CN112321553B - 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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- CN112321553B CN112321553B CN202011184520.4A CN202011184520A CN112321553B CN 112321553 B CN112321553 B CN 112321553B CN 202011184520 A CN202011184520 A CN 202011184520A CN 112321553 B CN112321553 B CN 112321553B
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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
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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
- C07D311/16—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, and generates difluoromethyl free radicals under the catalysis of visible light, and then aromatic propiolate generates free radical addition, oxidation and rearrangement reaction to obtain the 3-bit difluoromethyl substituted coumarin derivative. In particular to a method for preparing aromatic propiolic acid ester and derivatives thereof and [ bis (difluoroacetoxyl) iodine in a reaction tube]Benzene dissolved in DMAc and then applied to a blue 18W LED lampReacting at room temperature to synthesize a series of substituted difluoromethylcoumarin derivatives. In the structural general formula, R is 1 Selected from cyano, phenyl, methoxy, halogen, t-butyl, and the like; r 2 Selected 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 fluorine atom or fluorine-containing group is introduced into the organic micromolecule, so that the properties of lipophilicity, lipid solubility, metabolic stability, cell permeability and the like of the molecule can be remarkably improved. 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.
A number of difluoromethylation reactions based on difluoromethyl radicals have been reported. The difluoromethyl radical precursor used is zinc difluoromethylsulfinate, sodium difluoromethylsulfinate, difluoromethylsulfinyl chloride, difluoromethylbenzothiazolesulfone, difluoromethylphosphine, 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) 3 Under 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) Through the reaction of sodium difluoromethyl sulfinate, under the catalysis of eosin Y,the coumarin is reacted with the coumarin under the irradiation of a 5W blue LED lamp to prepare the coumarin. 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 cyclization of aromatic propiolate.
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 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 R 1 Selected from cyano, phenyl, methoxy, halogen, tert-butyl; r is 2 Selected 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 has stability and is 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 derivatives thereof (0.30 mmol) and [ bis (difluoroacetoxyl) iodine ] benzene (0.60 mmol) 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 a blue 18W LED lamp. 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 (0.30 mmol) and [ bis (difluoroacetoxyl) iodine]Benzene (0.60 mmol) was added to the reaction tube in sequence, 1.00mL of anhydrous DMAc was added to the reaction tube with a long needle syringe under the protection of nitrogen in the double row tube, the two reactants were dissolved with stirring, and reacted at room temperature under the illumination of a blue 18W LED lamp. After confirming the completion of the reaction by TLC, a large amount of water was added, washing was performed four times with ethyl acetate, washing was performed 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 with a yield of 84%. 1 H NMR(400MHz，CDCl 3 )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). 13 C NMR (100MHz，CDCl 3 )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). 19 F NMR(376MHz，CDCl 3 )δ-114.69(s，2F).HRMS ESI(m/z)：calcd for C 18 H 14 F 2 O 4 [M+ Na] + ：355.0752，found：355.0755.
Example 2
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- (4-chlorphenyl) propionate (0.30 mmol) and [ bis (difluoroacetoxyl) iodine]Benzene (0.60 mmol) was added sequentially to the reaction tube, 1.00mL of anhydrous DMAc was taken in under the protection of a double-row tube of nitrogen with a long needle syringe, the two reactants were dissolved with stirring and reacted at room temperature under the illumination of a blue 18W LED lamp. 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. 1 H NMR(400MHz，CDCl 3 )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). 13 C NMR(100MHz，CDCl 3 )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). 19 F NMR(376MHz，CDCl 3 )δ -113.76(s，2F).HRMS ESI(m/z)：calcd for C 16 H 9 ClF 2 O 2 [M+Na] + ：329.0151，found：329.0154.
Example 3
A10 mL Schlenk tube was first subjected to an anhydrous anaerobic treatment, and the reaction tube was removed at high temperature by means of a drying gunThe residual water in the wall, the pipe orifice and the pipe is replaced by nitrogen and air in the reaction pipe through a double-row pipe to create an anhydrous oxygen-free environment, and after the Schlenk pipe is cooled in a nitrogen atmosphere, 3-fluorophenyl 3-phenylpropionate (0.30 mmol) and [ bis (difluoroacetoxyl) iodine are added]Benzene (0.60 mmol) was added sequentially to the reaction tube, 1.00mL of anhydrous DMAc was taken in under the protection of a double-row tube of nitrogen with a long needle syringe, the two reactants were dissolved with stirring and reacted at room temperature under the illumination of a blue 18W LED lamp. 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 64% yield. 1 H NMR(400MHz，CDCl 3 )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). 13 C NMR(100MHz，CDCl 3 )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). 19 F NMR(376MHz， CDCl 3 )δ-102.34(s，1F)，-114.78(s，2F).HRMS ESI(m/z)：calcd for C 16 H 9 F 3 O 2 [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 (0.30 mmol) and [ bis (difluoroacetoxyl) iodine]Benzene (0.60 mmol) was added sequentially to the reaction tube and a long needle syringe was used in the double row tube1.00mL of anhydrous DMAc is taken out under the protection of nitrogen and is added into a reaction tube, and the two reactants are dissolved under stirring and react at room temperature under the illumination of a blue 18W LED lamp. 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. 1 H NMR(400MHz，CDCl 3 )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). 13 C NMR(100MHz，CDCl 3 )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. 19 F NMR(376MHz，CDCl 3 )δ -116.78(s，2F).HRMS ESI(m/z)：calcd for C 13 H 10 F 2 O 2 [M+Na] + ：259.0541，found：259.0544。
Claims (1)
1. A method for synthesizing difluoromethyl substituted coumarin derivative by aryl alkynoate cyclization under photocatalysis is characterized in that [ bis (difluoroacetoxyl) iodine]Benzene is a difluoromethyl source, and the method comprises the following specific steps: adding aryl alkyne acid ester and [ bis (difluoroacetoxyl) iodine under anhydrous and oxygen-free conditions]Benzene and N, N-dimethylacetamide react at room temperature under the illumination of a blue 18W LED lamp, and after the reaction is finished, the difluoromethyl substituted coumarin derivative is obtained through extraction, washing, drying and column chromatography separation, wherein the specific reaction is as follows, wherein R is 1 Selected from cyano, phenyl, methoxy, halogen, tert-butyl; r 2 Selected from cyclopropyl, phenyl, substituted phenyl.
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