CN117164544A - Preparation method of pyrone derivative containing carboxamide structure - Google Patents
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- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical class O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 title claims 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- -1 iodine Substances 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000003446 ligand Substances 0.000 claims 3
- 239000003513 alkali Substances 0.000 claims 2
- 239000002585 base Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 25
- 150000003857 carboxamides Chemical group 0.000 description 11
- 238000005810 carbonylation reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000004071 biological effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 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
- 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
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000001548 androgenic effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005936 thiocarbonylation reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of a pyrone derivative containing a formamide structure, which comprises the following steps: palladium acetate, triphenylphosphine, iodine, molybdenum carbonyl, N-diisopropylethylamine, water, 1, 3-eneyne compound and nitroarene are reacted for 24 hours at 100 ℃, and after the reaction is completed, the pyrone derivative containing the formamide structure is obtained by post treatment. According to the preparation method, nitroarene is used as a nitrogen source, and molybdenum carbonyl is used as a carbonyl source and a reducing agent, so that the operation is simple, the initial raw materials of the reaction are cheap and easy to obtain, the tolerance range of the substrate functional group is wide, and the reaction efficiency is high. Can synthesize various pyrone derivatives containing formamide structures according to actual needs, is convenient to operate and widens the practicability of the method.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a pyrone derivative containing a formamide structure.
Background
Pyranone derivatives are an important class of heterocyclic molecules which are widely present as core structures in a large number of natural products and exhibit a variety of pharmaceutical and biological activities, such as antibacterial, antifungal, androgenic, phytotoxic etc. (chem. Rev.2005,105, 4559-4580). Accordingly, there has been a great deal of attention directed to the synthesis of pyrones, and a great deal of attempts have been made in this regard. However, conventional synthetic strategies and metal catalyzed processes still suffer from drawbacks such as limited substrate range, harsh reaction conditions, and the like. Based on this, in recent years chemists have developed a series of methods for constructing pyrone derivatives by using various electrophiles and coupling reagents. Nevertheless, the pyranone derivative is still of great importance for the exploration of its synthetic methods as a molecule with diverse biological activities.
In recent years, transition metal catalyzed carbonylation reactions have become a very powerful and efficient synthetic means for preparing carbonyl-containing compounds. Such methods have attracted more and more attention not only in academia but also in industry due to their atomic economy, and are being brought to attention in the field of organic synthesis (chem. Rev.2019,119, 2090-2127). Therefore, in consideration of the synthesis value of the carbonylation reaction and the important biological activity of the pyrone derivative, the synthesis of the pyrone derivative by the simple and general carbonylation reaction has very broad development prospect. However, to our knowledge, methods for synthesizing pyrone derivatives by carbonylation reactions are very limited and are worthy of further research and development. Meanwhile, nitroaromatics are paid much attention as a compound which is widely available, low in cost and easy to obtain, and the reaction of taking nitroaromatics as nitrogen substitutes is well developed. Nevertheless, the field of carbonylation reactions with nitroarenes as nitrogen precursors is still worth further research and popularization.
Based on this, we developed a palladium-catalyzed carbonylation cyclization reaction for synthesizing pyrone derivatives containing a carboxamide structure. Starting from a simple and easily obtained 1, 3-eneyne compound and a nitroaromatic compound, molybdenum carbonyl is used as a carbonyl source and a reducing agent to synthesize a plurality of pyrone derivatives containing a formamide structure, and a new way is opened for the thiocarbonylation reaction of the nitroaromatic compound.
Disclosure of Invention
The invention provides a preparation method of a pyrone derivative containing a formamide structure, which has the advantages of simple steps, low-cost and easily-obtained reaction raw materials, compatibility with various functional groups, good reaction applicability, and new direction for synthesizing the pyrone derivative containing the formamide structure by taking nitroarene as a nitrogen source and molybdenum carbonyl as a carbonyl source and a reducing agent.
A process for the preparation of a pyrone derivative containing a carboxamide structure comprising the steps of: reacting a palladium catalyst, triphenylphosphine, iodine, molybdenum carbonyl, N-diisopropylethylamine, water, a 1, 3-eneyne compound and nitroarene for 20-28 hours at 90-110 ℃, and after the reaction is completed, carrying out post-treatment to obtain the pyrone derivative containing the formamide structure;
the structure of the 1, 3-eneyne compound is shown as a formula (II):
the structure of the nitroarene is shown in a formula (III):
Ar-NO 2 (III)；
the structure of the pyrone derivative containing the carboxamide structure is shown as a formula (I):
in the formulae (I) to (III), R is a substituted or unsubstituted phenyl, thiophene, naphthyl or C 1 ～C 8 Alkyl or C 5 ～C 8 Cycloalkyl, the substituent on the phenyl is C 1 ～C 4 Alkyl, cyano or halogen;
ar is a substituted aryl group;
the substituent on the aryl is C 1 ～C 4 Alkyl, C 1 ～C 4 Alkanoyl, C 1 ～C 4 Alkylthio, amino, trifluoromethyl or halogen.
The molar ratio of the palladium catalyst to the triphenylphosphine to the N, N-diisopropylethylamine is 0.1:0.1:1.5;
the substitution positions of R are para-position and meta-position; the substitution position on the aryl group of Ar is para.
The reaction formula is as follows:
in the invention, the optional post-treatment process comprises: filtering, mixing with silica gel, and purifying by column chromatography to obtain corresponding pyrone derivative containing formamide structure.
Preferably, R is a substituted or unsubstituted phenyl, thiophene, cyclohexyl, naphthyl, octyl, tert-butyl, and the substituent on the phenyl is methoxy, cyano or Cl. At this time, the 1, 3-eneyne compound is easily obtained, and the yield of the reaction is high.
Preferably, ar is a substituted phenyl group, and the substituent on the phenyl group is methyl, acetyl, methylthio, amino, trifluoromethyl, F or Br. At this time, the nitroaromatic hydrocarbon is easily obtained, and the yield of the reaction is high.
The 1, 3-eneyne compounds and nitroarenes described for the preparation of pyranone derivatives containing the carboxamide structure are relatively inexpensive and are widely available in nature, preferably 1, 3-eneyne compounds on a molar basis: nitroaromatics: palladium catalyst=1.2 to 1.5:1:0.05 to 0.1; as a further preference, the 1, 3-eneyne compound is: nitroaromatics: palladium catalyst= 1.5:1:0.1.
Preferably, the reaction time is 24 hours, and the reaction time is too long to increase the reaction cost, but on the contrary, it is difficult to ensure the completion of the reaction.
Preferably, the reaction is carried out in tetrahydrofuran in an amount to provide good dissolution of the starting materials, with 0.3mmol of 1, 3-eneyne compound using an amount of tetrahydrofuran of about 1 to 2mL.
Preferably, the palladium catalyst is palladium acetate, and among a plurality of palladium catalysts, palladium acetate is relatively inexpensive, and the reaction efficiency is relatively high when palladium acetate is used as the catalyst.
As a further preferred aspect, the pyrone derivative containing a carboxamide structure is one of the compounds represented by formula (I-1) -formula (I-5):
the compounds represented by the formulae (I-1) to (I-5) are known compounds.
In the preparation method, the 1, 3-eneyne compound, nitroarene, molybdenum carbonyl, palladium acetate, triphenylphosphine, iodine and N, N-diisopropylethylamine are generally commercially available products, and can be conveniently obtained from the market.
Compared with the prior art, the invention has the beneficial effects that: the nitroarene is used as a nitrogen source, the preparation method is simple, the operation is easy, the post-treatment is simple and convenient, the reaction starting materials are cheap and easy to obtain, the tolerance range of the substrate functional group is wide, and the reaction efficiency is high. Can synthesize various pyrone derivatives containing formamide structures according to actual needs, and has strong practicability.
Detailed Description
The invention is further described below in connection with specific embodiments.
Examples 1 to 15
Palladium acetate, triphenylphosphine, iodine, molybdenum carbonyl, N-diisopropylethylamine, water, 1, 3-eneyne compound (II) and nitroarene (III) are added into a 15mL sealed tube according to the raw material ratio of Table 1, tetrahydrofuran (1 mL) is then added, the mixture is uniformly mixed and stirred, the reaction is carried out according to the reaction conditions of Table 2, after the reaction is completed, filtration and silica gel sample mixing are carried out, and the corresponding pyrone derivative (I) containing a formamide structure is obtained through column chromatography purification, wherein the reaction process is shown as the following formula:
TABLE 1 amounts of raw materials to be added in examples 1 to 15
TABLE 2
In tables 1 and 2, T is the reaction temperature, T is the reaction time, tBu is T-butyl, me is methyl, CF 3 Is trifluoromethyl, iPr is isopropyl, OCF 3 Is trifluoromethoxy and Ph is phenyl.
Structure confirmation data for the compounds prepared in examples 1 to 5:
nuclear magnetic resonance of the carboxamide-containing pyranone derivative (I-1) prepared in example 1 1 H NMR 13 C NMR) detection data were:
1 H NMR(400MHz,CDCl 3 )δ7.75(d,J＝9.6Hz,1H),7.69(d,J＝7.2Hz,2H),7.53(t,J＝7.3Hz,1H),7.46(t,J＝7.3Hz,2H),7.19(s,1H),7.11–7.03(m,4H),6.34(d,J＝9.6Hz,1H),2.29(s,3H).
13 C NMR(101MHz,CDCl 3 )δ163.0,161.2,160.7,144.4,134.9,134.5,131.9,130.8,129.6,129.1,128.9,120.1,114.4,114.2,20.9.
nuclear magnetic resonance of the carboxamide-containing pyranone derivative (I-2) prepared in example 2 1 H NMR 13 C NMR) detection data were:
1 H NMR(400MHz,CDCl 3 )δ7.79(d,J＝9.5Hz,1H),7.70–7.67(m,4H),7.56(dd,J＝13.4,7.3Hz,2H),7.47(t,J＝7.6Hz,2H),7.42–7.37(m,2H),6.38(d,J＝9.6Hz,1H),2.55(s,3H).
13 C NMR(101MHz,CDCl 3 )δ197.7,163.5,161.8,160.6,144.3,138.0,137.6,132.2,130.8,129.6,129.3,129.0,128.1,125.1,124.6,119.4,114.5,114.1,26.8.
nuclear magnetic resonance of the pyrone derivative (I-3) having a carboxamide structure obtained in example 3 1 H NMR 13 C NMR) detection data were:
1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝9.6Hz,1H),7.69(d,J＝7.5Hz,2H),7.60–7.53(m,1H),7.48(t,J＝6.5Hz,2H),7.21–7.13(m,3H),6.96(t,J＝7.5Hz,2H),6.36(d,J＝9.6Hz,1H).
13 C NMR(101MHz,CDCl 3 )δ163.2,161.5,160.7,159.9(d,J＝245.0Hz),144.4,133.1(d,J＝2.5Hz),132.1,130.8,129.3,129.0,121.9(d,J＝8.0Hz),115.9(d,J＝22.5Hz),114.4,114.2.
nuclear magnetic resonance of the pyrone derivative (I-4) having a carboxamide structure obtained in example 4 1 H NMR 13 C NMR) detection data were:
1 H NMR(400MHz,CDCl 3 )δ7.91(s,1H),7.82(s,1H),7.61(d,J＝9.5Hz,1H),7.36–7.31(m,4H),7.13(d,J＝8.1Hz,2H),6.23(d,J＝9.5Hz,1H),2.32(s,3H).
13 C NMR(101MHz,CDCl 3 )δ163.3,160.8,156.0,144.4,135.1,134.8,131.9,129.8,129.8,127.3,126.8,120.1,113.8,113.7,21.0.
nuclear magnetic resonance of the carboxamide-containing pyranone derivative (I-5) prepared in example 5 1 H NMR 13 C NMR) detection data were:
1 H NMR(400 MHz,CDCl 3 )δ7.86(s,1H),7.46(d,J＝7.4 Hz,2H),7.16(d,J＝8.1 Hz,2H),6.10(d,J＝9.5 Hz,1H),3.11–3.04(m,1H),2.34(s,3H),1.88–1.76(m,4H),1.73–1.65(m,2H),1.38–1.19(m,4H).
13 C NMR(101 MHz,CDCl 3 )δ171.8,163.4,161.6,143.3,135.0,129.8,120.3,113.5,112.7,41.1,30.3,29.8,25.8,25.5,21.0。
Claims (9)
1. a process for the preparation of a pyrone derivative having a carboxamide structure comprising the steps of: reacting a palladium catalyst, a ligand, iodine, molybdenum carbonyl, alkali, water, a 1, 3-eneyne compound and nitroarene for 20-28 hours at the temperature of 90-110 ℃, and after the reaction is completed, carrying out post-treatment to obtain the pyrone derivative containing the formamide structure;
the structure of the 1, 3-eneyne compound is shown as a formula (II):
the structure of the nitroarene is shown in a formula (III):
Ar-NO 2 (III)；
the structure of the pyrone derivative containing the carboxamide structure is shown as a formula (I):
in the formulae (I) to (III), R is a substituted or unsubstituted phenyl, thiophene, naphthyl or C 1 ～C 8 Alkyl or C 5 ～C 8 Cycloalkyl, the substituent on the phenyl is C 1 ～C 4 Alkyl, cyano or halogen;
ar is a substituted aryl group;
the substituent on the aryl is C 1 ～C 4 Alkyl, C 1 ～C 4 Alkanoyl, C 1 ～C 4 Alkylthio, amino, trifluoromethyl or halogen.
2. The process for producing a pyrone derivative having a carboxamide structure according to claim 1, wherein R is a substituted or unsubstituted phenyl group, thiophene, cyclohexyl, naphthyl or octyl group, tert-butyl group, and the substituent on the phenyl group is methoxy, cyano or Cl.
3. The method for producing a pyrone derivative having a carboxamide structure according to claim 1, wherein Ar is a substituted phenyl group, and the substituent on the phenyl group is methyl, acetyl, methylthio, amino, trifluoromethyl, F or Br.
4. The process for producing a pyrone derivative having a carboxamide structure according to claim 1, wherein the 1, 3-eneyne compound is: nitroaromatics: molybdenum carbonyl: palladium catalyst: ligand: iodine: alkali: water=1.2 to 1.5:1.5 to 2:0.05 to 0.1:0.1 to 0.2:1.5 to 2.5:1 to 1.5:1 to 1.5.
5. The process for producing a pyrone derivative having a carboxamide structure according to claim 1, wherein tetrahydrofuran is used as a solvent for the reaction.
6. The method for producing a pyrone derivative having a carboxamide structure according to claim 1, wherein the palladium catalyst is palladium acetate.
7. The method for producing a pyrone derivative having a carboxamide structure according to claim 1, wherein said ligand is triphenylphosphine.
8. The process for producing a pyrone derivative having a carboxamide structure according to claim 1, wherein said base is N, N-diisopropylethylamine.
9. The method for producing a pyrone derivative having a carboxamide structure according to claim 1, wherein the pyrone derivative having a carboxamide structure is one of the compounds represented by the formula (I-1) -formula (I-5):
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