CN111138338A - Synthesis method of photocatalytic fluoroalkyl indoline - Google Patents
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Abstract
The invention discloses a synthesis method of photocatalytic fluoroalkyl indoline, which comprises the following steps: step 1, 2-allylaniline compound is used as raw material, RF source is fluorizating reagent providing fluorine source, Blue LEDs are used as light source, EosinY Na is used as photocatalyst, TMEDA is used as alkali additive, and MeCN/H solvent is added2Carrying out reaction in O; step 2, extracting the reaction product, combining organic phases, drying, filtering, and concentrating under reduced pressure to obtain a crude product; and 3, further carrying out chromatography purification on the crude product to obtain a target product, namely fluoroalkyl indoline. The invention has the beneficial effects that: visible light is a cheap, clean and pollution-free green energy; with MeCN/H2O is used as a mixed solvent, accords with the green chemical concept, is environment-friendly, and has simple post-treatment and simple and convenient operation; the method has the advantages of simple reaction device, mild conditions, realization at room temperature, energy consumption saving and high yield of the target product.
Description
Technical Field
The invention relates to a synthesis method of photocatalytic fluoroalkyl indoline, belonging to the technical field of synthesis and application of organic compounds.
Background
Indolines are a class of structural units with biological activity, are commonly found in alkaloids and other natural products, and are of great interest in the fields of organic synthesis and drug development. In the agricultural field, indolines are key intermediates for a variety of plant growth regulators; in the field of new energy, indoline compounds are widely applied to novel solar cell materials. Natural products and drugs based on indoline framework structures are widely used in the treatment of certain diseases, such as: physostigmine (-) -Physostigmine is a reversible cholinesterase inhibitor and can be used for treating glaucoma; the angiotensin enzyme inhibitor pentapril; strychnine is a highly toxic alkaloid used for capturing fur animals, and hydrochloride thereof can be used as an excitant of the central nervous system and the like; quebracho (+) -Aspidospiridine is an important anti-tumor drug; the benzazetidine (+) Benzastatin can be used for preventing and treating cerebral ischemia, protecting nerve cell activity and the like.
Strong electronegativity of fluorine and small atomic radius
Close to the hydrogen and oxygen atoms. When fluorine or fluorine-containing groups replace hydrogen atoms, the three-dimensional structure and charge distribution of the molecule can be changed, so that the acid-base property, the nucleophilicity and the metabolic stability of the molecule are influenced. The C-F bond is highly stable and may participate in the formation of hydrogen bonds, the presence of which enhances the stability of the fluorochemical. Due to the physicochemical characteristics of fluorine, fluorine atoms or fluorine-containing groups are introduced into organic molecules, so that the fat solubility and the stability of the compound can be obviously improved. Currently, about 20-30% of the drugs and 30-40% of the pesticides contain at least one fluorine atom. Thus, the introduction of fluorine-containing groups into organic molecules has long been of interest to chemists.
Therefore, the introduction of fluorine-containing groups into the indoline skeleton can obviously improve the lipid solubility and metabolic stability of the compound, and is beneficial to the absorption and the function of the medicament containing the indoline skeleton structure in vivo. The development of efficient introduction of fluorine-containing groups into organic molecules has become a key research content in the field of organic synthesis. At present, the synthesis of fluoroalkyl indoline compounds mainly adopts a transition metal catalysis means. In 2014, southern science and technology university Liu and the like developed an amination trifluoromethylation reaction of Cu catalyzed unsaturated olefin and nitrogen-containing nucleophilic group molecules, no additional ligand is needed, functional group tolerance is good, aliphatic amine, aromatic amine, sulfanilamide, carbamate, urea and the like can be used as nucleophilic groups in the reaction, and a series of pyrrole and indoline compounds containing trifluoromethyl are synthesized. Shortly after they have provided a trifluoromethyl source as (TMS) CF3, they reported Cu catalyzed the amination trifluoromethylation of unsaturated olefins, and enriched the existing olefin trifluoromethylation process by using the less expensive electrophilic trifluoromethylating reagent (TMS) CF3 to provide a fluorine source. In 2015, Sodeoka et al reported that CuI catalyzed the amination trifluoromethylation reaction of olefins, and the authors focused on the reaction mechanism: the kinetic study shows that the initial rate of the reaction is related to the Togni reagent, the CuI and the amine substrate, and the mechanism research method has guiding significance on the design of the related reaction. In 2017, Sodeoka et al also reported a simple and efficient method for synthesizing perfluoroalkyl heterocyclic amines, including ternary, five-membered, six-membered heterocyclic amines and the like, and obtained a plurality of perfluoroalkyl compounds. In 2017, Zhang and the like develop an olefin amination trifluoromethylation reaction taking CF3SO2Na as a fluorine source under the catalysis of Cu, the tolerance of functional groups of the reaction is good, authors mainly investigate the influence of different substituent groups on nitrogen on the reaction, in the reaction system, the substitution of electron-donating groups on nitrogen atoms is beneficial to the reaction, and gram-scale reaction is realized.
However, these methods still have some drawbacks:
(1) transition metal catalysis generally requires high-temperature heating, and is easy to induce side reactions; the catalyst is difficult to recover and easy to remain in the product;
(2) heterocyclic fluorination reagents are generally expensive and not conducive to large-scale use;
(3) organic solvents are more or less toxic and expensive, causing a certain pollution to the environment.
It is therefore essential to develop a more efficient, environmentally friendly process for the synthesis of fluoroalkyl indolines. The visible light is rich in storage and convenient to use in nature, is a cheap, clean and pollution-free green energy source, has the characteristic of high-efficiency and mild reaction, and injects new activity for the development of organic synthetic chemistry.
Disclosure of Invention
The invention aims to provide a synthesis method of photocatalytic fluoroalkyl indoline, which explores novel fluoroalkyl/cyclization reaction conditions catalyzed by visible light by means of visible light catalysis under the catalysis of a photocatalyst, develops a mild, economic and effective synthesis methodology and synthesizes fluoroalkyl indoline compounds with important physiological activity.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a synthesis method of photocatalytic fluoroalkyl indoline comprises the following steps:
step 1, reacting a 2-allylaniline compound with a fluorination reagent according to the following method:
wherein: r is Ts, Cbz or Boc; RF is CF3，CF2COOH，CF2COOEt，HCF2，C3F7Or CH2CF3；
The 2-allylaniline compound is used as a raw material, the RF source is a fluorizating reagent for providing a fluorine source, the BlueLEDs are used for providing a light source, the EosinY Na is used as a photocatalyst, the TMEDA is used as an alkali additive, and the solvent MeCN/H is added2Carrying out reaction in O;
step 2, extracting the reaction product, combining organic phases, drying, filtering, and concentrating under reduced pressure to obtain a crude product;
and 3, further carrying out chromatography purification on the crude product to obtain a target product, namely fluoroalkyl indoline.
Preferably, in the step 1, the molar ratio of the 2-allylaniline compound, the fluorinating agent, the sodium eosin and the tetramethylethylenediamine is 1: 1-3: 0.01-0.05: 1-2.
Preferably, in the step 1, the reaction temperature is set to be 5-30 ℃, the stirring power is 45W, the reaction time is 5-10 h, and the progress of TLC is monitored until the reaction is finished.
Preferably, in step 2, extraction is carried out with DCM.
Preferably, in step 2, drying is performed with anhydrous magnesium sulfate.
Preferably, in the step 3, the crude product is subjected to chromatographic purification by using 200-300-mesh petroleum ether/ethyl acetate as an eluent to obtain a target product. More preferably, the molar ratio of petroleum ether to ethyl acetate is 20:1 to 10: 1.
Compared with the prior art, the invention has the following beneficial effects:
(1) the visible light is rich in storage in nature and convenient to use, and is a cheap, clean and pollution-free green energy source;
(2) the organic solvent has certain toxicity and is easy to volatilize, and compared with the organic solvent, water is low in price and is an ideal reaction medium2O is used as a mixed solvent, accords with the green chemical concept, is environment-friendly, and has simple post-treatment and simple and convenient operation;
(3) the method has the advantages of simple reaction device, mild conditions, realization at room temperature, energy consumption saving and high yield of the target product.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, other embodiments used by those skilled in the art without any creative effort belong to the protection scope of the present invention.
Example 1: preparation of 1-tosyl-2- (2,2, 2-trifluoroethyl) indoline
A10 mL Schlenk flask was charged with a magnetic stirrer, the substrates N- (2-allylphenyl) -4-methylbenzenesulfonamide (28.7mg,0.1mmol), EosinY Na (1.57mg,0.002mmol,2 mol%) were added in that order, nitrogen purged for 15min to remove oxygen from the reaction system, and dried MeCN (2mL) and H were added via syringe2O (2mL), organic base TMEDA (0.015mL, 1equiv.), CF were added to the reaction mixture in sequence3I (0.3mmol, 3 equiv.). And (2) continuously stirring the reaction system under the irradiation of 10W blue LEDs, monitoring the reaction by TLC (thin layer chromatography) until the reaction is finished, removing the solvent under reduced pressure, and separating and purifying by column chromatography to obtain the target product 1-tosyl-2- (2,2, 2-trifluoroethyl) indoline (eluent: petroleum ether/ethyl acetate: 20: 1-10: 1).
1-tosyl-2- (2,2, 2-trifluoroethyl) indoline was a colorless oil, yield 76%.
1H NMR(300MHz,Chloroform-d)δ7.69(d,J＝8.1Hz,1H),7.63–7.46(m,2H),7.23(d,J＝4.5Hz,1H),7.22–7.14(m,2H),7.06(d,J＝4.5Hz,2H),4.50–4.36(m,1H),3.07–2.85(m,2H),2.77(dd,J＝16.6,3.3Hz,1H),2.58–2.40(m,1H),2.36(s,3H).
13C NMR(75MHz,Chloroform-d)δ144.4,140.7,134.1,130.6,129.8,128.1,127.1,125.2,125.1,117.3,56.8,56.8,40.8,40.4,34.1,21.6.
19F NMR(565MHz,Chloroform-d)δ-63.09(t,J＝10.7Hz).
HRMS(ESI)m/z calcd for C17H16F3NO2S[M+H]+:356.0927,found:356.0952.
Example 2: preparation of 1-tosyl-2- (2,2, 2-trifluoroethyl) indoline
A10 mL Schlenk flask was charged with a magnetic stirrer, the substrates N- (2-allylphenyl) -4-methylbenzenesulfonamide (28.7mg,0.1mmol), EosinY Na (1.57mg,0.002mmol,2 mol%) were added in that order, nitrogen purged for 15min to remove oxygen from the reaction system, and dried MeCN (2mL) and dry MeCN were added via syringeH2O (2mL), organic base TMEDA (0.015mL, 1equiv.), CF were added to the reaction mixture in sequence3I (0.3mmol, 3 equiv.). And (2) continuously stirring the reaction system under the irradiation of 10W blue LEDs, monitoring the reaction by TLC (thin layer chromatography) until the reaction is finished, removing the solvent under reduced pressure, and separating and purifying by column chromatography to obtain the target product 1-tosyl-2- (2,2, 2-trifluoroethyl) indoline (eluent: petroleum ether/ethyl acetate: 20: 1-10: 1).
1-tosyl-2- (2,2, 2-trifluoroethyl) indoline was a colorless oil in 80% yield.
Example 3: preparation of 1-tosyl-2- (2,2, 2-trifluoroethyl) indoline
A10 mL Schlenk flask was charged with a magnetic stirrer, the substrates N- (2-allylphenyl) -4-methylbenzenesulfonamide (28.7mg,0.1mmol), EosinY Na (1.57mg,0.002mmol,2 mol%) were added in that order, nitrogen purged for 15min to remove oxygen from the reaction system, and dried MeCN (2mL) and H were added via syringe2O (2mL), organic base TMEDA (0.015mL, 1equiv.), CF were added to the reaction mixture in sequence3I (0.3mmol, 3 equiv.). And (2) continuously stirring the reaction system under the irradiation of 10W blue LEDs, monitoring the reaction by TLC (thin layer chromatography) until the reaction is finished, removing the solvent under reduced pressure, and separating and purifying by column chromatography to obtain the target product 1-tosyl-2- (2,2, 2-trifluoroethyl) indoline (eluent: petroleum ether/ethyl acetate: 20: 1-10: 1).
1-tosyl-2- (2,2, 2-trifluoroethyl) indoline was a colorless oil, yield 77%.
Example 4: preparation of 1-tosyl-2- (3,3, 3-trifluoropropyl) indoline
A10 mL Schlenk flask was charged with a magnetic stirrer, the substrates N- (2-allylphenyl) -4-methylbenzenesulfonamide (28.7mg,0.1mmol), EosinY Na (1.57mg,0.002mmol,2 mol%) were added in that order, nitrogen purged for 15min to remove oxygen from the reaction system, and dried MeCN (2mL) and H were added via syringe2O (2mL), organic base TMEDA (0.015mL, 1equiv.), CF were added to the reaction mixture in sequence3CH2I (0.3mmol, 3 equiv.). The reaction system is placed under the irradiation of 10W blue LEDs for continuous stirring, and the TLC is used for monitoring the reaction until the reaction is completedAnd removing the solvent under reduced pressure, and performing column chromatography separation and purification to obtain the target product 1-tosyl-2- (2,2, 2-trifluoroethyl) indoline (eluent: petroleum ether/ethyl acetate: 20: 1-10: 1).
1-tosyl-2- (3,3, 3-trifluoropropyl) indoline was a colorless oil in 81% yield.
1H NMR(300MHz,Chloroform-d)δ7.68(d,J＝8.2Hz,1H),7.50–7.38(m,2H),7.23(s,1H),7.14(d,J＝8.0Hz,2H),7.06(d,J＝7.4Hz,2H),4.27(q,J＝7.5Hz,1H),2.70(dd,J＝16.3,9.0Hz,1H),2.41(s,1H),2.35(s,3H),1.95–1.74(m,2H),1.25(s,2H).
13C NMR(75MHz,Chloroform-d)δ144.1,140.9,134.7,132.4,129.6,128.0,127.0,125.5,125.1,61.3,34.7,30.8,30.4,30.1,29.7,28.8,21.6.
19F NMR(565MHz,Chloroform-d)δ-66.20(t,J＝10.9Hz).
HRMS(ESI)m/z calcd for C18H18F3NO2S[M+H]+:370.1083,found:370.1160.
Example 5:
preparation of 2- (4,4,4,4,4,4, 4-heptafluroo-4 l8-but-2-yn-1-yl) -1-tosylindoline
A10 mL Schlenk flask was charged with a magnetic stirrer, the substrates N- (2-allylphenyl) -4-methylbenzenesulfonamide (28.7mg,0.1mmol), EosinY Na (1.57mg,0.002mmol,2 mol%), nitrogen purged for 15min to remove oxygen from the reaction, dried MeCN (2mL) and H2O (2mL) were added via syringe, and the organic bases TMEDA (0.015mL, 1equiv.), C3F7I (0.3mmol, 3equiv.) were added to the reaction mixture. And (2) continuously stirring the reaction system under the irradiation of 10W blue LEDs, monitoring the reaction by TLC (thin layer chromatography) until the reaction is finished, removing the solvent under reduced pressure, and separating and purifying by column chromatography to obtain the target product 1-tosyl-2- (2,2, 2-trifluoroethyl) indoline (eluent: petroleum ether/ethyl acetate: 20: 1-10: 1).
2- (4,4,4,4,4,4,4, 4-heptafluroo-4 l8-but-2-yn-1-yl) -1-cosylindoline was a colorless oil in 94% yield.
1H NMR(300MHz,Chloroform-d)δ7.71(d,J＝8.0Hz,1H),7.56(d,J＝7.8Hz,2H),7.19(d,J＝7.9Hz,3H),7.07(s,2H),4.54(t,J＝9.5Hz,1H),3.06–2.84(m,2H),2.78(d,J＝16.3Hz,1H),2.59–2.41(m,1H),2.36(s,3H).
13C NMR(75MHz,Chloroform-d)δ144.4,134.1,130.6,129.8,128.2,125.3,125.1,117.3,56.1,37.4,34.9,34.9,29.7,21.6.
19F NMR(565MHz,Chloroform-d)δ-80.33(t,J＝9.7Hz),-111.21–-112.28(m),-114.35–-115.01(m),-127.79(dd,J＝30.8,5.4Hz).
HRMS(ESI)m/z calcd for C19H16F7NO2S[M+H]+:456.0863,found:456.0918.
Claims (7)
1. A synthesis method of photocatalysis fluoroalkyl indoline is characterized by comprising the following steps:
step 1, reacting a 2-allylaniline compound with a fluorination reagent according to the following method:
wherein: r is Ts, Cbz or Boc; RF is CF3，CF2COOH，CF2COOEt，HCF2，C3F7Or CH2CF3；
The 2-allylaniline compound is used as a raw material, the RF source is a fluorizating reagent for providing a fluorine source, the Blue LEDs are used as a light source, the EosinY Na is used as a photocatalyst, the TMEDA is used as an alkali additive, and the solvent MeCN/H is added2Carrying out reaction in O;
step 2, extracting the reaction product, combining organic phases, drying, filtering, and concentrating under reduced pressure to obtain a crude product;
and 3, further carrying out chromatography purification on the crude product to obtain a target product, namely fluoroalkyl indoline.
2. The method for synthesizing fluoroalkyl indoline according to claim 1, wherein the method comprises the following steps: in the step 1, the molar ratio of the 2-allylaniline compound, the fluorinating agent, the eosin sodium and the tetramethylethylenediamine is 1: 1-3: 0.01-0.05: 1-2.
3. The method for synthesizing fluoroalkyl indoline according to claim 1, wherein the method comprises the following steps: in the step 1, the reaction temperature is set to be 5-30 ℃, the stirring power is 45W, the reaction time is 5-10 h, and the progress is monitored by TLC until the reaction is finished.
4. The method for synthesizing fluoroalkyl indoline according to claim 1, wherein the method comprises the following steps: in step 2, DCM is used for extraction.
5. The method for synthesizing fluoroalkyl indoline according to claim 1, wherein the method comprises the following steps: in step 2, drying is performed with anhydrous magnesium sulfate.
6. The method for synthesizing fluoroalkyl indoline according to claim 1, wherein the method comprises the following steps: and 3, performing chromatographic purification on the crude product by using 200-300-mesh petroleum ether/ethyl acetate as an eluent to obtain a target product.
7. The method for synthesizing fluoroalkyl indoline according to claim 6, wherein the method comprises the following steps: the molar ratio of the petroleum ether to the ethyl acetate is 20: 1-10: 1.
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| WO2024031753A1 (en) * | 2022-08-09 | 2024-02-15 | 苏州大学 | Indoline compound and preparation method therefor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2844264A1 (en) * | 2002-09-11 | 2004-03-12 | Rhodia Chimie Sa | New halogenated S-alpha-aminoalkyl thicarbonylsulfanyl compounds, useful as reagents in radical addition reactions, especially for the preparation of biologically active trifluoromethylamine compounds |
| CN101142183A (en) * | 2005-03-16 | 2008-03-12 | 默克公司 | Mitotic kinesin inhibitors |
| CN102675280A (en) * | 2011-03-09 | 2012-09-19 | 中国科学院上海有机化学研究所 | Trifluoromethyl-containing indole ketone compound, and preparation method and application thereof |
| CN103288708A (en) * | 2013-04-02 | 2013-09-11 | 中国人民解放军防化学院 | Preparation method for 1-aryl-2-indolinone derivatives |
-
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- 2020-01-20 CN CN202010067429.8A patent/CN111138338A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2844264A1 (en) * | 2002-09-11 | 2004-03-12 | Rhodia Chimie Sa | New halogenated S-alpha-aminoalkyl thicarbonylsulfanyl compounds, useful as reagents in radical addition reactions, especially for the preparation of biologically active trifluoromethylamine compounds |
| CN101142183A (en) * | 2005-03-16 | 2008-03-12 | 默克公司 | Mitotic kinesin inhibitors |
| CN102675280A (en) * | 2011-03-09 | 2012-09-19 | 中国科学院上海有机化学研究所 | Trifluoromethyl-containing indole ketone compound, and preparation method and application thereof |
| CN103288708A (en) * | 2013-04-02 | 2013-09-11 | 中国人民解放军防化学院 | Preparation method for 1-aryl-2-indolinone derivatives |
Non-Patent Citations (1)
| Title |
|---|
| 邹帅: ""光催化异喹啉-1-酮及氟烷基吲哚啉的合成研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024031753A1 (en) * | 2022-08-09 | 2024-02-15 | 苏州大学 | Indoline compound and preparation method therefor |
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