0.000 claims abstract description 4
- 230000000171 quenching effect Effects 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 47
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000003208 petroleum Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 238000007112 amidation reaction Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000011541 reaction mixture Substances 0.000 abstract 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 23
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 14
- 235000019445 benzyl alcohol Nutrition 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 description 3
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- ORLGLBZRQYOWNA-UHFFFAOYSA-N 4-methylpyridin-2-amine Chemical compound CC1=CC=NC(N)=C1 ORLGLBZRQYOWNA-UHFFFAOYSA-N 0.000 description 2
- MAXBVGJEFDMHNV-UHFFFAOYSA-N 5-chloropyridin-2-amine Chemical compound NC1=CC=C(Cl)C=N1 MAXBVGJEFDMHNV-UHFFFAOYSA-N 0.000 description 2
- CMBSSVKZOPZBKW-UHFFFAOYSA-N 5-methylpyridin-2-amine Chemical compound CC1=CC=C(N)N=C1 CMBSSVKZOPZBKW-UHFFFAOYSA-N 0.000 description 2
- 229950011175 aminopicoline Drugs 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- IIEJGTQVBJHMDL-UHFFFAOYSA-N 2-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-[2-oxo-2-[3-(sulfamoylamino)pyrrolidin-1-yl]ethyl]-1,3,4-oxadiazole Chemical compound C1CN(CC1NS(=O)(=O)N)C(=O)CC2=NN=C(O2)C3=CN=C(N=C3)NC4CC5=CC=CC=C5C4 IIEJGTQVBJHMDL-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000005536 L01XE08 - Nilotinib Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- BCTQJXQXJVLSIG-UHFFFAOYSA-N mepronil Chemical compound CC(C)OC1=CC=CC(NC(=O)C=2C(=CC=CC=2)C)=C1 BCTQJXQXJVLSIG-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- HHZIURLSWUIHRB-UHFFFAOYSA-N nilotinib Chemical compound C1=NC(C)=CN1C1=CC(NC(=O)C=2C=C(NC=3N=C(C=CN=3)C=3C=NC=CC=3)C(C)=CC=2)=CC(C(F)(F)F)=C1 HHZIURLSWUIHRB-UHFFFAOYSA-N 0.000 description 1
- 229960001346 nilotinib Drugs 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine, which comprises the steps of sequentially adding the heteroaromatic amine, a catalyst, alcohol and a solvent into a reactor, placing the reactor into a heat collection type magnetic stirrer by using oxygen in air as an oxidant, and heating and stirring in an oil bath; and monitoring by TLC until the reaction is complete, quenching the reaction, extracting the reaction mixture, carrying out column chromatography separation, and distilling under reduced pressure to obtain the amide compound. The method takes copper salt as a catalyst and takes O in air 2 The alcohol and the heteroaromatic amine are subjected to amidation reaction under the heating condition as an oxidant, and various amide compounds are directly and efficiently synthesized. The raw materials used in the reaction are nontoxic and environment-friendly, the catalyst is cheap and easy to obtain, the operation process is simple, the product yield is high, the functional group compatibility is good, and the problems that a toxic reagent, an additional additive and an oxidant are required, the reaction system is complex, the cost is high, the yield is low, the functional group compatibility is poor and the like in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine.
Background
Amides are one of the important organic compounds, both as nitrogen-containing derivatives of carboxylic acids and as products of substitution of the hydrogen on the nitrogen atom of ammonia or amines by acyl groups. Amide bonds are present in natural polypeptide compounds and macromolecular polymers and are important constituent units of many natural products, medical reagents, pesticides and coloring agents. For example, the common non-anti-inflammatory antipyretic analgesics Paracetamol, the nerve drug Melanonin, the leukemia drug Nilotinib, the bactericide Mepronil, the herbicide Alachlor and the like all contain amide structures. In view of the wide application of amide compounds, chemists are constantly searching for efficient synthesis methods of amide compounds.
The commonly used amide synthesis methods mainly include the reaction of carboxylic acids and their derivatives with ammonia or amines, the reaction of azides with amines, the reaction of aldehydes with amines, etc. The above method usually requires the use of stoichiometric amount of condensing agent, expensive metal catalyst or hazardous and toxic reaction raw materials, and has harsh conditions, difficult product separation and serious environmental pollution. In the prior art, amide is usually synthesized by alcohol and amine, and the method has the advantages of non-toxic and cheap substrate, mild reaction condition, easy product separation and the like. However, there still exist some disadvantages such as the need for using a noble metal catalyst or adding an excessive amount of an oxidizing agent or an additive in the reaction, poor functional group compatibility, low product yield, etc. Therefore, it is highly desirable to provide a simple, efficient, environmentally friendly, and low-cost amide synthesis method by those skilled in the art.
Disclosure of Invention
The invention aims at the problems and provides a method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine. Solves the problems of complex reaction system, low product yield and high cost in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine, which comprises the following steps:
s1: adding the heteroaromatic amine, a catalyst, alcohol and a solvent into a round-bottom flask in sequence, putting the round-bottom flask into a heat collection type magnetic stirrer by taking oxygen in air as an oxidant, and heating and stirring in an oil bath;
s2: and monitoring by TLC until the reaction is complete, quenching the reaction, extracting the mixture obtained by the reaction, performing column chromatography separation, and distilling under reduced pressure to obtain the amide product.
Further, the alcohol has the following general structural formula:
wherein R is 1 Is one or more of hydrogen, methyl, methoxyl, cyano, cl and Br; the heteroaromatic amine has the following structural general formula:
wherein R is 2 Is one or more of methyl, nitro, cyano, F, cl, br and I.
Further, the amide compound has the following structural general formula:
wherein R is 1 Is one or more of hydrogen, methyl, methoxyl, cyano, cl and Br; r 2 Is one or more of methyl, nitro, cyano, F, cl, br and I.
Further, the reaction process has the following reaction formula:
further, the catalyst is copper salt, and the copper salt is CuI.
Further, the molar ratio of the heteroaromatic amine, the catalyst and the alcohol is 10.
Further, the solvent isN, N-dimethylformamide.
Further, the heating temperature is 110 ℃.
Further, the step S2 quenches the reaction with saturated saline.
Further, the extractant used in the extraction is ethyl acetate.
Further, the eluent for column chromatography separation is a mixture of petroleum ether and ethyl acetate in a volume ratio of 7.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a method for synthesizing amide by catalyzing air oxidation of alcohol and heteroaromatic amine with copper 2 The alcohol and the heteroaromatic amine are subjected to amidation reaction under the heating condition as an oxidant, and a plurality of amide compounds are simply and efficiently synthesized. The method has the advantages of low toxicity of reaction raw materials, environmental protection, cheap and easily obtained catalyst, simple reaction system, high product yield and good functional group compatibility, and solves the problems of the prior art that dangerous and toxic raw materials are required to be used, the reaction system is complex, the product yield is low, the functional group compatibility is poor, the cost is high and the like.
Drawings
FIG. 1 is a scheme showing that of Compound 3aa in example 1 1 Nuclear magnetic resonance spectrum of H-NMR;
FIG. 2 is a photograph of Compound 3aa in example 1 13 Nuclear magnetic resonance spectrum of C-NMR;
FIG. 3 is a photograph of Compound 3ab of example 2 1 Nuclear magnetic resonance spectrum of H-NMR;
FIG. 4 is a photograph of Compound 3ab of example 2 13 Nuclear magnetic resonance spectrum of C-NMR;
FIG. 5 is a drawing of Compound 3ac of example 3 1 Nuclear magnetic resonance spectrum of H-NMR;
FIG. 6 is a photograph of Compound 3ac of example 3 13 Nuclear magnetic resonance spectrum of C-NMR;
FIG. 7 is a photograph of Compound 3ad of example 4 1 Nuclear magnetic resonance spectrum of H-NMR;
FIG. 8 shows the preparation of Compound 3ad in example 4 13 Nuclear magnetic resonance spectrum of C-NMR;
FIG. 9 is of the compound 3ba in example 5 1 Nuclear magnetic resonance spectrum of H-NMR;
FIG. 10 shows a schematic representation of compound 3ba in example 5 13 Nuclear magnetic resonance spectrum of C-NMR;
FIG. 11 is a drawing showing the preparation of Compound 3ca in example 6 1 Nuclear magnetic resonance spectrum of H-NMR;
FIG. 12 is a drawing showing the preparation of Compound 3ca in example 6 13 Nuclear magnetic resonance spectrum of C-NMR;
FIG. 13 shows the preparation of compound 3da in example 7 1 Nuclear magnetic resonance spectrum of H-NMR;
FIG. 14 is a drawing of compound 3da from example 7 13 Nuclear magnetic resonance spectrum of C-NMR.
Detailed Description
In order to make the objects and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
In this embodiment, a method for synthesizing amide by oxidizing alcohol and heteroaromatic amine with copper catalysis in air includes the following steps:
s1: adding a heteroaromatic amine, a catalyst and an alcohol with a molar ratio of 10;
s2: monitoring by TLC until the reaction is complete, quenching the reaction by using saturated saline solution, extracting by using ethyl acetate, then carrying out column chromatography separation and reduced pressure distillation to obtain an amide product, wherein an eluent used for the column chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 7.
The alcohol in this example has the following general structural formula:
the heteroaromatic amine has the following structural general formula:
the amide compound synthesized by the method has the following structural general formula:
wherein R is 1 Is one or more of hydrogen, methyl, methoxyl, cyano, cl and Br; r 2 Is one or more of methyl, nitro, cyano, F, cl, br and I.
The reaction formula of the reaction process of the synthesis method is as follows:
wherein the copper salt catalyst is CuI; the solvent isN, N-dimethylformamide.
Example 1
In this embodiment, a method for synthesizing amide by oxidizing alcohol and heteroaromatic amine with copper catalysis in air includes the following steps:
s1: 0.5 mmol (47 mg) of 2-aminopyridine (2 a), 0.15 mmol (28.5 mg) of the catalyst CuI, 1.25 mmol (130. Mu.L) of benzyl alcohol (1 a) and 1.0 mL of solventN, NSequentially adding Dimethylformamide (DMF) into a round-bottom flask with a magnetic stirrer, heating to 110 ℃ by taking oxygen in air as an oxidant, and stirring for 10 hours;
s2: the reaction was monitored by TLC to be complete, the reaction was quenched with saturated brine, extracted with ethyl acetate, and the organic phase mixture was subjected to column chromatography using a mixture of petroleum ether and ethyl acetate at a volume ratio of 7. The reaction of benzyl alcohol with 2-aminopyridine is as follows:
referring to FIGS. 1-2, characterization data for compound 3aa are as follows:
yellow solid, m.p. 81-82 ℃; 1 H NMR (500 MHz, CDCl 3 ): δ 8.96 (s, 1H), 8.41 (d, J = 8.5 Hz, 1H), 8.21-8.20 (m, 1H), 7.93 (d, J = 7.5 Hz，2H), 7.75 (t, J = 8.5 Hz, 1H), 7.56 (t, J = 7.0 Hz, 1H), 7.49 (t, J = 7.5 Hz, 2H), 7.05 (t, J = 6.0 Hz, 1H); 13 C NMR (150 MHz, CDCl 3 ): δ 165.8, 151.6, 147.8, 138.5, 134.3, 132.2, 128.8, 127.2, 119.9, 114.3; HRMS (ESI) calcd for (C 12 H 10 N 2 NaO + [M+Na] + ) 221.0785; found 221.0693。
example 2
In this embodiment, a method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine includes the following steps:
s1: 0.5 mmol (54 mg) of 2-amino-5-methylpyridine (2 b), 0.15 mmol (28.5 mg) of catalyst CuI, 1.25 mmol (130. Mu.L) of benzyl alcohol (1 a) and 1.0 mL of solventN, NSequentially adding Dimethylformamide (DMF) into a round-bottom flask with a magnetic stirrer, heating to 110 ℃ by taking oxygen in air as an oxidant, and stirring for 12 hours;
s2: the reaction was monitored by TLC to completion, quenched with saturated brine, extracted with ethyl acetate, and the organic phase mixture was subjected to column chromatography using a mixture of petroleum ether and ethyl acetate at a volume ratio of 7. The reaction of benzyl alcohol with 2-amino-5-methylpyridine is as follows:
referring to figures 3-4, characterization data for compound 3ab are as follows:
yellow solid，m.p. 99-100℃; 1 H NMR (400 MHz, CDCl 3 ): 8.98 (s, 1H), 8.30 (d, J = 8.4 Hz, 1H), 7.97 (s, 1H), 7.91 (d, J = 7.2 Hz, 2H), 7.57-7.53 (m, 2H), 7.47 (t, J = 8.0 Hz, 2H), 2.27 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 165.8, 149.5, 147.7, 139.0, 134.5, 132.0, 129.2, 128.7, 127.2, 113.7, 17.8; HRMS (ESI) calcd for (C 13 H 13 N 2 O + [M+H] + ) 213.1022; found 213.1030。
Example 3
In this embodiment, a method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine includes the following steps:
s1: 0.5 mmol (64 mg) of 2-amino-5-chloropyridine (2 c), 0.15 mmol (28.5 mg) of catalyst CuI, 1.25 mmol (130. Mu.L) of benzyl alcohol (1 a) and 1.0 mL of solventN, NSequentially adding Dimethylformamide (DMF) into a round-bottom flask with a magnetic stirrer, heating to 110 ℃ by taking oxygen in air as an oxidant, and stirring for 12 hours;
s2: the reaction was monitored by TLC to completion, quenched with saturated brine, extracted with ethyl acetate, and the organic phase mixture was subjected to column chromatography using a mixture of petroleum ether and ethyl acetate at a volume ratio of 7. The reaction of benzyl alcohol with 2-amino 5-chloropyridine is as follows:
referring to FIGS. 5-6, characterization data for compound 3ac is as follows:
white solid, m.p. 120-121 ℃; 1 H NMR (400 MHz, CDCl 3 ): δ 8.75 (s, 1H), 8.39 (d, J = 8.8 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.91 (d, J = 6.8 Hz, 2H), 7.72 (dd, J = 9.2, 2.8 Hz, 1H), 7.58 (t, J = 7.6 Hz, 1H), 7.5 (t, J = 8.0 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ 165.6, 149.9, 146.5, 138.1, 134.0, 132.4, 128.9, 127.2, 126.9, 114.8; HRMS (ESI) calcd for (C 12 H 9 ClN 2 NaO + [M+Na] + ) 255.0296; found 255.0289。
example 4
S1: 0.5 mmol (53 mg) of 2-amino-4-methylpyridine (2 d), 0.15 mmol (28.5 mg) of catalyst CuI, 1.25 mmol (130. Mu.L) of benzyl alcohol (1 a) and 1.0 mL of solventN, NSequentially adding Dimethylformamide (DMF) into a round-bottom flask with a magnetic stirrer, heating to 110 ℃ by taking oxygen in air as an oxidant, and stirring for 10 hours;
s2: the reaction was monitored by TLC to completion, quenched with saturated brine, extracted with ethyl acetate, and the organic phase mixture was subjected to column chromatography using a mixture of petroleum ether and ethyl acetate at a volume ratio of 7. The reaction of benzyl alcohol with 2-amino-4-methylpyridine is as follows:
referring to FIGS. 7-8, characterization data for compound 3ad is as follows:
a green liquid; 1 H NMR (400 MHz, CDCl 3 ): δ 9.09 (s, 1H), 8.26 (s, 1H), 8.00 (d, J = 5.2 Hz, 1H), 7.92 (d, J = 7.2 Hz, 2H), 7.55 (t, J = 7.2 Hz, 1H), 7.47 (t, J = 8.0 Hz, 2H), 6.86 (d, J = 5.6 Hz, 1H), 2.39 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 165.9, 151.7, 150.0, 147.3, 134.4, 132.1, 128.7, 127.2, 121.0, 114.8, 21.4; HRMS (ESI) calcd for (C 13 H 12 N 2 NaO + [M+Na] + ) 235.0842; found 235.0840。
example 5
S1: 0.5 mmol (47 mg) of 2-aminopyridine (2 a), 0.15 mmol (28.5 mg) of the catalyst CuI, 1.25 mmol (153 mg) of 4-methylbenzyl-alcohol (1 b) and 1.0 mL of solventN, N-Dimethylformamide (DMF) was added sequentially to a round bottom flask with magnetic stir bar using oxygen in air as the oxygenHeating the oxidant to 110 ℃, and stirring for 10 h;
s2: the reaction was monitored by TLC to completion, quenched with saturated brine, extracted with ethyl acetate, and the organic phase mixture was subjected to column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 7. The reaction of 4-methylbenzyl alcohol with 2-aminopyridine is as follows:
referring to FIGS. 9-10, characterization data for compound 3ba is as follows:
yellow solid, m.p. 103-104 ℃; 1 H NMR (400 MHz, CDCl 3 ): δ 8.72 (s, 1H), 8.39 (d, J = 8.4 Hz, 1H), 8.27-8.26 (m, 1H), 7.83 (d, J = 8.0 Hz, 2H), 7.75 (t, J= 8.0 Hz, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.06 (t, J = 6.0 Hz, 1H), 2.43 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 165.6, 151.7, 147.8, 142.8, 138.4, 131.4, 129.5, 127.2, 119.8, 114.1, 21.5; HRMS (ESI) calcd for (C 13 H 12 N 2 NaO + [M+Na] + ) 235.0842; found 235.0835。
example 6
In this embodiment, a method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine includes the following steps:
s1: 0.5 mmol (47 mg) of 2-aminopyridine (2 a), 0.15 mmol (28.5 mg) of catalyst CuI, 1.25 mmol (178 mg) of 4-chlorobenzyl alcohol (1 c) and 1.0 mL of solventN, NSequentially adding Dimethylformamide (DMF) into a round-bottom flask with a magnetic stirrer, heating to 110 ℃ by taking oxygen in air as an oxidant, and stirring for 12 hours;
s2: the reaction was monitored by TLC to completion, quenched with saturated brine, extracted with ethyl acetate, and the organic phase mixture was subjected to column chromatography using a mixture of petroleum ether and ethyl acetate at a volume ratio of 7. The reaction of 4-chlorobenzyl alcohol with 2-aminopyridine is as follows:
referring to FIGS. 11-12, characterization data for compound 3ca is as follows:
white solid, m.p. 141-142 ℃; 1 H NMR (400 MHz, CDCl 3 ): δ 9.07 (s, 1H), 8.59 (d, J = 8.0 Hz, 1H), 8.08 (d, J = 8.4 Hz, 2H), 7.99 (t, J = 8.4 Hz, 1H), 7.67 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 4.8 Hz, 1H), 7.02 (t, J = 4.4 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 165.3, 162.8, 151.8, 147.7, 138.5, 129.2, 126.4, 119.7, 114.2, 114.0; HRMS (ESI) calcd for (C 12 H 10 ClN 2 O + [M+H] + ) 233.0476; found 233.0476。
example 7
In this embodiment, a method for synthesizing amide by oxidizing alcohol and heteroaromatic amine with copper catalysis in air includes the following steps:
s1: 0.5 mmol (47 mg) of 2-aminopyridine (2 a), 0.15 mmol (28.5 mg) of catalyst CuI, 1.25 mmol (141. Mu.L) of 2-methylbenzyl alcohol (1 d) and 1.0 mL of solventN, N-Sequentially adding Dimethylformamide (DMF) into a round-bottom flask with a magnetic stirrer, heating to 110 ℃ by taking oxygen in the air as an oxidant, and stirring for 14 hours;
s2: the reaction was monitored by TLC to completion, quenched with saturated brine, extracted with ethyl acetate, and the organic phase mixture was subjected to column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 7. The reaction of 2-methylbenzyl alcohol with 2-aminopyridine is as follows:
referring to FIGS. 13-14, characterization data for compound 3da is as follows:
yellow solid, m.p. 111-112 ℃; 1 H NMR (400 MHz, CDCl 3 ): δ 8.95 (s, 1H), 8.38 (d, J = 8.4 Hz, 1H), 7.93 (d, J = 4.4 Hz, 1H), 7.74 (t, J = 8.4 Hz, 1H), 7.52 (d, J = 6.8 Hz, 1H), 7.38 (t, J = 6.4 Hz, 1H), 7.27-7.23 (m, 2H), 6.99 (dd, J= 8.0, 5.2, 1H), 2.52 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 168.4, 151.6, 147.7, 138.5, 136.5, 135.9, 131.3, 130.5, 126.9, 125.9, 119.8, 114.1, 19.9; HRMS (ESI) calcd for (C 13 H 12 N 2 NaO + [M+Na] + ) 235.0842; found: 235.0835。
examples 8-9 the amount of catalyst was adjusted based on equation (12) as shown in the following table, and the remaining steps were as in the above examples, wherein reactants 1a (1.25 mmol), 2a (0.5 mmol), solvent were 1.0 mL, the ratio of catalyst in the table was the ratio of catalyst to heteroaromatic amine, and O in air was used as the ratio of catalyst to heteroaromatic amine 2 As an oxidizing agent.
As can be seen from the characterization data of the compounds prepared in the above examples, the method of the present invention uses alcohol and heteroaromatic amine as raw materials, copper salt as a catalyst, and O in air 2 The amide compound is an oxidant, is synthesized under the heating condition, has cheap and easily obtained reaction raw materials, simple reaction system and high product yield of more than 75 percent.
In conclusion, the method of the invention takes copper salt as a catalyst and takes O in air 2 The alcohol and the heteroaromatic amine are subjected to amidation reaction under the heating condition as an oxidant. The method has the advantages of nontoxic and environment-friendly raw materials, cheap and easily-obtained catalyst, simple reaction system, high product yield, wide substrate range and good functional group compatibility, and solves the problems ofThe prior art has the problems of complex reaction system, hazardous and toxic raw materials, low yield, poor functional group compatibility, high cost and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine is characterized in that: the method comprises the following steps:
s1: adding the heteroaromatic amine, a catalyst, alcohol and a solvent into a round-bottom flask in sequence, putting the round-bottom flask into a heat collection type magnetic stirrer by taking oxygen in air as an oxidant, and heating and stirring in an oil bath;
s2: and monitoring by TLC until the reaction is complete, quenching the reaction, extracting a mixture obtained by the reaction, carrying out column chromatography separation, and carrying out reduced pressure distillation to obtain an amide product.
2. The method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine according to claim 1, characterized in that: the alcohol has the following structural formula:
wherein R is 1 Is one or more of hydrogen, methyl, methoxyl, cyano, cl and Br; the heteroaromatic amine has the following structural general formula:
wherein R is 2 Is one or more of methyl, nitryl, cyano, F, cl, br and I.
3. The process of claim 1 for the synthesis of an amide by copper catalyzed air oxidation of an alcohol with a heteroaromatic amine, wherein: the amide compound has the following structural general formula:
4. the method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine according to claim 1, characterized in that: the catalyst is copper salt, and the copper salt is CuI.
5. The method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine according to claim 1, characterized in that: the molar ratio of heteroaromatic amine, catalyst to alcohol is 10.
6. The process of claim 1 for the synthesis of an amide by copper catalyzed air oxidation of an alcohol with a heteroaromatic amine, wherein: the solvent isN, N-dimethylformamide.
7. The method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine according to claim 1, characterized in that: the heating temperature was 110 ℃.
8. The method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine according to claim 1, characterized in that: the step S2 is to quench the reaction by using saturated saline solution.
9. The method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine according to claim 1, characterized in that: the extractant in the extraction process is ethyl acetate.
10. The method for synthesizing amide by copper-catalyzed air oxidation of alcohol and heteroaromatic amine according to claim 1, characterized in that: and an eluent in the column chromatography separation is a mixture of petroleum ether and ethyl acetate with the volume ratio of 7.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053558A (en) * | 2018-09-19 | 2018-12-21 | 贵州大学 | A kind of synthetic method of N- heterocyclic amide derivative |
| CN115353487A (en) * | 2022-09-01 | 2022-11-18 | 东北电力大学 | Method for synthesizing N- (2-pyridyl) amide compound under air bubbling condition |
-
2022
- 2022-09-01 CN CN202211060300.XA patent/CN115353486A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053558A (en) * | 2018-09-19 | 2018-12-21 | 贵州大学 | A kind of synthetic method of N- heterocyclic amide derivative |
| CN115353487A (en) * | 2022-09-01 | 2022-11-18 | 东北电力大学 | Method for synthesizing N- (2-pyridyl) amide compound under air bubbling condition |
Non-Patent Citations (14)
| Title |
|---|
| AFSANEH RASHIDIZADEH，等: "Tandem oxidative amidation of alcohols catalyzed by copper modified well-ordered mesoporous graphitic carbon nitride", 《SOLID STATE SCIENCES》, vol. 109, 15 September 2020 (2020-09-15), pages 106427, XP086356932, DOI: 10.1016/j.solidstatesciences.2020.106427 * |
| BEHNAM GHOLIPOUR，等: "Single-pot tandem oxidative/C–H modification amidation process using ultrasmall PdNPencapsulated porous organosilica nanotubes", 《RSC ADV.》, vol. 12, 2 February 2022 (2022-02-02), pages 4276 - 4287 * |
| DAO-QING DONG，等: "Transformation of aldehydes or alcohols to amides at room temperature under aqueous conditions", 《CHINESE CHEMICAL LETTERS》, vol. 28, 9 March 2017 (2017-03-09), pages 1597 - 1599, XP085129701, DOI: 10.1016/j.cclet.2017.03.008 * |
| HAOJIE MA，等: "Copper(I)-catalysed aerobic oxidative selective cleavage of CAC bond with DMAP: Facile access to N-substituted benzamides", 《TETRAHEDRON LETTERS》, vol. 75, 24 May 2021 (2021-05-24), pages 153199, XP086629016, DOI: 10.1016/j.tetlet.2021.153199 * |
| JOHANNES SCHÖRGENHUMER，等: "SNS-Ligands for Ru-Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions", 《ORG. PROCESS RES. DEV.》, vol. 22, 8 June 2018 (2018-06-08), pages 862 - 870 * |
| LANQING DENG，等: "Green, versatile, and scale-up synthesis of amides by aerobic oxidative amination over Ag2O/P-C3N4 photocatalyst", 《CHEMICAL ENGINEERING SCIENCE》, vol. 261, 1 August 2022 (2022-08-01), pages 117960 * |
| MARYAM MIRZA-AGHAYAN，等: "Ultrasound-assisted direct oxidative amidation of benzyl alcohols catalyzed by graphite oxide", 《ULTRASONICS SONOCH》, vol. 32, 11 February 2016 (2016-02-11), pages 37 - 43 * |
| RENUKA M.K.，等: "A polymer supported Cu(II) catalyst for oxidative amidation of benzyl alcohol and substituted amines in TBHP/H2O", 《CATALYSIS COMMUNICATIONS》, vol. 104, 26 October 2017 (2017-10-26), pages 71 - 77, XP085300389, DOI: 10.1016/j.catcom.2017.10.023 * |
| RENZHONG FU，等: "An efficient, eco-friendly and sustainable tandem oxidative amidation of alcohols with amines catalyzed by heteropolyanion-based ionic liquids via a bifunctional catalysis process", 《TETRAHEDRON》, vol. 72, 4 November 2016 (2016-11-04), pages 8319 - 8326, XP029810958, DOI: 10.1016/j.tet.2016.11.002 * |
| SADEGH ROSTAMNIA，等: "Efficient tandem aqueous room temperature oxidative amidations catalysed by supported Pd nanoparticles on graphene oxide", 《CATAL. SCI. TECHNOL.》, vol. 6, 6 January 2016 (2016-01-06), pages 4124 - 4133 * |
| SELLAPPAN SELVAMURUGAN，等: "Ruthenium(II) carbonyl complexes containing bidentate 2-oxo-1, 2- dihydroquinoline-3-carbaldehyde hydrazone ligands as efficient catalysts for catalytic amidation reaction", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》, vol. 803, 15 December 2015 (2015-12-15), pages 119 - 127, XP029383311, DOI: 10.1016/j.jorganchem.2015.11.017 * |
| SIZHUO YANG，等: "Copper-catalyzed dehydrogenative reaction: synthesis of amide from aldehydes and aminopyridine", 《TETRAHEDRON》, vol. 69, 23 May 2013 (2013-05-23), pages 6431 - 6435, XP028570785, DOI: 10.1016/j.tet.2013.05.072 * |
| YEFENG ZHU，等: "Solvent-Controlled Copper-Catalyzed Oxidation of Benzylic Alcohols to Aldehydes and Esters", 《EUR. J. ORG. CHEM.》, 12 June 2013 (2013-06-12), pages 4503 - 4508 * |
| 杨威，等: "铜催化醇与氨基吡啶在有氧条件下合成酰胺", 《高等学校化学学报》, vol. 44, no. 8, 31 August 2023 (2023-08-31), pages 20230029 * |
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