CN114539157B - Method for preparing 4-iodo-N-aryl pyrazole compound by iodine-promoted oxidation method - Google Patents
Method for preparing 4-iodo-N-aryl pyrazole compound by iodine-promoted oxidation method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000003647 oxidation Effects 0.000 title claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011630 iodine Substances 0.000 claims abstract description 19
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000006192 iodination reaction Methods 0.000 claims abstract description 9
- 230000026045 iodination Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000004440 column chromatography Methods 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
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- 238000003786 synthesis reaction Methods 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 4
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- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 3
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- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 2
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- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 2
- KSCRVOKQPYZBHZ-IXPOFIJOSA-N benzyl n-[(2s)-1-[[(2s)-1-[[(2s)-1-(1,3-benzothiazol-2-yl)-1-oxo-3-[(3s)-2-oxopyrrolidin-3-yl]propan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-methyl-1-oxobutan-2-yl]carbamate Chemical compound N([C@H](C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C[C@H]1C(NCC1)=O)C(=O)C=1SC2=CC=CC=C2N=1)C(C)C)C(=O)OCC1=CC=CC=C1 KSCRVOKQPYZBHZ-IXPOFIJOSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- RZEKVGVHFLEQIL-UHFFFAOYSA-N celecoxib Chemical compound C1=CC(C)=CC=C1C1=CC(C(F)(F)F)=NN1C1=CC=C(S(N)(=O)=O)C=C1 RZEKVGVHFLEQIL-UHFFFAOYSA-N 0.000 description 2
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- JZCPYUJPEARBJL-UHFFFAOYSA-N rimonabant Chemical compound CC=1C(C(=O)NN2CCCCC2)=NN(C=2C(=CC(Cl)=CC=2)Cl)C=1C1=CC=C(Cl)C=C1 JZCPYUJPEARBJL-UHFFFAOYSA-N 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
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- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical group C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
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- REDUQXCPUSNJOL-UHFFFAOYSA-N C(C1=CC=CC=C1)NC(CN(C(C1=CC=C(C=C1)C(C)C)=O)CC1=CC=C(C=C1)C(NO)=O)=O Chemical compound C(C1=CC=CC=C1)NC(CN(C(C1=CC=C(C=C1)C(C)C)=O)CC1=CC=C(C=C1)C(NO)=O)=O REDUQXCPUSNJOL-UHFFFAOYSA-N 0.000 description 1
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- 240000007594 Oryza sativa Species 0.000 description 1
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- 241000607479 Yersinia pestis Species 0.000 description 1
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- 230000003579 anti-obesity Effects 0.000 description 1
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- 238000005899 aromatization reaction Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members 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
- C07D233/70—One oxygen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing a 4-iodo-N-aryl pyrazole compound by an iodine-promoted oxidation method, which relates to the technical field of organic synthesis and comprises the following steps: the invention provides a method for preparing 4-iodo-N-aryl pyrazoles by taking N-aryl-3-pyrazolidines as an initial raw material, dimethyl sulfoxide as a reaction solvent, iodine as a catalyst and an iodination reagent, and carrying out dehydroaromatization/iodination series process on the N-aryl-3-pyrazolidines under the reaction condition of heating at 100-120 ℃.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for preparing 4-iodo-N-aryl pyrazole compounds by an iodine-promoted oxidation method.
Background
Currently, more than half of the compounds and drugs belong to the class of heterocyclic compounds. Pyrazole is an important five-membered nitrogen heterocyclic compound, widely exists in natural products and bioactive molecules, is an important building block for constructing bioactive compounds in the research and development of new drugs, and is an important framework unit in the total synthesis of alkaloid natural products. N-arylpyrazoles are important components in the N-arylpyrazoles, are hot spots for research, and are derived based on the structure, so that the obtained novel compounds possibly show different biological activities, and are beneficial to the discovery of pesticides or medical leads. For example, the pesticide fipronil is found by Bayer company, has broad insecticidal spectrum, can prevent and control lepidoptera pests such as vegetables, rice, cotton and the like, has acaricidal activity, and a plurality of derivatives with high-efficiency insecticidal activity are created and successfully marketed by a plurality of domestic and foreign companies by taking fipronil structure as a guide; celecoxib (Celebrex) is a drug used for relieving symptoms and signs of osteoarthritis, relieving symptoms and signs of adult rheumatoid arthritis, and treating adult acute pain.
Many methods for synthesizing N-arylpyrazoles have been developed, with the most common synthetic strategies being: obtained by the ring condensation reaction of N-arylhydrazine with 1, 3-dicarbonyl compound or its analogue. Therefore, the development of the pyrazole compound with cheap and easily available raw materials, simple steps, convenient operation, mild conditions and high efficiency is a focus of attention of organic chemistry and pharmacy workers. Thus, a method for synthesizing pyrazole derivatives by the dehydroaromatization/iodination of N-aryl-3-pyrazolidinones remains of considerable interest and value.
Disclosure of Invention
The invention aims to provide a method which has mild reaction conditions, simple operation steps and post-treatment processes and high yield and is suitable for preparing a large amount of 4-iodo-N-aryl pyrazole compounds.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides a method for preparing a 4-iodo-N-aryl pyrazole compound by an iodine-promoted oxidation method, which comprises the following steps: n-aryl-3-pyrazolidinone compound is taken as an initial raw material, dimethyl sulfoxide (DMSO) is taken as a reaction solvent, iodine is taken as a catalyst and an iodination reagent, and under the reaction condition of heating at 100-120 ℃, the N-aryl-3-pyrazolidinone compound is subjected to dehydroaromatization/iodination tandem to prepare the 4-iodo-N-arylpyrazole compound.
Further, the N-aryl-3-pyrazolidinone compoundThe structural formula of (1) is shown in the formula 1, R in the formula 1 1 =h, 2-Me, 2-Cl, 2,4-Cl, 3-Br, 3-OMe, 4-Me, 4-F, 4-Cl, 4-Br or 4-CF 3 ;R 2 =h or Ph;
further, the structural formula of the 4-iodo-N-aryl pyrazole compound is shown in formula 2, wherein R in formula 2 1 =h, 2-Me, 2-Cl, 2,4-Cl, 3-Br, 3-OMe, 4-Me, 4-F, 4-Cl, 4-Br or 4-CF 3 ;R 2 =h or Ph;
further, the reaction time is 18-24 hours.
Further, the mass ratio of the N-aryl-3-pyrazolidinone compound to iodine is (32.4-48.0): 55.8.
further, the reaction was carried out under an air atmosphere.
Further, after the reaction is finished at 100-120 ℃, the method also comprises the processes of extraction, drying and column chromatography separation.
Further, after the reaction, cooling to room temperature, then adding saturated sodium thiosulfate aqueous solution and ethyl acetate (volume ratio is 1:1), extracting for 3 times, taking an organic layer solution, drying with anhydrous sodium sulfate, evaporating the solvent, and separating the crude product by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to obtain the N-arylpyrazole compound.
The invention takes N-aryl-3-pyrazolidinone compound as an initial raw material (0.20 mmol,32.4mg-48.0 mg), then dimethyl sulfoxide solvent is added for dissolution, iodine is taken as a catalyst and an iodination reagent, the reaction is carried out for 18-24 hours under the reaction condition of air (monitored by thin layer chromatography), the temperature is cooled to room temperature, then water is added, ethyl acetate (volume ratio of 1:1) is extracted for 3 times, organic layer solution is taken, anhydrous sodium sulfate is dried, solvent is evaporated, and crude product is separated by column chromatography (eluent, petroleum ether: ethyl acetate), thus obtaining the N-arylpyrazole compound (yield is 28% -88%). The invention has the advantages of cheap and easily obtained raw materials, mild reaction conditions, better compatibility of functional groups, simple operation steps and post-treatment process and higher efficiency; the reaction does not need any complex reaction conditions such as transition metal catalysts, and the like, so that the pollution of the medicine caused by harmful metal impurities introduced by medicinal bioactive molecules is avoided; meanwhile, iodine atoms are introduced on the pyrazole ring through aromatization/iodination reaction, the product can be further applied to metal-catalyzed coupling reaction and halogen/metal exchange reaction, is easy to derivatize, synthesizes the N-aryl pyrazole compound with diversified structures, and provides a research foundation for research on pharmaceutical chemistry and biological activity of related molecules.
The 4-iodo-N-aryl pyrazole compound prepared by the invention can be applied to the synthesis of drug intermediates.
The invention discloses the following technical effects:
1. the reaction condition is mild, a transition metal catalyst is not needed, the reaction is carried out at the temperature of 100-120 ℃, the operation is simple, and the preparation of the 4-iodo-N-aryl pyrazole compound in large quantity is facilitated.
2. The reaction has better atom economy and high product yield.
3. The reaction substrate has wide range and strong functional group compatibility.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a synthetic route diagram of the preparation method of the present invention;
FIG. 2 is a synthetic scheme for 4-iodo-N-arylpyrazole compound 2a of example 1;
FIG. 3 is a synthetic scheme for 4-iodo-N-arylpyrazole compound 2b of example 2;
FIG. 4 is a synthetic scheme for 4-iodo-N-arylpyrazole compound 2c of example 3;
FIG. 5 is a synthetic scheme for 4-iodo-N-arylpyrazole compound 2d of example 4;
FIG. 6 is a synthetic scheme for 4-iodo-N-arylpyrazole compound 2e of example 5;
FIG. 7 is a synthetic scheme for 4-iodo-N-arylpyrazole compound 2f of example 6;
FIG. 8 is a synthetic scheme for 2g of 4-iodo-N-arylpyrazoles in example 7;
FIG. 9 is a synthetic scheme for 4-iodo-N-arylpyrazoles 2h of example 8;
FIG. 10 is a synthetic scheme for 4-iodo-N-arylpyrazole compound 2i of example 9;
FIG. 11 is a synthetic scheme for 4-iodo-N-arylpyrazole compound 2j of example 10;
FIG. 12 is a synthetic scheme for 4-iodo-N-arylpyrazole compound 2k of example 11;
FIG. 13 is a synthetic scheme showing the synthesis of 2l of 4-iodo-N-arylpyrazole compound of example 12;
FIG. 14 is a synthetic scheme for 4-iodo-N-arylpyrazole compound 2m of example 13;
FIG. 15 is a scheme showing the reaction of compound 2d for synthesizing the pyrazole fungicide Metyletracrol analog.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The synthetic route diagram of the preparation method of the invention is shown in figure 1.
Example 1
Synthesis of 4-iodo-N-arylpyrazole Compound 2a (synthetic scheme see FIG. 2):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, N-aryl-3-pyrazolidinone 1a (0.20 mmol,32.4 mg) was weighed and added, then dimethyl sulfoxide solvent (2.0 mL) was added for dissolution, the reaction tube was capped, transferred to an oil bath at 100deg.C, and reacted under reaction conditions of air for 24 hours (monitored by thin layer chromatography). After the reaction of the raw material 1a is completed, the reaction tube is cooled to room temperature, then saturated sodium thiosulfate solution (5.0 mL) is added, ethyl acetate (5.0 mL) is extracted for 3 times, the organic layer solution is taken, anhydrous sodium sulfate is dried, and evaporated to drynessThe solvent was then separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give N-arylpyrazoles 2a (49.4 mg, 86% yield). 1 H NMR(400MHz,DMSO-d 6 ):δ10.96(s,1H),8.43(s,1H),7.68-7.66(m,2H),7.45-7.41(m,2H),7.22-7.18(m,1H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ162.8,139.4,132.6,129.6,125.3,116.8,49.2.
Example 2
Synthesis of 4-iodo-N-arylpyrazole Compound 2b (synthetic scheme see FIG. 3):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, N-aryl-3-pyrazolidinone 1b (0.20 mmol,35.4 mg) was weighed and added, then dimethyl sulfoxide solvent (2.0 mL) was added for dissolution, the reaction tube was capped, transferred to an oil bath at 100deg.C, and reacted under reaction conditions of air for 18 hours (monitored by thin layer chromatography). After the reaction of the raw material 1b was completed, the reaction tube was cooled to room temperature, then a saturated sodium thiosulfate solution (5.0 mL) was added, ethyl acetate (5.0 mL) was extracted 3 times, an organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give N-arylpyrazoles 2b (52.0 mg, yield 87%). 1 H NMR(400MHz,DMSO-d 6 ):δ10.87(s,1H),8.37(s,1H),7.56-7.53(m,2H),7.24-7.22(m,2H),2.29(s,3H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ162.5,137.2,134.5,132.3,129.9,116.8,48.6,20.4.
Example 3
Synthesis of 4-iodo-N-arylpyrazole Compound 2c (synthetic scheme see FIG. 4):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, N-aryl-3-pyrazolidinone 1c (0.20 mmol,36.0 mg) was weighed and then dissolved in dimethyl sulfoxide solvent (2.0 mL), the reaction tube was capped, transferred to an oil bath at 100deg.C, and reacted under reaction conditions of air for 20 hours (monitored by thin layer chromatography). After the reaction of the raw material 1c is completed, the reaction tube is cooled to room temperature, and thenSaturated sodium thiosulfate solution (5.0 mL) was added, extraction was performed 3 times with ethyl acetate (5.0 mL), the organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated off, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give N-arylpyrazoles 2c (40.4 mg, yield 66%). 1 H NMR(400MHz,DMSO-d 6 ):δ10.93(s,1H),8.42(s,1H),7.72-7.68(m,2H),7.32-7.27(m,2H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ162.8,159.6(d,J C-F =240.2Hz),136.0(d,J C-F =2.6Hz),132.7,118.7(d,J C-F =8.2Hz),116.2(d,J C-F =22.9Hz),49.2; 19 F NMR(376MHz,DMSO-d 6 ):δ-117.85to-117.92(m,1F).
Example 4
Synthesis of 4-iodo-N-arylpyrazole Compound 2d (synthetic scheme see FIG. 5):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, N-aryl-3-pyrazolidinone 1d (0.20 mmol,39.2 mg) was weighed and added, then dimethyl sulfoxide solvent (2.0 mL) was added for dissolution, the reaction tube was capped, transferred to an oil bath at 100℃and reacted under a reaction condition of air for 20 hours (monitored by thin layer chromatography). After the reaction of the starting material 1d was completed, the reaction tube was cooled to room temperature, then a saturated sodium thiosulfate solution (5.0 mL) was added, ethyl acetate (5.0 mL) was extracted 3 times, an organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give N-arylpyrazoles 2d (54.2 mg, yield 85%). 1 H NMR(400MHz,DMSO-d 6 ):δ11.03(s,1H),8.48(s,1H),7.71-7.67(m,2H),7.51-7.47(m,2H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ162.9,138.2,132.8,129.4,129.1,118.3,50.0.
Example 5
Synthesis of 4-iodo-N-arylpyrazole Compound 2e (synthetic scheme see FIG. 6):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added to weigh N-aryl-3-pyrazolidinones1e (0.20 mmol,48.0 mg) was added, followed by dissolution in dimethyl sulfoxide solvent (2.0 mL), covering the reaction tube, transferring to a 100deg.C oil bath, and reacting for 20 hours under air reaction conditions (monitored by thin layer chromatography). After the reaction of the raw material 1e was completed, the reaction tube was cooled to room temperature, then a saturated sodium thiosulfate solution (5.0 mL) was added, ethyl acetate (5.0 mL) was extracted 3 times, an organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give N-arylpyrazoles 2e (53.5 mg, yield 73%). 1 H NMR(400MHz,DMSO-d 6 ):δ11.03(br,s,1H),8.48(s,1H),7.65-7.60(m,4H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ163.3,139.0,133.2,132.7,119.1,117.6,50.5.
Example 6
Synthesis of 4-iodo-N-arylpyrazole Compound 2f (synthetic scheme see FIG. 7):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, N-aryl-3-pyrazolidinone 1f (0.20 mmol,46.0 mg) was weighed and added, then dimethyl sulfoxide solvent (2.0 mL) was added for dissolution, the reaction tube was capped, transferred to an oil bath at 100℃and reacted for 18 hours under a reaction condition of air (monitored by thin layer chromatography). After the reaction of the raw material 1f was completed, the reaction tube was cooled to room temperature, then a saturated sodium thiosulfate solution (5.0 mL) was added, ethyl acetate (5.0 mL) was extracted 3 times, an organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give N-arylpyrazoles 2f (61.0 mg, yield 86%). 1 H NMR(400MHz,DMSO-d 6 ):δ11.20(s,1H),8.62(s,1H),7.89-7.87(m,2H),7.81-7.79(m,2H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ163.3,142.0,133.4,126.9(q,J C-F =3.7Hz),125.0(q,J C-F =32.0Hz),124.3(q,J C-F =270.0Hz),116.8,51.5; 19 F NMR(376MHz,DMSO-d 6 ):δ-60.49(s,3F).
Example 7
Synthesis of 2g of 4-iodo-N-arylpyrazole (synthetic scheme: FIG. 8):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, 1g (0.20 mmol,35.2 mg) of N-aryl-3-pyrazolidinone was weighed and added, then dimethyl sulfoxide solvent (2.0 mL) was added for dissolution, the reaction tube was capped, transferred to an oil bath at 100℃and reacted under a reaction condition of air for 18 hours (monitored by thin layer chromatography). After the reaction of 1g of the starting material was completed, the reaction tube was cooled to room temperature, then a saturated sodium thiosulfate solution (5.0 mL) was added, extraction was performed 3 times with ethyl acetate (5.0 mL), an organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give 2g of N-arylpyrazoles (50.4 mg, yield 84%). 1 H NMR(400MHz,DMSO-d 6 ):δ10.64(s,1H),7.93(s,1H),7.36-7.32(m,1H),7.31-7.29(m,3H),2.26(s,3H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ162.2,139.5,136.1,132.2,131.4,127.7,126.8,125.4,46.8,18.1.
Example 8
Synthesis of 4-iodo-N-arylpyrazole Compound 2h (synthetic scheme see FIG. 9):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, N-aryl-3-pyrazolidinone was weighed for 1h (0.20 mmol,39.2 mg) and then dissolved in dimethyl sulfoxide solvent (2.0 mL), the reaction tube was capped, transferred to a 100deg.C oil bath, and reacted for 18 hours under air reaction conditions (monitored by thin layer chromatography). After the reaction of the starting material 1h was completed, the reaction tube was cooled to room temperature, then a saturated sodium thiosulfate solution (5.0 mL) was added, ethyl acetate (5.0 mL) was extracted 3 times, an organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give an N-arylpyrazole compound for 2h (56.2 mg, yield 88%). 1 H NMR(400MHz,DMSO-d 6 ):δ10.86(s,1H),8.04(s,1H),7.64-7.62(m,1H),7.54-7.51(m,1H),7.48-7.44(m,1H),7.44-7.39(m,1H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ162.6,137.5,136.8,130.6,129.2,128.3,127.5,127.3,48.1.
Example 9
Synthesis of 4-iodo-N-arylpyrazole Compound 2i (synthetic scheme see FIG. 10):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, N-aryl-3-pyrazolidinone 1i (0.20 mmol,39.2 mg) was weighed and added, then dimethyl sulfoxide solvent (2.0 mL) was added for dissolution, the reaction tube was capped, transferred to an oil bath at 100deg.C, and reacted under reaction conditions of air for 22 hours (monitored by thin layer chromatography). After the reaction of the raw material 1i was completed, the reaction tube was cooled to room temperature, then a saturated sodium thiosulfate solution (5.0 mL) was added, ethyl acetate (5.0 mL) was extracted 3 times, an organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give N-arylpyrazoles 2i (53.5 mg, yield 83%). 1 H NMR(400MHz,DMSO-d 6 ):δ11.08(s,1H),8.53(s,1H),7.77-7.76(m,1H),7.66-7.64(m,1H),7.47-7.43(m,1H),7.26-7.23(m,1H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ163.0,140.4,134.0,133.1,131.2,124.8,116.4,115.1,50.5.
Example 10
Synthesis of 4-iodo-N-arylpyrazole Compound 2j (synthetic scheme see FIG. 11):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, N-aryl-3-pyrazolidinone 1j (0.20 mmol,48.0 mg) was weighed and added, then dimethyl sulfoxide solvent (2.0 mL) was added for dissolution, the reaction tube was capped, transferred to an oil bath at 100℃and reacted for 18 hours under the reaction condition of air (monitored by thin layer chromatography). After the reaction of the raw material 1j is completed, the reaction tube is cooled to room temperature, then saturated sodium thiosulfate solution (5.0 mL) is added, ethyl acetate (5.0 mL) is extracted for 3 times, an organic layer solution is taken, anhydrous sodium sulfate is dried, the solvent is evaporated, and then the crude product is separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to obtain the N-aryl pyrazole compoundProduct 2j (52.0 mg, 71% yield). 1 H NMR(400MHz,DMSO-d 6 ):δ11.09(br,s,1H),8.53(s,1H),7.90(s,1H),7.71-7.66(m,1H),7.41-7.37(m,2H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ163.0,140.5,133.1,131.5,127.7,122.4,119.2,115.5,50.5.
Example 11
Synthesis of 4-iodo-N-arylpyrazole Compound 2k (synthetic scheme see FIG. 12):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, N-aryl-3-pyrazolidinone 1k (0.20 mmol,46.0 mg) was weighed and added, then dimethyl sulfoxide solvent (2.0 mL) was added for dissolution, the reaction tube was capped, transferred to an oil bath at 100℃and reacted for 18 hours under a reaction condition of air (monitored by thin layer chromatography). After the reaction of the raw material 1k was completed, the reaction tube was cooled to room temperature, then a saturated sodium thiosulfate solution (5.0 mL) was added, ethyl acetate (5.0 mL) was extracted 3 times, an organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give N-arylpyrazoles 2k (44.7 mg, yield 63%). Compound 2k can be used for the synthesis of the antiobesity drug rimonabant (rimonabant) and its analogues. 1 H NMR(400MHz,DMSO-d 6 ):δ10.94(s,1H),8.06(s,1H),7.84(s,1H),7.55(d,J=1.0Hz,2H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ162.8,136.9,136.6,132.5,130.1,128.6,128.4,128.2,48.4.
Example 12
Synthesis of 4-iodo-N-arylpyrazole Compound 2l (synthetic scheme see FIG. 13):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, 1L (0.20 mmol,38.4 mg) of N-aryl-3-pyrazolidinone was weighed and added, then dimethyl sulfoxide solvent (2.0 mL) was added for dissolution, the reaction tube was capped, transferred to an oil bath at 100℃and reacted under a reaction condition of air for 24 hours (monitored by thin layer chromatography). After the reaction of 1l of the starting material was completed, the reaction tube was cooled to room temperature, and then a saturated sodium thiosulfate solution (5.0 mL) was added,ethyl acetate (5.0 mL) was extracted 3 times, the organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated to dryness, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give 2l of N-arylpyrazoles (20.0 mg, yield 32%). The reason for the lower yield of compound 12: part of the raw materials are decomposed during the reaction. 1 H NMR(400MHz,DMSO-d 6 ):δ10.96(br,s,1H),8.48(s,1H),7.35-7.31(m,1H),7.26-7.24(m,2H),6.78-6.76(m,1H),3.79(s,3H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ162.6,160.2,140.5,132.8,130.4,111.1,108.8,102.3,55.4,49.3.
Example 13
Synthesis of 4-iodo-N-arylpyrazole Compound 2m (synthetic scheme see FIG. 14):
in a 25mL reaction tube, a magnetic stirrer and iodine (1.1 equiv,55.8 mg) were added, N-aryl-3-pyrazolidinone 1m (0.20 mmol,47.6 mg) was weighed and then dissolved in dimethyl sulfoxide solvent (2.0 mL), the reaction tube was capped, transferred to an oil bath at 120℃and reacted under reaction conditions of air for 24 hours (monitored by thin layer chromatography). After the reaction of the starting material 1m was completed, the reaction tube was cooled to room temperature, then a saturated sodium thiosulfate solution (5.0 mL) was added, ethyl acetate (5.0 mL) was extracted 3 times, an organic layer solution was taken, dried over anhydrous sodium sulfate, and the solvent was evaporated, then the crude product was separated by column chromatography (eluent, petroleum ether: ethyl acetate=5:1, volume ratio) to give N-arylpyrazoles 2m (20.1 mg, yield 28%). The reason for the lower yield of compound 13: part of the raw materials are decomposed during the reaction. 1 H NMR(400MHz,DMSO-d 6 ):δ10.89(s,1H),7.41-7.39(m,3H),7.31-7.18(m,5H),7.11-7.09(m,2H); 13 C{ 1 H}NMR(100MHz,DMSO-d 6 ):δ162.1,143.7,139.7,130.1,129.9,129.0,128.8,128.6,126.7,124.2,52.7.
The 4-iodo-N-aryl pyrazole compound prepared by the invention can be applied to synthesis of drug intermediates, for example, the compound 2d can be used for synthesis of a pyrazole fungicide Metyletraprole analogue, and a route diagram is shown in figure 15.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (2)
1. The method for preparing the 4-iodo-N-aryl pyrazole compound by using the iodine-promoted oxidation method is characterized by comprising the following steps of: the method comprises the steps of taking N-aryl-3-pyrazolidinone compounds as initial raw materials, dimethyl sulfoxide as a reaction solvent, iodine as a catalyst and an iodination reagent, and carrying out dehydroaromatization/iodination tandem on the N-aryl-3-pyrazolidinone compounds under the reaction condition of heating at 100-120 ℃ to prepare 4-iodo-N-arylpyrazoles;
the structural formula of the N-aryl-3-pyrazolidinone compound is shown as formula 1, R in formula 1 1 =h, 2-Me, 2-Cl, 3-Br, 3-OMe, 4-Me, 4-F, 4-Cl, 4-Br or 4-CF 3 ;R 2 =h or Ph;
the structural formula of the 4-iodo-N-aryl pyrazole compound is shown in formula 2, R in formula 2 1 =h, 2-Me, 2-Cl, 3-Br, 3-OMe, 4-Me, 4-F, 4-Cl, 4-Br or 4-CF 3 ;R 2 =h or Ph;
the reaction time is 18-24 hours;
the mass ratio of the N-aryl-3-pyrazolidinone compound to iodine is (32.4-48.0): 55.8;
the reaction was carried out under an air atmosphere.
2. The method for preparing 4-iodo-N-arylpyrazoles by iodine-promoted oxidation according to claim 1, wherein the method further comprises extraction, drying and column chromatography separation after the reaction is completed at 100-120 ℃.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2055364A (en) * | 1979-06-18 | 1981-03-04 | Richardson Merrell Inc | 4-Aroylimidazol-2-ones |
CN106632086A (en) * | 2016-12-30 | 2017-05-10 | 江西省林业科学院 | 2-(2-iodoaryl)quinazoline compound and preparation method thereof |
CN108976170A (en) * | 2018-08-14 | 2018-12-11 | 华南理工大学 | A kind of 5- trifluoromethyl -4H- imidazoline -4- ketone derivatives and synthetic method |
CN111233617A (en) * | 2020-03-30 | 2020-06-05 | 荆楚理工学院 | Synthesis method of 1-iodoalkyne compound |
-
2022
- 2022-03-03 CN CN202210202423.6A patent/CN114539157B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2055364A (en) * | 1979-06-18 | 1981-03-04 | Richardson Merrell Inc | 4-Aroylimidazol-2-ones |
CN106632086A (en) * | 2016-12-30 | 2017-05-10 | 江西省林业科学院 | 2-(2-iodoaryl)quinazoline compound and preparation method thereof |
CN108976170A (en) * | 2018-08-14 | 2018-12-11 | 华南理工大学 | A kind of 5- trifluoromethyl -4H- imidazoline -4- ketone derivatives and synthetic method |
CN111233617A (en) * | 2020-03-30 | 2020-06-05 | 荆楚理工学院 | Synthesis method of 1-iodoalkyne compound |
Non-Patent Citations (7)
Title |
---|
A highly efficient metal-free approach to metaand multiple-substituted phenols via a simple oxidation of cyclohexenones;Yu-Feng Liang et al.;《Green Chemistry》;第18卷;6462–6467 * |
Conversion of Simple Cyclohexanones into Catechols;Yu-Feng Liang et al.;《Journal of the American Chemical Society》;第138卷;12271-12277 * |
Emerging Role of Green Oxidant I2/DMSO in Organic Synthesis;Pedavenkatagari Narayana Reddy et al.;《Current Organic Synthesis》;第15卷;815-838 * |
Iodine-Catalyzed Oxidative Aromatization: A Metal-Free Concise Approach to meta-Substituted Phenols from Cyclohex-2-enones;Shi-Ke Wang et al.;《Adv. Synth. Catal.》;第358卷;4093-4099 * |
Iodine-mediated facile dehydrogenation of dihydropyridazin-3(2H)one;Vivek T. Humne et al.;《Chinese Chemical Letters》;第22卷;1435-1438 * |
六氢吡咯吲哚生物碱Esermethole 的全合成;彭天凤 等;《云南大学学报( 自然科学版) 》;第43卷(第3期);562-569 * |
分子碘催化氧化C(sp3)—H 功能化反应的研究进展;张露文 等;《有机化学》;第41卷;1359-1395 * |
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