CN111732535A - Photochemical synthesis method of heteroaryl amine compound - Google Patents

Photochemical synthesis method of heteroaryl amine compound Download PDF

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CN111732535A
CN111732535A CN202010793052.4A CN202010793052A CN111732535A CN 111732535 A CN111732535 A CN 111732535A CN 202010793052 A CN202010793052 A CN 202010793052A CN 111732535 A CN111732535 A CN 111732535A
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synthesis method
photochemical synthesis
photochemical
heteroaryl
photocatalyst
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CN111732535B (en
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张恩选
刘志清
肖毅
卢江平
侯庆龙
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Asychem Pharmaceuticals Tianjin Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
    • C07D231/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/36—Nitrogen atoms

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Abstract

The invention provides a photochemical synthesis method of a heteroaryl amine compound. The photochemical synthesis method comprises the following steps: step S1, mixing the raw materials including the heteroaryl nitro compound, the solvent and the photocatalyst to obtain a mixture; and step S2, carrying out photocatalytic reduction reaction on the mixture under the illumination condition to obtain a product system containing the heteroaryl amine compound. The photochemical synthesis method realizes the photocatalytic reduction of various heteroaryl nitro compounds under the illumination condition, and obtains the heteroaryl amine compounds with higher yield. The photocatalyst is the existing commonly used catalyst, has no strict requirements on equipment, is easy to recover, and reduces the safety risk of the heteroaryl amine compound and the catalyst cost. The whole reaction process of the photocatalysis does not need to add any metal reagent and reducing agent, the conversion rate of the reaction is higher, and the post-treatment is simple and easy to operate, so that the photocatalysis is safer and more environment-friendly.

Description

Photochemical synthesis method of heteroaryl amine compound
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a photochemical synthesis method of a heteroaryl amine compound.
Background
The synthesis of arylamine compounds plays an important role in organic synthesis unit reaction. Is widely used in the fields of dye, agricultural chemicals, surfactant, chelating agent, medicine synthesis and the like, such as arylamine medicines: local anesthetics such as benzocaine and procaine hydrochloride. The reduction of aromatic nitro compounds is a common method for preparing aromatic amine by chemical production at present.
The reduction of aromatic nitro compounds to prepare aromatic amines mainly comprises the following methods: an active metal reduction method; a metal hydride reduction method; a catalytic hydrogenation process; electrochemical reduction, and the like. The active metal reduction method is the most classical nitro compound reduction method, for example, the metallic iron/hydrochloric acid reduction method adopted by Lih-Chu and the like in the U.S. patent application with the patent application publication number of US2018134698A1, and the tin chloride/ethanol heating reduction method adopted by Forma and the like in the patent application with the patent application publication number of WO 2016171755A 1. The metal hydride reduction method usually uses sodium borohydride or lithium aluminum hydride as a reducing agent, and the method has the disadvantages of high reagent price, high reaction probability when meeting moisture and high potential safety hazard. The most common catalytic hydrogenation process is palladium on carbon hydrogenation（MedChemComm,2016,vol.7.11,2159-2166）And a raney nickel hydrogenation method (WO 2008143674), which has higher requirements on equipment and high safety risk, and has higher production cost due to the adoption of noble metals such as palladium, rhodium, platinum and the like in the production process. Electrolytic reduction processes, e.g. Ravichand C, with Ti/TiO2Realizes the electro-reduction of nitro compound for the electrode under the action of sulfuric acid（Journal of Applied Electrochemistry,1994,24,1256- 1261）However, the system is generally in an acid environment, and is opposite to the bottomThe requirement of the structure of the object is high.
The method for catalytically reducing nitro-compounds by using platinum nanowires as catalysts is disclosed in Chinese patent application with publication number CN201110006899.4, and needs to be carried out at 0-100 ℃ and 0.1-1.0 atmospheric pressure, so that high temperature and high pressure are avoided, and a reaction device is simple, so that the method is a very promising reduction method. Scale-up of catalyst preparation and cost control still face significant challenges.
Disclosure of Invention
The invention mainly aims to provide a photochemical synthesis method of a heteroaryl amine compound, and aims to solve the problems of high environmental protection pressure, high potential safety hazard and high preparation cost caused by a catalyst of a traditional reduction method of an aromatic nitro compound in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a photochemical synthesis method of a heteroarylamine-based compound, the photochemical synthesis method comprising: step S1, mixing the raw materials including the heteroaryl nitro compound, the solvent and the photocatalyst to obtain a mixture; and step S2, carrying out photocatalytic reduction reaction on the mixture under the illumination condition to obtain a product system containing the heteroaryl amine compound.
Further, the structural general formula of the heteroaryl nitro compound is I or II:
Figure 291322DEST_PATH_IMAGE001
Figure 549128DEST_PATH_IMAGE002
structural general formula I structural general formula II
Wherein n and m are each independently 0 or 1, Y, Z are each independently selected from the group consisting of chemically acceptable CR7、N、NR8O, S, and Y, Z at least one of N, NR8And O, S, R1、R2、R3、R4、R5、R6、R7、R8Each independently selected from H, substituted or unsubstituted C1~C20Alkyl, substituted or unsubstituted C1~C20Alkoxy, substituted or unsubstituted C6~C20Aryl, halogen, ester, hydroxyl, amide, nitro, -CF3、-CHF2One kind of (1).
Further, the above R1、R2、R3、R4、R5、R6、R7、R8Each independently selected from substituted or unsubstituted C1~C10Linear alkyl, substituted or unsubstituted C of3~C10Branched alkyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C10Any one of the aryl groups of (1).
Further, the above R1、R2、R3、R4、R5、R6、R7、R8Each independently selected from methoxy, -Cl, -CHF2Any one of them.
Further, the above solvent is selected from C1~C6Alcohol or C1~C6Of an alcohol, preferably C1~C6The alcohol is selected from one or more of methanol, ethanol, ethylene glycol, isopropanol, n-butanol, tert-butanol, and cyclohexanol, preferably C1~C6The volume ratio of the alcohol to the water in the alcohol aqueous solution is 10: 1-50: 1.
The active component of the photocatalyst is nano titanium dioxide, the mass ratio of the heteroaryl nitro compound to the nano titanium dioxide is preferably 1: 1-1: 5, the particle size of the nano titanium dioxide is preferably 15-200 nm, the particle size is preferably 30-60 nm, and the nano titanium dioxide is further preferably selected from one or more of rutile type nano titanium dioxide, anatase type nano titanium dioxide and microspheres loaded with the nano titanium dioxide.
Further, in the step S2, the temperature of the photocatalytic reduction reaction is 30 to 40 ℃, the time of the photocatalytic reduction reaction is preferably 2 to 15 hours, the wavelength of light in the illumination condition is preferably 310 to 400nm, preferably 340 to 385nm, and the light source in the illumination condition is preferably an LED lamp or a laser.
Further, the raw materials also comprise a dissolving assistant agent, preferably the dissolving assistant agent is selected from one or more of tetrahydrofuran, acetone, ethyl acetate and polyethylene glycol-400.
Further, the raw materials also comprise additives, preferably the additives are selected from one or more of triethylamine, triethanolamine, sodium sulfite, sodium sulfide, EDTA, formic acid and ascorbic acid.
Further, the photochemical synthesis method further comprises: performing centrifugal separation on the product system to obtain clear liquid and solid; carrying out reduced pressure concentration treatment on the clear liquid to obtain a heteroaryl amine compound and a recovered solvent; cleaning and drying the solid to recover the photocatalyst; the recovered solvent is preferably returned to step S1 to be used as a solvent, and the recovered photocatalyst is preferably returned to step S1 to be used as a photocatalyst.
Further, the structural formula of the heteroaryl amine compound is as follows:
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、
Figure 548493DEST_PATH_IMAGE004
、
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、
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、
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、
Figure 813067DEST_PATH_IMAGE008
、
Figure 485357DEST_PATH_IMAGE009
、
Figure 452176DEST_PATH_IMAGE010
、
Figure 863303DEST_PATH_IMAGE011
any one of them.
By applying the technical scheme, the photochemical synthesis method of the invention uses the photocatalyst, under the illumination condition, the surface of the catalyst can form photoproduction holes and photoproduction electrons, and the photoproduction electrons can generate active hydrogen under the action of water to further reduce nitro; namely, the photocatalytic reduction of various heteroaryl nitro compounds is realized under the illumination condition, and the heteroaryl amine compounds with higher yield are obtained. The photocatalyst is the existing commonly used catalyst, has no strict requirements on equipment, is easy to recover, and reduces the safety risk of the heteroaryl amine compound and the catalyst cost. The whole reaction process of the photocatalysis does not need to add any metal reagent and reducing agent, the conversion rate of the reaction is higher, and the post-treatment is simple and easy to operate, so that the photocatalysis is safer and more environment-friendly.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art, the problems of large environmental protection pressure, large potential safety hazard and high preparation cost caused by the catalyst of the traditional reduction method of the aromatic nitro compound exist in the prior art, and in order to solve the problems, the invention provides a photochemical synthesis method of the heteroaryl amine compound.
In one exemplary embodiment of the present application, there is provided a photochemical synthesis method of a heteroarylamine compound, the photochemical synthesis method comprising: step S1, mixing the raw materials including the heteroaryl nitro compound, the solvent and the photocatalyst to obtain a mixture; and step S2, carrying out photocatalytic reduction reaction on the mixture under the illumination condition to obtain a product system containing the heteroaryl amine compound.
According to the photochemical synthesis method, the photocatalyst is used, under the condition of illumination, photoproduction holes and photoproduction electrons are formed on the surface of the catalyst, and the photoproduction electrons and water react to generate active hydrogen so as to further reduce nitro; namely, the photocatalytic reduction of various heteroaryl nitro compounds is realized under the illumination condition, and the heteroaryl amine compounds with higher yield are obtained. The photocatalyst is the existing commonly used catalyst, has no strict requirements on equipment, is easy to recover, and reduces the safety risk of the heteroaryl amine compound and the catalyst cost. The whole reaction process of the photocatalysis does not need to add any metal reagent and reducing agent, the conversion rate of the reaction is higher, and the post-treatment is simple and easy to operate, so that the photocatalysis is safer and more environment-friendly.
In one embodiment of the present application, the heteroaryl nitro compound has a general structural formula I or II:
Figure 158149DEST_PATH_IMAGE001
Figure 775075DEST_PATH_IMAGE002
structural general formula I structural general formula II
Wherein n and m are each independently 0 or 1, Y, Z are each independently selected from the group consisting of chemically acceptable CR7、N、NR8O, S, and Y, Z at least one of N, NR8And O, S, R1、R2、R3、R4、R5、R6、R7、R8Each independently selected from H, substituted or unsubstituted C1~C20Alkyl, substituted or unsubstituted C1~C20Alkoxy, substituted or unsubstituted C6~C20Aryl, halogen, ester, hydroxyl, amide, nitro, -CF3、-CHF2One kind of (1).
The heteroaryl nitro compound which accords with the structural general formulas I and II has better reaction effect under the photocatalytic reduction reaction condition, and has wider application in the fields of chemical industry and medicine.
In order to further improve the reactivity of the heteroaryl nitro compound under the photocatalytic reduction reaction conditions of the present application, the above R is preferably used1、R2、R3、R4、R5、R6、R7、R8Each independently selected from substituted or unsubstituted C1~C10Linear alkyl, substituted or unsubstituted C of3~C10Branched alkyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C10Any one of the aryl groups of (1).
In one embodiment of the present application, R is as defined above1、R2、R3、R4、R5、R6、R7、R8Each independently selected from methoxy, -Cl, -CHF2Any one of them.
The heteroaryl nitro compound with the substituent group is more beneficial to obtaining the corresponding heteroaryl amine compound with high yield and high practicability.
In order to further improve the solubility of the raw materials for the reaction and to improve the reaction efficiency, it is preferable that the solvent is selected from C1~C6Alcohol or C1~C6Of an alcohol, preferably C1~C6The alcohol is selected from one or more of methanol, ethanol, ethylene glycol, isopropanol, n-butanol, tert-butanol, and cyclohexanol, preferably C1~C6The volume ratio of the alcohol to the water in the alcohol aqueous solution is 10: 1-50: 1.
In an embodiment of the application, the active component of the photocatalyst is nano titanium dioxide, preferably, the mass ratio of the heteroaryl nitro compound to the nano titanium dioxide is 1:1 to 1:5, preferably, the particle size of the nano titanium dioxide is 15 to 200nm, preferably 30 to 60nm, and further preferably, the nano titanium dioxide is one or more selected from rutile nano titanium dioxide, anatase nano titanium dioxide, and nano titanium dioxide-loaded microspheres.
The preferable particle size of the nano titanium dioxide catalyst and the mass ratio of the heteroaryl nitro compound to the nano titanium dioxide are beneficial to further improving the efficiency of the photocatalytic reduction reaction.
In order to improve the efficiency of the photocatalytic reduction reaction, it is preferable that in step S2, the temperature of the photocatalytic reduction reaction is 30 to 40 ℃, the time of the photocatalytic reduction reaction is 2 to 15 hours, the wavelength of light in the illumination condition is 310 to 400nm, and 340 to 385nm, and the light source in the illumination condition is an LED lamp or a laser.
In one embodiment of the present application, the raw materials further comprise a solubilizing reagent, preferably the solubilizing reagent is one or more selected from tetrahydrofuran, acetone, ethyl acetate, ethylene glycol, diethylene glycol, and polyethylene glycol-400.
The solubility of the nitro substrate in the isopropanol solvent is poor, which is not beneficial to further amplification and industrial application of the reaction, and the addition of the solubilizing aid reagent can be beneficial to further improving the solubility of the reaction raw materials in the solvent, reducing the dosage of the solvent and improving the reaction efficiency of the raw materials without influencing the precursor of the reaction process.
In one embodiment of the present application, the raw material further comprises an additive, preferably the additive is one or more selected from triethylamine, triethanolamine, sodium sulfite, sodium sulfide, EDTA, formic acid, and ascorbic acid.
The additive can be matched with a photocatalyst, so that the photocatalytic reduction reaction can be promoted, and the efficiency of the photocatalytic reduction reaction can be improved. The catalyst generates photoproduction holes and electrons under illumination, the holes and the electrons are easy to combine with each other, the efficiency of the electrons is reduced, the additive can be combined with the photoproduction holes, the service life of the photoproduction electrons is prolonged, and the reaction rate is improved; the acidic substrate is preferably an acidic additive, and the basic substrate is preferably a basic additive.
In an embodiment of the present application, the photochemical synthesis method further includes: performing centrifugal separation on the product system to obtain clear liquid and solid; carrying out reduced pressure concentration treatment on the clear liquid to obtain a heteroaryl amine compound and a recovered solvent; cleaning and drying the solid to recover the photocatalyst; the recovered solvent is preferably returned to step S1 to be used as a solvent, and the recovered photocatalyst is preferably returned to step S1 to be used as a photocatalyst.
In the present invention, the solvent and the nano titania catalyst are recovered by the above method and returned to the photocatalytic reduction reaction for recycling, and among them, the recovered photocatalyst is preferably returned to step S1 and used as a photocatalyst 1 to 10 times. On one hand, the environmental pollution is reduced, on the other hand, the production cost is reduced, and the economic benefit is improved.
In one embodiment of the present application, the structural formula of the heteroarylamine compound is:
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、
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、
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、
Figure 364877DEST_PATH_IMAGE006
、
Figure 571868DEST_PATH_IMAGE007
、
Figure 29525DEST_PATH_IMAGE008
、
Figure 689177DEST_PATH_IMAGE009
、
Figure 382326DEST_PATH_IMAGE010
、
Figure 37298DEST_PATH_IMAGE011
any one of them.
The heteroaryl amine compound with the structure can be widely applied to the fields of chemical industry and medicine.
The following description will explain advantageous effects of the present application with reference to specific examples.
Example 1
Dissolving 2-methoxy-5-nitropyridine (0.1 g, 0.65 mmol) in isopropanol (10 mL), stirring for clarification, adding 0.5 mL of purified water, then adding 0.5 g of rutile nano titanium dioxide with the particle size of 30 nm, stirring for 0.5 h, placing in a photochemical reactor, irradiating for 6 h at the temperature of 30 ℃ by using a 365nm LED lamp as a light source, monitoring by HPLC (high performance liquid chromatography) after the raw materials disappear, stopping irradiating to obtain a product system, placing the product system in a centrifuge for centrifugal separation, performing reduced pressure concentration on an upper layer organic phase, and performing column chromatography to obtain 7.52 g of reddish brown liquid 2-methoxy-5-aminopyridine, wherein the separation yield is 93.4%, and the nuclear magnetic spectrum data is as follows:1H-NMR (400 MHz，CDCl3) ： 3.39 (br s, 2H),3.84 (s, 3H), 6.58 (d, J = 8.8 Hz, 1H), 7.01 (d, J = 8.9 Hz, 1H), 7.64 (d, J= 2.4 Hz, 1H) 。
example 2
Example 2 is different from example 1 in that 0.1 g of rutile nano titanium dioxide with the particle size of 30 nm is added, the mixture is irradiated for 15 hours by using an LED lamp with the particle size of 365nm as a light source, and the upper organic phase is subjected to reduced pressure concentration column chromatography to obtain 63mg of 2-methoxy-5-aminopyridine, wherein the separation yield is 78.2%.
Example 3
Example 3 is different from example 1 in that 0.2 g rutile nano titanium dioxide with the particle size of 30 nm is added, the mixture is irradiated for 10 hours by using an LED lamp with the particle size of 365nm as a light source, and the upper organic phase is subjected to reduced pressure concentration column chromatography to obtain a reddish brown liquid 2-methoxy-5-aminopyridine 68mg, wherein the separation yield is 85.2%.
Example 4
Example 4 is different from example 2 in that 0.05 g of rutile type nano titanium dioxide having a particle size of 30 nm was added, and the upper organic phase was subjected to column chromatography by concentration under reduced pressure to obtain 57mg of 2-methoxy-5-aminopyridine as a reddish brown liquid, which was isolated in a yield of 70.8%.
Example 5
Example 5 is different from example 1 in that 0.5 g anatase type nano titanium dioxide is added as catalyst, under 40 deg.C, 365nm LED lamp is used as light source to irradiate for 9 h, the upper organic phase is processed by decompression concentration column chromatography to obtain reddish brown liquid 2-methoxy-5-aminopyridine 70mg, the separation yield is 86.7%.
Example 6
Example 6 is different from example 1 in that the particle size of rutile nano titanium dioxide is 15nm, the rutile nano titanium dioxide is irradiated for 6.5 h by using 365nm LED lamp as light source, and the upper organic phase is subjected to reduced pressure concentration column chromatography to obtain a reddish brown liquid 2-methoxy-5-aminopyridine 73mg, and the separation yield is 90.2%.
Example 7
Example 7 is different from example 1 in that the particle size of rutile nano titanium dioxide is 200nm, the rutile nano titanium dioxide is irradiated for 6.5 h by using 365nm LED lamp as light source, and the upper organic phase is subjected to reduced pressure concentration column chromatography to obtain a reddish brown liquid 2-methoxy-5-aminopyridine 68mg, and the separation yield is 84.2%.
Example 8
Example 8 is different from example 1 in that the particle size of rutile nano titanium dioxide is 45nm, and the upper organic phase is subjected to column chromatography by concentration under reduced pressure to obtain a reddish brown liquid, namely 75mg of 2-methoxy-5-aminopyridine, and the separation yield is 93.2%.
Example 9
Example 9 is different from example 1 in that the particle size of rutile nano titanium dioxide is 60nm, and the upper organic phase is subjected to column chromatography by concentration under reduced pressure to obtain 2-methoxy-5-aminopyridine 74m g as a red brown liquid, and the separation yield is 91.9%.
Example 10
Example 10 differs from example 1 in that 1.0 mL of purified water was added, the mixture was irradiated with 365nm LED lamp for 8 hours, and the upper organic phase was subjected to column chromatography under reduced pressure to give 73mg of 2-methoxy-5-aminopyridine as a reddish brown liquid, which was isolated in a yield of 90.2%.
Example 11
Example 11 is different from example 1 in that 0.2 mL of purified water was added, the mixture was irradiated with 365nm LED lamp for 8 hours, and the upper organic phase was subjected to column chromatography under reduced pressure to give 70mg of 2-methoxy-5-aminopyridine as a reddish brown liquid, which was isolated in 86.9% yield.
Example 12
Example 12 differs from example 1 in that 0.15 mL of purified water was added, the mixture was irradiated with 365nm LED lamp for 8 hours, and the upper organic phase was subjected to column chromatography under reduced pressure to give 66mg of 2-methoxy-5-aminopyridine as a reddish brown liquid, which was isolated in 81.9% yield.
Example 13
Example 13 differs from example 10 in that 2-methoxy-5-nitropyridine (0.1 g, 0.65 mmol) was dissolved in 10mL of methanol, irradiated with 365nm LED lamp for 2 hours, and the upper organic phase was subjected to column chromatography under reduced pressure to give 56 mg of 2-methoxy-5-aminopyridine as a reddish brown liquid, which was isolated in a yield of 69.5%.
Example 14
Example 14 differs from example 10 in that 2-methoxy-5-nitropyridine (0.1 g, 0.65 mmol) was dissolved in 10mL of ethanol, irradiated with 365nm LED lamp for 3.5 h, and the upper organic phase was subjected to column chromatography under reduced pressure to give 59 mg of 2-methoxy-5-aminopyridine as a reddish brown liquid, which was isolated in 73.3% yield.
Example 15
Example 15 differs from example 10 in that 2-methoxy-5-nitropyridine (0.1 g, 0.65 mmol) was dissolved in 10mL of ethylene glycol, irradiated with 365nm LED lamp for 8 hours, and the upper organic phase was subjected to column chromatography under reduced pressure to give 61 mg of 2-methoxy-5-aminopyridine as a reddish brown liquid, which was isolated in a yield of 75.4%.
Example 16
Example 16 differs from example 10 in that 2-methoxy-5-nitropyridine (0.1 g, 0.65 mmol) was dissolved in 10mL of t-butanol, irradiated with 365nm LED lamp for 8 hours, and the upper organic phase was subjected to column chromatography by concentration under reduced pressure to give 69 mg of 2-methoxy-5-aminopyridine as a reddish brown liquid, which was isolated in 86.1% yield.
Example 17
Example 17 differs from example 16 in that 0.2 ml of purified water was added, HPLC showed the content of 2-methoxy-5-aminopyridine in the product system to be 89.8%, and the upper organic phase was subjected to column chromatography by concentration under reduced pressure to give 70mg of 2-methoxy-5-aminopyridine as a reddish brown liquid, which was isolated in 86.9% yield.
Example 18
Example 18 is different from example 2 in that 1mL of triethylamine is added as an additive, a 365nm LED lamp is used as a light source for irradiating for 2 hours, the reaction system is placed in a centrifuge for centrifugal separation, the upper organic phase is subjected to reduced pressure concentration and column chromatography to obtain a reddish brown liquid 2-methoxy-5-aminopyridine 57mg, and the separation yield is 71.1%.
Example 19
Example 19 differs from example 18 in that 1mL of triethanolamine was added as an additive, the mixture was irradiated with 365nm LED lamp for 2.5 hours, the reaction system was centrifuged in a centrifuge, the upper organic phase was concentrated under reduced pressure and subjected to column chromatography to give 77 mg of 2-methoxy-5-aminopyridine as a reddish brown liquid, and the isolation yield was 95.6%.
Example 20
Adding 2-methoxy-5-nitropyridine (0.1 g, 0.65 mmol) into a mixed solvent of isopropanol and tetrahydrofuran (isopropanol: tetrahydrofuran =5:5, 10 ml), stirring for clarification, adding 0.5 ml of purified water, then adding 0.5 g of rutile nano titanium dioxide as a catalyst to obtain a white suspension, stirring for 0.5 h, placing the white suspension in a photochemical reactor, irradiating for 6 h by using a 365nm LED lamp as a light source, monitoring by TLC or HPLC (high performance liquid chromatography) to stop the illumination of the raw materials to obtain a product system, placing the reaction system in a centrifuge for centrifugal separation, concentrating an upper organic phase under reduced pressure, and performing column chromatography to obtain 70mg of a reddish brown liquid, wherein the separation yield is 86.9%.
Example 21
Adding 2-methoxy-5-nitropyridine (0.1 g, 0.65 mmol) into a mixed solvent of isopropanol and PEG-400 (isopropanol: PEG-400=5:5, 10 ml), stirring for clarification, adding 0.5 ml of purified water, then adding 0.5 g of rutile nano titanium dioxide as a catalyst to obtain a white suspension, stirring for 0.5 h, placing in a photochemical reactor, irradiating for 7.5 h by using a 365nm LED lamp as a light source, monitoring by TLC or HPLC (high performance liquid chromatography) to stop the illumination of the raw material to obtain a product system, placing the reaction system in a centrifuge for centrifugal separation, concentrating an upper organic phase under reduced pressure, performing column chromatography to obtain a reddish brown liquid of 66mg of 2-methoxy-5-aminopyridine, wherein the separation yield is 82.7%.
Example 22
Example 22 is different from example 1 in that the wavelength of the LED lamp is 310nm, the illumination is 20h, the upper organic phase is concentrated under reduced pressure and then subjected to column chromatography to obtain 22.3mg of 2-methoxy-5-aminopyridine serving as a reddish brown liquid, and the isolation yield is 28%.
Example 23
Example 23 is different from example 1 in that the wavelength of the LED lamp is 400nm, the illumination is 20h, the upper organic phase is decompressed and concentrated, and column chromatography is carried out to obtain 24mg of 2-methoxy-5-aminopyridine serving as a red-brown liquid, and the separation yield is 30%.
Example 24
Example 24 is different from example 1 in that the wavelength of the LED lamp is 385nm, the illumination is 12h, the upper organic phase is decompressed and concentrated, column chromatography is carried out to obtain 64mg of 2-methoxy-5-aminopyridine serving as a reddish brown liquid, and the isolation yield is 79.5%.
Example 25
Example 25 is different from example 1 in that the wavelength of the LED lamp is 340nm, the illumination is 12h, the upper organic phase is decompressed and concentrated, and column chromatography is carried out to obtain the reddish brown liquid 2-methoxy-5-aminopyridine 65.2mg, and the isolation yield is 81%.
Example 26
Example 26 differs from example 1 in that the wavelength of the LED lamp is 450nm, the illumination time is 24h, the upper organic phase is concentrated under reduced pressure, and no 2-methoxy-5-aminopyridine is generated in column chromatography.
Example 27
Dissolving 1- (difluoromethyl) -4-nitropyrazole (1 g, 6.1 mmol) in isopropanol (100 mL), stirring for clarification, adding 5mL of purified water and 10mL of triethanolamine, then adding 1g of rutile nano titanium dioxide as a catalyst, stirring for 0.5 h, placing in a photochemical reactor, irradiating for 6.5 h by using a 365nm LED lamp as a light source, monitoring by HPLC (high performance liquid chromatography) to stop the illumination when the raw materials disappear, obtaining a product system, placing the product system in a centrifuge for centrifugal separation, and concentrating an upper organic phase under reduced pressure to obtain 656 mg of 1- (difluoromethyl) -4-aminopyrazole, wherein the separation yield is 80.4%. The nuclear magnetic hydrogen spectrum data is as follows:1H-NMR(400 MHz，CDCl3)：7.31（s, 2H），7.05（t,J=60Hz 1H），3.30-2.94（hr,s, 2H）。
example 28
Dissolving 2-chloro-3-nitropyridine (1 g, 6.3 mmol) in isopropanol (100 mL), stirring for clarification, adding 5mL of purified water and 10mL of triethanolamine, then adding 1g of rutile nano titanium dioxide as a catalyst, stirring for 0.5 h, placing in a photochemical reactor, irradiating for 7.5 h by using a 365nm LED lamp as a light source, monitoring by TLC or HPLC (high performance liquid chromatography) that the raw materials disappear, stopping illumination to obtain a product system, placing the product system in a centrifuge for centrifugal separation, and concentrating an upper organic phase under reduced pressure to obtain 646 mg of 2-chloro-3-aminopyridine, wherein the separation yield is 82.3%. The nuclear magnetic hydrogen spectrum data is as follows:1H-NMR (400 MHz，CDCl3) ：7.80 (dd, J= 3.5, 0.72 Hz, 1H)，7.06-7.02 (m, 2H)，4.09 (s, 2H) 。
example 29
Dissolving 4, 6-dichloro-5-nitropyrimidine (1 g, 5.2 mmol) in isopropanol (100 mL), stirring for clarification, adding 5mL of purified water and 10mL of triethanolamine, then adding 1g of rutile nano titanium dioxide as a catalyst, stirring for 0.5 h, placing in a photochemical reactor, irradiating for 5h by using a 365nm LED lamp as a light source, monitoring by TLC or HPLC (high performance liquid chromatography) that the raw materials disappear, stopping irradiation to obtain a product system, placing the product system in a centrifuge for centrifugal separation, and concentrating an upper organic phase under reduced pressure to obtain 732 mg of 4, 6-dichloro-5-aminopyrimidine with the separation yield of 86.6%. The nuclear magnetic hydrogen spectrum data is as follows:1H NMR(400 MHz，CDCl3)： 3.60 (br s, 2H)，8.21 (s, 1H)。
example 30
Example 30 differs from example 18 in that the content of 2-methoxy-5-aminopyridine in the product system was 96.8% by HPLC after irradiation with 365nm laser as light source and the upper organic phase was concentrated under reduced pressure to obtain 73mg of 2-methoxy-5-aminopyridine as a reddish brown liquid with an isolated yield of 90.7%.
Example 31
Dissolving 3-nitrothiophene (1 g, 7.74 mmol) in isopropanol (100 mL), stirring for clarification, adding 10mL of purified water and 10mL of triethanolamine, then adding 1g of rutile nano titanium dioxide as a catalyst to obtain a white suspension, stirring for 0.5 h, and placing in a photochemical reactorIn the reactor, a 365nm LED lamp is used as a light source for irradiating for 7.5 h, TLC or HPLC monitors that the raw materials disappear and stops irradiating to obtain a product system, the product system is placed in a centrifuge for centrifugal separation, and an upper organic phase is subjected to reduced pressure concentration to obtain 3-aminothiophene, 614 mg, wherein the separation yield is 80.1%. The nuclear magnetic hydrogen spectrum data is as follows:1H NMR(400 MHz，CDCl3)：4.50 (br s, 2H)，6.17 (d J=3.0Hz,1H), 6.65 (d J=5.2Hz,1H), 7.13 (d J=5.2Hz,1H)。
example 32
Dissolving ethyl 2- ((2, 6-dichloro-5-nitropyrimidin-4-yl) oxy) benzoate (1 g, 2.79 mmol) in isopropanol (100 mL), stirring for clarification, adding 10mL of purified water and 10mL of triethanolamine, then adding 1g of rutile nano titanium dioxide as a catalyst to obtain a white suspension, stirring for 0.5 h, placing in a photochemical reactor, irradiating for 2h by using a 365nm LED lamp as a light source, monitoring by TLC or HPLC (high performance liquid chromatography) that the raw materials disappear and stopping the irradiation to obtain a product system, placing the product system in a centrifuge for centrifugal separation, and concentrating an upper organic phase under reduced pressure to obtain 970mg of ethyl 2- ((2, 6-dichloro-5-aminopyrimidin-4-yl) oxy) benzoate with the separation yield of 95%. The nuclear magnetic hydrogen spectrum data is as follows:1H NMR (300 MHz, acetone-d6): = 8.12(d, J= 7.6 Hz, 1 H), 7.81(dd, J= 7.2 Hz, 1 H), 7.57 (dd, J= 7.7 Hz, 1 H),7.46 (d, J=8.4 Hz,1 H), 4.24 (q, J= 6.9 Hz, 2 H), 1.20 (t, J= 6.9 Hz, 3 H)。
example 33
Dissolving 2-methoxy-5-nitropyrimidine (1 g, 6.45 mmol) in isopropanol (100 mL), stirring for clarification, adding 10mL of purified water and 10mL of triethanolamine, then adding 1g of rutile nano titanium dioxide as a catalyst, stirring for 0.5 h, placing in a photochemical reactor, irradiating for 5.5 h by using a 365nm LED lamp as a light source, monitoring by TLC or HPLC (high performance liquid chromatography) that the raw materials disappear and stopping the illumination to obtain a product system, placing the product system in a centrifuge for centrifugal separation, and concentrating an upper organic phase under reduced pressure to obtain 716mg of 2-methoxy-5-aminopyrimidine, wherein the separation yield is 88.8%. The nuclear magnetic hydrogen spectrum data is as follows:1H NMR(400 MHz,DMSO-d6) 8.05 (s, 2H), 3.94 (s, 3H)。
example 34
Dissolving N- (5-nitropyrimidine-2-yl) acetamide (1 g, 5.49 mmol) in isopropanol (100 mL), stirring for clarification, adding 10mL of purified water and 10mL of triethanolamine, then adding 1g of rutile nano titanium dioxide as a catalyst, stirring for 0.5 h, placing in a photochemical reactor, irradiating for 6.5 h by using a 365nm LED lamp as a light source, monitoring by TLC or HPLC that the raw materials disappear, stopping the irradiation to obtain a product system, placing the product system in a centrifuge for centrifugal separation, and concentrating an upper organic phase under reduced pressure to obtain 705mg of N- (5-aminopyrimidine-2-yl) acetamide, wherein the separation yield is 84.4%. The nuclear magnetic hydrogen spectrum data is as follows:1H NMR (400 MHz,DMSO-d6) 2.03 (s, 3H), 2.86 (br s, 1H)，5.28 (s, 2H),7.99 (s, 2H)。
example 35
Dissolving 2, 4-dichloro-6-methyl-5-nitropyrimidine (1 g, 4.8 mmol) in isopropanol (100 mL), stirring for clarification, adding 10mL of purified water and 10mL of triethanolamine, then adding 1g of rutile nano titanium dioxide as a catalyst, wherein the system is a white suspension, stirring for 0.5 h, placing in a photochemical reactor, irradiating for 6.5 h by using a 365nm LED lamp as a light source, monitoring by TLC or HPLC (high performance liquid chromatography) that the raw materials disappear and stopping the irradiation to obtain a product system, placing the product system in a centrifuge for centrifugal separation, and concentrating an upper organic phase under reduced pressure to obtain 735mg of 2, 4-dichloro-6-methylpyrimidine-5-amine, wherein the separation yield is 86%. The nuclear magnetic hydrogen spectrum data is as follows:1H NMR (CDCl3): 2.32 (s, 3H, CH3), 6.08 (s, 2H, NH2, D2O exchangeable) 。
the catalyst in the above embodiment is recovered and reused in the above catalytic reaction, and the catalytic activity is reduced with the increase of the number of times of recycling the recovered catalyst, but the recycling of the recovered catalyst can maximize the utilization of the catalyst and reduce the amount of three wastes and the production cost.
The following are examples utilizing recovered catalysts:
dissolving 2-methoxy-5-nitropyridine (20 g, 130 mmol) in isopropanol (2000 mL), stirring for clarification, adding 100 mL of purified water and 200 mL of triethanolamine additive, then adding 20 g of recycled rutile nano titanium dioxide as a catalyst, stirring for 0.5 h, placing the mixture in a photochemical reactor, irradiating for 4h by using a 365nm LED lamp as a light source, and monitoring by HPLC (high performance liquid chromatography) that the raw materials disappear and the light irradiation is stopped to obtain a product system. The catalyst was repeatedly recovered and used 10 times, and the specific reaction conditions for recovering and using the catalyst were as in this example, 10 times of light reaction IPC (HPLC content) and the data of the separation yield of the heteroaromatic amine compound are shown in table 1 below.
Figure 790491DEST_PATH_IMAGE012
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
according to the photochemical synthesis method, the photocatalyst is used, under the condition of illumination, photoproduction holes and photoproduction electrons are formed on the surface of the catalyst, and the photoproduction electrons and water react to generate active hydrogen so as to further reduce nitro; namely, the photocatalytic reduction of various heteroaryl nitro compounds is realized under the illumination condition, and the heteroaryl amine compounds with higher yield are obtained. The photocatalyst is the existing commonly used catalyst, has no strict requirements on equipment, is easy to recover, and reduces the safety risk of the heteroaryl amine compound and the catalyst cost. The whole reaction process of the photocatalysis does not need to add any metal reagent and reducing agent, the conversion rate of the reaction is higher, and the post-treatment is simple and easy to operate, so that the photocatalysis is safer and more environment-friendly.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (25)

1. A photochemical synthesis method of a heteroarylamine compound, comprising:
step S1, mixing the raw materials including the heteroaryl nitro compound, the solvent and the photocatalyst to obtain a mixture;
and step S2, carrying out photocatalytic reduction reaction on the mixture under the illumination condition to obtain a product system containing the heteroaryl amine compound.
2. The photochemical synthesis method according to claim 1, wherein the heteroarylnitro-group compound has the general structural formula I or II:
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structural general formula I structural general formula II
Wherein n and m are each independently 0 or 1, Y, Z are each independently selected from the group consisting of chemically acceptable CR7、N、NR8O, S, and Y, Z at least one of N, NR8And O, S, R1、R2、R3、R4、R5、R6、R7、R8Each independently selected from H, substituted or unsubstituted C1~C20Alkyl, substituted or unsubstituted C1~C20Alkoxy, substituted or unsubstituted C6~C20Aryl, halogen, ester, hydroxyl, amide, nitro, -CF3、-CHF2One kind of (1).
3. The photochemical synthesis method of claim 2, wherein R is1、R2、R3、R4、R5、R6、R7、R8Each independently selected from substituted or unsubstituted C1~C10Linear alkyl, substituted or unsubstituted C of3~C10Branched alkyl, substituted or unsubstituted C1~C10Alkoxy, substituted orUnsubstituted C6~C10Any one of the aryl groups of (1).
4. The photochemical synthesis method according to any one of claims 3, characterized in that R is1、R2、R3、R4、R5、R6、R7、R8Each independently selected from methoxy, -Cl, -CHF2Any one of them.
5. The photochemical synthesis process of claim 1, wherein the solvent is selected from the group consisting of C1~C6Alcohol or C1~C6An aqueous alcohol solution of (a).
6. The photochemical synthesis method of claim 5, wherein C is1~C6The alcohol is selected from one or more of methanol, ethanol, ethylene glycol, isopropanol, n-butanol, tert-butanol and cyclohexanol.
7. The photochemical synthesis method of claim 5, wherein C is1~C6The volume ratio of the alcohol to the water in the alcohol aqueous solution is 10: 1-50: 1.
8. The photochemical synthesis method according to claim 1, characterized in that the active component of the photocatalyst is nano-titania.
9. The photochemical synthesis method according to claim 8, wherein the mass ratio of the heteroaryl nitro compound to the nano titanium dioxide is 1: 1-1: 5.
10. The photochemical synthesis method according to claim 8, wherein the particle size of the nano-titania is 15-200 nm.
11. The photochemical synthesis method according to claim 10, wherein the particle size of the nano-titania is 30-60 nm.
12. The photochemical synthesis method according to claim 8, characterized in that the nano titania is selected from one or more of rutile type nano titania, anatase type nano titania, nano titania supported microspheres.
13. The photochemical synthesis method according to claim 1, wherein in step S2, the temperature of the photocatalytic reduction reaction is 30 to 40 ℃.
14. The photochemical synthesis method according to claim 1, wherein the time of the photocatalytic reduction reaction is 2 to 15 hours.
15. The photochemical synthesis method according to claim 1, wherein the light wavelength in the light irradiation condition is 310 to 400 nm.
16. The photochemical synthesis method according to claim 15, wherein the light wavelength in the light irradiation condition is 340-385 nm.
17. The photochemical synthesis method of claim 1, wherein the light source is LED lamp or laser.
18. The photochemical synthesis method according to any one of claims 1 to 17, characterized in that the starting material further comprises a solubilizing agent.
19. The photochemical synthesis method of claim 18, wherein the solubilizing reagent is selected from one or more of tetrahydrofuran, acetone, ethyl acetate, polyethylene glycol-400.
20. Photochemical synthesis process according to any one of claims 1-17, characterized in that the starting material further comprises additives.
21. The photochemical synthesis process of claim 20, wherein the additive is selected from one or more of triethylamine, triethanolamine, sodium sulfite, sodium sulfide, EDTA, formic acid, ascorbic acid.
22. The photochemical synthesis method of claim 1, further comprising:
carrying out centrifugal separation on the product system to obtain clear liquid and solid;
carrying out reduced pressure concentration treatment on the clear liquid to obtain a heteroaryl amine compound and a recovered solvent;
and washing and drying the solid to recover the photocatalyst.
23. The photochemical synthesis process of claim 22, wherein the recovered solvent is returned to step S1 for use as the solvent.
24. The photochemical synthesis method according to claim 22, wherein the recovered photocatalyst is returned to step S1 to be used as the photocatalyst.
25. The photochemical synthesis method of claim 1, wherein the heteroarylamine compound has the formula:
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、
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、
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、
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、
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、
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、
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、
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、
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any one of them.
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