CN112321553A - Method for synthesizing 3-position difluoromethyl substituted coumarin derivative from aryl alkyne acid ester - Google Patents
Method for synthesizing 3-position difluoromethyl substituted coumarin derivative from aryl alkyne acid ester Download PDFInfo
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- CN112321553A CN112321553A CN202011184520.4A CN202011184520A CN112321553A CN 112321553 A CN112321553 A CN 112321553A CN 202011184520 A CN202011184520 A CN 202011184520A CN 112321553 A CN112321553 A CN 112321553A
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/12—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 3 and unsubstituted in position 7
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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Abstract
The invention relates to the field of organic synthesis, in particular to a 3-position difluoromethyl substituted coumarin derivative synthesized by cyclization of aromatic propiolate. Using [ bis (difluoroacetoxy) iodide]Benzene is used as a difluoromethylation reagent to generate a difluoromethyl radical under the catalysis of visible light, and then aromatic propiolate is subjected to radical addition, oxidation and rearrangement reaction to obtain the 3-position difluoromethyl substituted coumarin derivative. Specifically, aromatic propiolate and its derivative, [ bis (difluoroacetoxyl) iodine, are reacted in a reaction tube]Dissolving benzene with DMAc, reacting at room temperature under the illumination of a blue 18W LED lamp, and synthesizing a series of substituted difluoromethylcoumarin derivatives. In the structural general formula, R is1Selected from cyano, phenyl, methoxy, halogen, t-butyl, and the like; r2Selected from cyclopropyl, phenyl, substituted phenyl and the like. The invention adopts cheap and easily obtained [ bis (difluoroacetoxyl) iodine]As a difluoromethyl source, under the action of no photocatalyst, 3-position difluoromethyl substituted coumarin derivatives are prepared from aromatic propiolate, and the synthetic method is simple, convenient and fast and is very convenient to operate.
Description
Technical Field
The invention belongs to the field of organic synthesis, and relates to a method for synthesizing a 3-position difluoromethyl substituted coumarin derivative by using aryl alkynoate to close a ring.
Background
The introduction of fluorine atoms or fluorine-containing groups into small organic molecules can significantly improve the properties of lipophilicity, lipid solubility, metabolic stability, cell permeability and the like of the molecules. Therefore, research on fluorine-containing organic compounds is increasing, and it is found that fluorine-containing organic compounds play an important role in the fields of medicine, materials, agriculture, and the like. Difluoromethyl is an important group in fluorine-containing functional groups, can be used as an isostere of-NH, -OH or-SH, and is introduced into drug molecules to change the physicochemical property and the pharmacological activity of the drug.
Many difluoromethylation reactions based on difluoromethyl radicals have been reported previously. The difluoromethyl radical precursor used is zinc difluoromethylsulfinate, sodium difluoromethylsulfinate, difluoromethylsulfinyl chloride, difluoromethylbenzothiazolesulfone, difluoromethylphosphine salt, etc. However, the use of these difluoromethylating agents either requires multi-step synthesis or the use of expensive metal catalysts during the difluoromethylation reaction. In 2017, Maruoka et al used [ bis (difluoroacetoxyl) iodo ] benzene as a difluoromethylation reagent to realize direct difluoromethylation of aromatic heterocycles. However, the difluoromethylation of arylalkynates with [ bis (difluoroacetoxy) iodo ] benzene as the difluoromethylating agent was not reported.
The current method for synthesizing the 3-position difluoromethyl substituted coumarin comprises the following steps: 1) benziconate and difluoromethylbenzothiazolesulfone in fac-Ir (ppy)3Under the catalysis of (3), ring closing is carried out under the irradiation of a 5W blue LED lamp. However, the method uses an expensive metal photocatalyst, and the synthesis of the difluoromethylbenzothiazole sulfone requires multi-step reactions. 2) Prepared by reacting sodium difluoromethylsulfinate with coumarin under the catalysis of eosin Y and the irradiation of a 5W blue LED lamp. However, sodium difluoromethylsulfenamide used in this method is synthesized from difluoromethylbenzothiazolesulfone as a starting material.
According to the method, the [ bis (difluoroacetoxyl) iodine ] benzene is used as a difluoromethylation reagent, difluoromethyl free radicals are generated under the catalysis of visible light, and then aromatic propiolate is subjected to free radical addition, oxidation and rearrangement reaction to obtain the 3-position difluoromethyl substituted coumarin derivative. [ bis (difluoroacetoxy) iodo ] benzene can be conveniently prepared by reacting iodobenzene acetate with difluoroacetic acid in 1 step. In addition, the method used in the patent does not need a photocatalyst and is simple and convenient to operate.
Disclosure of Invention
The invention aims to synthesize a 3-position difluoromethyl substituted coumarin derivative by using aryl propiolate through ring closure.
A method for synthesizing difluoromethyl substituted coumarin derivatives by aryl alkynate cyclization under photocatalysis is characterized in that [ bis (difluoroacetoxyl) iodo ] benzene is used as a difluoromethyl source. The method comprises the following specific steps: adding aryl alkyne acid ester, [ bis (difluoroacetoxyl) iodine ] benzene and N, N-dimethylacetamide under the anhydrous and oxygen-free conditions, and reacting at room temperature under the illumination of a blue 18W LED lamp. After the reaction is finished, the difluoromethyl substituted coumarin derivative is obtained through extraction, washing, drying and column chromatography separation.
The reaction general formula of the difluoromethylation method is shown as follows, wherein R1Selected from cyano, phenyl, methoxy, halogen, tert-butyl; r2Selected from cyclopropyl, phenyl, substituted phenyl;
table 1 the structures of difluoromethylcoumarin derivatives synthesized by the present invention are shown in the following table:
compared with the prior art, the invention has the advantages that:
1. the reaction used in the invention does not need a photocatalyst and an oxidant, and the condition operation is simple and relatively mild.
2. [ bis (difluoroacetoxy) iodo ] benzene is stable and easy to prepare
3. [ bis (difluoroacetoxy) iodo ] benzene is both the source of difluoromethyl in the reaction and the oxidant, and plays an important role in oxidizing radicals to carbenium ions, which are then rearranged into the structure of coumarin.
The specific implementation mode is as follows:
the invention provides a method for synthesizing 3-position difluoromethylcoumarin derivatives from aromatic propiolate, and the reaction formula is as follows:
the operation steps are as follows:
firstly, carrying out anhydrous anaerobic treatment on a 10mL Schlenk tube, removing residual water on the wall, the mouth and the tube of the reaction tube at high temperature through a baking gun, carrying out nitrogen gas replacement and air replacement in the reaction tube through double-row tubes to create an anhydrous anaerobic environment, after the Schlenk tube is cooled in a nitrogen atmosphere, sequentially adding aromatic propiolate and a derivative thereof (0.30mmol) and [ bis (difluoroacetoxyl) iodine ] benzene (0.60mmol) into the reaction tube, adding 1.00mL of anhydrous DMAc into the reaction tube under the protection of the double-row tubes of nitrogen gas through a long-needle injector, dissolving two reactants under stirring, and carrying out room-temperature reaction under the illumination of blue 18W LED light. After TLC to confirm the reaction is complete, a large amount of water is added for washing, extraction is carried out for four times by ethyl acetate, saturated sodium chloride solution is washed for two times, an organic phase is taken and dried by anhydrous sodium sulfate, a solvent is removed by rotary evaporation, and a residue is purified by silica gel column chromatography to obtain a product (a mobile phase system is petroleum ether: ethyl acetate).
The following is specifically illustrated by way of example:
example 1
Firstly, carrying out anhydrous anaerobic treatment on a 10mL Schlenk tube, removing residual water on the wall, the mouth and the tube of a reaction tube at high temperature through a baking gun, carrying out nitrogen gas replacement and air replacement in the reaction tube through a double-row tube to create an anhydrous anaerobic environment, and cooling the Schlenk tube in a nitrogen atmosphere, and then carrying out anhydrous anaerobic treatment on 3, 5-dimethoxyphenyl 3-phenylpropionate (0.30mmol) and [ bis (difluoroacetoxyl) iodine]Benzene (0.60mmol) was added to the reaction tube in sequence, 1.00mL of anhydrous DMAc was taken into the reaction tube with a long needle syringe under the protection of nitrogen in the double row tube, and the two reactants were dissolved with stirring and reacted at room temperature under the illumination of blue 18W LED light. After confirming the reaction was complete by TLC, a large amount of water was added and washed, extracted four times with ethyl acetate, washed twice with saturated sodium chloride solution, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and the residue was purified by silica gel column chromatography to give the product as a white solid in 84% yield.1H NMR(400MHz，CDCl3)δ7.55(t，J＝3.2Hz，3H)，7.33-7.31(m，2H)， 6.74(d，J＝2.4Hz，1H)，6.52(t，J＝53.2Hz，1H)，6.02(d，J＝2.8Hz，1H)，3.96(s，3H)，3.62(s，3H).13C NMR (100MHz，CDCl3)δ157.71，156.48，156.19，148.33，138.70，132.14，129.77，128.75，128.40，120.14，118.43(t，J ＝22.0Hz，1C)，111.88(t，J＝238.5Hz，1C)，104.45(d，J＝2.0Hz，1C)，100.94，56.56(d，J＝6.0Hz，1C)，55.72 (d，J＝4.0Hz，1C).19F NMR(376MHz，CDCl3)δ-114.69(s，2F).HRMS ESI(m/z)：calcd for C18H14F2O4[M+ Na]+：355.0752，found：355.0755.
Example 2
Firstly, carrying out anhydrous anaerobic treatment on a 10mL Schlenk tube, removing residual moisture in the wall, the mouth and the tube of a reaction tube at high temperature through a drying gun, carrying out nitrogen gas and air replacement in the reaction tube through a double-row tube to create an anhydrous anaerobic environment, and cooling the Schlenk tube in a nitrogen atmosphereThen, 3- (4-chlorophenyl) propionate (0.30mmol) and [ bis (difluoroacetoxy) iodide were added]Benzene (0.60mmol) was added to the reaction tube in sequence, 1.00mL of anhydrous DMAc was taken into the reaction tube with a long needle syringe under the protection of nitrogen in the double row tube, and the two reactants were dissolved with stirring and reacted at room temperature under the illumination of blue 18W LED light. After confirming the reaction was complete by TLC, a large amount of water was added and washed, extracted four times with ethyl acetate, washed twice with saturated sodium chloride solution, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and the residue was purified by silica gel column chromatography to give the product as a pale yellow oil in 74% yield.1H NMR(400MHz，CDCl3)δ7.64(t，J＝1.2，1H)，7.54(d，J＝8.3Hz，2H)，7.41 (d，J＝8.4Hz，1H)，7.29(d，J＝8.4Hz，2H)，7.25(t，J＝7.3Hz，1H)，7.09(d，J＝7.2Hz，1H)，6.68(t，J＝53.3Hz， 1H).13C NMR(100MHz，CDCl3)δ158.18，155.24，153.68，136.08，133.79，130.29，129.90，129.13，128.38， 124.94，119.44，118.26(t，J＝22.0Hz，1C)，117.23，111.53(t，J＝237.0Hz，1C).19F NMR(376MHz，CDCl3)δ -113.76(s，2F).HRMS ESI(m/z)：calcd for C16H9ClF2O2[M+Na]+：329.0151，found：329.0154.
Example 3
Firstly, carrying out anhydrous anaerobic treatment on a 10mL Schlenk tube, removing residual water on the wall, the mouth and the tube of a reaction tube at high temperature through a baking gun, carrying out nitrogen gas replacement and air replacement in the reaction tube through a double-row tube to create an anhydrous anaerobic environment, and cooling the Schlenk tube in a nitrogen atmosphere, and then carrying out anhydrous anaerobic treatment on 3-fluorophenyl 3-phenylpropionate (0.30mmol) and [ bis (difluoroacetoxyl) iodine]Benzene (0.60mmol) was added to the reaction tube in sequence, 1.00mL of anhydrous DMAc was taken into the reaction tube with a long needle syringe under the protection of nitrogen in the double row tube, and the two reactants were dissolved with stirring and reacted at room temperature under the illumination of blue 18W LED light. After confirming the completion of the reaction by TLC, washing with a large amount of water and washing with waterThe ethyl acetate was extracted four times, washed twice with saturated sodium chloride solution, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and the residue was purified by silica gel column chromatography to give the product as a white solid in 64% yield.1H NMR(400MHz，CDCl3)δ7.58-7.57(m，3H)，7.34-7.31(m，2H)，7.14-7.10(m， 2H)，6.95(td，J＝8.0Hz，2.4Hz，1H)，6.49(t，J＝53.2Hz，1H).13C NMR(100MHz，CDCl3)δ166.79，164.24， 157.56，156.05，155.03(d，J＝13.0Hz，1C)，131.59，130.72(d，J＝10.0Hz，1C)，130.02，128.98，128.38，116.39， 113.01(d，J＝23.0Hz，1C)，111.75(t，J＝237.0Hz，1C)，104.59(d，J＝26.0Hz，1C).19F NMR(376MHz， CDCl3)δ-102.34(s，1F)，-114.78(s，2F).HRMS ESI(m/z)：calcd for C16H9F3O2[M+Na]+：313.0447，found： 313.0450.
Example 4
Firstly, carrying out anhydrous anaerobic treatment on a 10mL Schlenk tube, removing residual water on the wall, the mouth and the tube of a reaction tube at high temperature through a drying gun, carrying out nitrogen gas replacement and air replacement in the reaction tube through a double-row tube to create an anhydrous anaerobic environment, and cooling the Schlenk tube in a nitrogen atmosphere, and then carrying out anhydrous anaerobic treatment on 3-cyclopropyl propionate phenyl (0.30mmol) and [ bis (difluoroacetoxyl) iodine]Benzene (0.60mmol) was added to the reaction tube in sequence, 1.00mL of anhydrous DMAc was taken into the reaction tube with a long needle syringe under the protection of nitrogen in the double row tube, and the two reactants were dissolved with stirring and reacted at room temperature under the illumination of blue 18W LED light. After confirming the reaction was complete by TLC, a large amount of water was added and washed, extracted four times with ethyl acetate, washed twice with saturated sodium chloride solution, the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and the residue was purified by silica gel column chromatography to give the product as a white solid in 23% yield.1H NMR(400MHz，CDCl3)δ8.17(d，J＝8.0Hz，1H)，7.59(td，J＝8.4Hz，1.2Hz， 1H)，7.37-7.33(m，2H)，7.18(t，J＝53.6Hz，1H)，2.06-1.99(m，1H)，1.35-1.32(m，2H)，0.91(q，J＝6.0Hz，2H). 13C NMR(100MHz，CDCl3)δ158.66，157.22(d，J＝3.0Hz，1C)，153.44，133.14，127.27，124.61，120.26(t，J＝ 22.3Hz，1C)，120.18，117.27，111.78(t，J＝239.0Hz，1C)，10.83，8.06，0.14.19F NMR(376MHz，CDCl3)δ -116.78(s，2F).HRMS ESI(m/z)：calcd for C13H10F2O2[M+Na]+：259.0541，found：259.0544。
Claims (2)
1. A method for synthesizing difluoromethyl substituted coumarin derivatives by cyclization of aryl alkynoate under photocatalysis is characterized in that [ bis (difluoroacetoxyl) iodo ] benzene is used as a difluoromethyl source. The method comprises the following specific steps: adding aryl alkyne acid ester, [ bis (difluoroacetoxyl) iodine ] benzene and N, N-dimethylacetamide under the anhydrous and oxygen-free conditions, and reacting at room temperature under the illumination of a blue 18W LED lamp. After the reaction is finished, the difluoromethyl substituted coumarin derivative is obtained through extraction, washing, drying and column chromatography separation.
2. The difluoromethylation method according to claim 1, having the general reaction formula wherein R is1Selected from cyano, phenyl, methoxy, halogen, tert-butyl; r2Selected from cyclopropyl, phenyl, substituted phenyl;
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805069A (en) * | 2022-04-29 | 2022-07-29 | 天津科技大学 | Method for synthesizing alpha difluoro ester derivative from terminal olefin |
| CN115785052A (en) * | 2022-11-21 | 2023-03-14 | 河南大学 | Method for synthesizing isocoumarin with high selectivity under catalysis of polyacid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805069A (en) * | 2022-04-29 | 2022-07-29 | 天津科技大学 | Method for synthesizing alpha difluoro ester derivative from terminal olefin |
| CN114805069B (en) * | 2022-04-29 | 2023-09-29 | 天津科技大学 | Method for synthesizing alpha difluoro ester derivative from terminal olefin |
| CN115785052A (en) * | 2022-11-21 | 2023-03-14 | 河南大学 | Method for synthesizing isocoumarin with high selectivity under catalysis of polyacid |
| CN115785052B (en) * | 2022-11-21 | 2024-01-26 | 河南大学 | Method for synthesizing isocoumarin with high selectivity under catalysis of polyacid |
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