CN116162041B - Preparation method of azo compound - Google Patents

Preparation method of azo compound Download PDF

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CN116162041B
CN116162041B CN202310449400.XA CN202310449400A CN116162041B CN 116162041 B CN116162041 B CN 116162041B CN 202310449400 A CN202310449400 A CN 202310449400A CN 116162041 B CN116162041 B CN 116162041B
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photosensitizer
reaction
preparation
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CN116162041A (en
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张跃宗
万洪刚
孔令蜜
郑楠
王达伟
宋汪泽
张照阳
虞裔
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Dalian University of Technology
Jiangsu Zhongli Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a preparation method of azo compounds, which comprises the following steps: under the condition of 10-30W white light, through ionic g-C 3 N 4 The nano particles are used as photosensitizer, air is used as oxidant, hydrazine compounds are subjected to dehydrogenation oxidation reaction in water at room temperature, after 6-24 h, azo compounds are finally obtained with high conversion rate, the reaction condition is mild, the product yield is moderate to good, and the substrate range is wide; the ionic g-C used 3 N 4 The nano particles as photosensitizers show excellent photocatalytic activity, can induce dehydrogenation and oxidization of hydrazine compounds in a water phase, can be recycled repeatedly, and provides a green and sustainable way for the photocatalytic reaction in the water phase.

Description

Preparation method of azo compound
Technical Field
The invention relates to a preparation method of azo compounds, belonging to the technical field of organic synthesis.
Background
Azo compounds are an important class of organic compounds. Azo parent core structures are commonly used in dyes, pharmaceuticals, chemical sensors, smart responsive materials, free radical initiators, food additives (J. Am. chem. Soc. 133 (2011) 3788-3791;ACS Sustainable Chem. Eng. 8 (2020) 14377-14385; chem. Soc. Rev. 41 (2012) 1809-1825.). However, the synthesis method of azo compounds is limited, has low efficiency, and produces a large amount of organic waste liquid, waste gas, waste residue and the like. Therefore, the development of a green and efficient synthesis method for preparing azo compounds has important research significance.
Currently, a strategy of dehydrogenation oxidation reaction is mainly adopted for the synthesis of azo compounds. In 2017, hashimoto et al used a strongly basic system of potassium t-butoxide and liquid ammonia to prepare azo compounds (angelw. Chem. Int. Ed. 2017, 56, 870-873). Some metal-catalyzed dehydrooxidation processes were developed, but most dehydrooxidation reactions require a transition metal catalyst and a stoichiometric oxidant to produce azo compounds (chem. Sci. 2012, 3, 883-886; angel. Chem. Int. Ed. 2021, 60, 6382-6385;Org. Biomol. Chem. 2020, 183471-3474 and Angew. Chem. Int. Ed. 2016, 55, 2171-2175). In recent years, some transition metals or organic dyes have been used as photocatalysts for dehydrogenation oxidation reaction with oxygen (air) as an oxidizing agent to prepare azo compounds (ACS Sustainable chem. Eng. 2020, 8, 14377-14385; green chem. 2019, 21, 4055-4061; ACS catalyst. 2018, 8, 7727-7733).
However, most of the dehydrogenation oxidation reactions reported so far are based on photocatalysis of homogeneous small molecule photosensitizers in organic solvents, lacking reusability and recyclability of photosensitizers. Therefore, there is a need to develop reusable water-compatible heterogeneous photosensitizers to achieve green synthesis of azo compounds.
Disclosure of Invention
In order to achieve the above purpose, the present invention provides the following technical solutions:
a process for preparing photosensitizer comprises dissolving polymer P1 or P2 in DMF solvent, and adding g-C 3 N 4 Dispersing in ethanol/sodium hydroxide solution, mixing P1 or P2 solution with g-C 3 N 4 Is mixed with the dispersion liquid of the above to obtain a mixed liquid, and is slowly added into deionized water in a dropwise manner to obtain a mixed liquidStirring overnight and lyophilizing to obtain ionic g-C 3 N 4 Nanoparticle 1 or 2, the photosensitizer;
the ionic g-C 3 N 4 Nanoparticle 1 or 2 can be redissolved in deionized water to prepare ionic g-C 3 N 4 Mother liquor of nanoparticle 1 or 2;
the g-C 3 N 4 The grain size of the particles is 50nm; the g-C 3 N 4 The mass ratio of the P-type compound to P1 or P2 is 1:10;
the structural formula of the P1 is as follows:
Figure SMS_1
the structural formula of the P2 is as follows:
Figure SMS_2
。
the photosensitizer is prepared according to the preparation method.
The preparation method of azo compounds adopts the photosensitizer to catalyze, under the condition of 10-30W visible light, hydrazine compounds are subjected to dehydrogenation oxidation reaction with air at room temperature in water, and after reaction is carried out for 6-24 h, azo compounds are obtained, wherein the reaction formula is as follows:
Figure SMS_3
the structural general formula of the hydrazine compound is as follows:
Figure SMS_4
the structural general formula of the azo compound is as follows:
Figure SMS_5
wherein R is 1 And R is 2 Is hydrogenAlkyl or halogen;
g-C in the photosensitizer 3 N 4 The mass ratio of the dosage of the hydrazine compound to the hydrazine compound is 1:10000-1:240.
The preparation method also comprises a photosensitive agent recycling step, wherein the photosensitive agent recycling step comprises the following steps: and extracting the azo compound obtained after the dehydrogenation oxidation reaction by ethyl acetate, layering, centrifuging solid insoluble matters in the water phase at a high speed, collecting precipitate, placing the precipitate in a vacuum oven, further pumping the solvent to obtain a recovered photosensitizer, and adding the recovered photosensitizer into the dehydrogenation oxidation reaction again.
The preparation method of P1 and P2 is as follows:
vacuum-pumping the pressure-resistant sealed reaction bottle, adding nitrogen protection, adding an aromatic sulfonyl azide monomer M1 or M2, an ether aldehyde monomer M3 or M4 and a cyclic amino acid monomer M5 or M6 into the reaction bottle, dissolving in a mixed solvent of ethanol and DMF (ethanol/DMF=1/1, v/v), continuously stirring for 20 h at 150 ℃, and stopping the reaction; and respectively settling and washing three times by using methyl tertiary butyl ether and ethanol, centrifuging and collecting precipitate, and vacuum drying the product to constant weight to obtain the corresponding P1 (M1+M3+M5) and P2 (M2+M4+M6).
Wherein the monomer structures of M1-M6 are as follows:
M1:
Figure SMS_6
M2:/>
Figure SMS_7
M3:
Figure SMS_8
M4: />
Figure SMS_9
M5: />
Figure SMS_10
M6:
Figure SMS_11
wherein, the structures of P1 and P2 are respectively as follows:
P1、
Figure SMS_12
M w = 37600 g/mol, M w /M n = 1.68。
P2、
Figure SMS_13
M w = 32800 g/mol, M w /M n = 1.35。
g-C in the photosensitizer 3 N 4 The mass ratio of the dosage of the hydrazine compound to the hydrazine compound is 1:10000-1:240.
Further, the preparation method further comprises a photosensitive agent recycling step, wherein the photosensitive agent recycling step comprises the following steps: extracting the azo compound obtained after the dehydrogenation oxidation reaction by ethyl acetate, layering, centrifuging solid insoluble matters in the water phase at a high speed, collecting precipitate, placing the precipitate in a vacuum oven, further pumping the solvent to obtain a recovered photosensitizer, and adding the recovered photosensitizer into the dehydrogenation oxidation reaction again.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the polymer of the zwitter ion to encapsulate the g-C 3 N 4 By g-C 3 N 4 Electrostatic attraction of the charge of (2) and the charge of the polymer carrier to form a nanoparticle with a size of 300nm micron order, g-C 3 N 4 The polymer is coated on the inner layer and the outer layer, the polymer fragment with good hydrophilicity is used for reducing the dosage of the nitrogen carbide to 200ppm, and the polymer with amphoteric ion is coated on the g-C 3 N 4 As the container can attract reactants, the hydrazine compound as a reaction substrate is a hydrophobic substrate, so the hydrazine compound can be easily entrapped with the polymer of the zwitterion to g-C 3 N 4 The hydrophobic portions of the nanoparticles of (2) are bound by hydrophobic forces, thereby entering the interior of the nanoparticle, allowing the reactants and g-C 3 N 4 The local concentration in the nanoparticle is significantly increased, fromAnd results of better catalytic efficiency are achieved with lower catalyst addition.
The reaction is carried out in the water phase, other organic solvents are not needed, waste is little, and the method is environment-friendly. The reaction can be carried out at room temperature without heating, and has simple operation and high conversion rate.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a compound 2a produced in example 5 of the present invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the compound 2b produced in example 7 of the present invention.
FIG. 3 shows the ionic g-C in example 3 of the present invention 3 N 4 Particle size distribution profile of nanoparticle 1.
FIG. 4 shows the ionic g-C in example 4 of the present invention 3 N 4 Particle size distribution profile of nanoparticles 2.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1, P1 preparation method:
vacuum-pumping the pressure-resistant sealed reaction bottle, adding nitrogen protection, adding M1 (0.5 mmol,190.0 mg), M3 (0.55 mmol,221.19 mg) and M5 (3.0 mmol,387.24 mg) into the nitrogen-protected reaction bottle, dissolving in a mixed solvent of ethanol and DMF (ethanol 5mL +DMF 5 mL), continuously stirring at 150 ℃ for 20 h, and stopping the reaction; respectively settling and washing three times by using methyl tertiary butyl ether and ethanol, centrifugally collecting sediment, carrying out vacuum drying on the product until the weight is constant to obtain the corresponding P1 (M1+M3+M5), and obtaining the product with the yield of 85%,M w = 37600 g/mol, M w /M n = 1.68。
the characterization results are as follows:
1 H NMR (400 MHz, d 6 -DMSO): δ 7.90 – 7.63 (4H), 7.20 (8H), 6.88 (4H), 4.10-4.62 (8H), 3.70 (4H), 3.53 (8H), 3.33 (4H), 2.90 (4H), 1.66 (8H)。
example 2, P2 preparation method:
vacuum-pumping the pressure-resistant sealed reaction bottle, adding nitrogen protection, adding M2 (0.5 mmol,282.06 mg), M4 (0.55 mmol,172.77 mg) and M6 (3.0 mmol,345.18 mg) into the nitrogen-protected reaction bottle, dissolving in a mixed solvent of ethanol and DMF (ethanol 5mL +DMF 5 mL), continuously stirring at 150 ℃ for 20 h, and stopping the reaction; respectively settling and washing three times by using methyl tertiary butyl ether and ethanol, centrifugally collecting sediment, carrying out vacuum drying on the product until the weight is constant to obtain the corresponding P2 (M2+M4+M6), and obtaining the product with the yield of 85 percent,M w = 32800 g/mol, M w /M n = 1.35。
the characterization results are as follows:
1 H NMR (400 MHz, d 6 -DMSO):δ 7.80 (4H), 7.50 (4H), 7.12 (4H), 6.87 (4H), 5.15 (4H), 4.46 (3H), 4.07 (5H), 3.78 (4H), 3.42 (4H), 2.89 (4H), 2.35 (4H), 1.91 (4H), 1.52 (4H), 1.25 (4H)。
example 3 ionic g-C 3 N 4 Preparation of nanoparticle 1:
will g-C 3 N 4 50nm (1 mg) in ethanol/sodium hydroxide solution (1 mL, naOH mass 50 mg) and heating to 50 o C promoting dispersion to prepare g-C 3 N 4 Dispersing liquid, dissolving P1 (10 mg) in DMF (1 mL) to prepare a polymer solution, and mixing the above g-C 3 N 4 The dispersion was mixed with the polymer solution in a volume ratio of 1:1 (i.e., 1mLg-C 3 N 4 Dispersing liquid+1 mL polymer solution) and stirring uniformly to obtain g-C 3 N 4 P1 mixture (2 mL), dropwise adding the mixture (2 mL) into deionized water (18 mL) at a rate of 50 μL per minute, and stirring overnight to obtain ionic g-C 3 N 4 The nanoparticle 1 aqueous solution is freeze-dried and the solvent is sufficiently removed to obtain the ionic g-C 3 N 4 Nanoparticle 1 was reconstituted in deionized water (20 mL) to give ionic g-C 3 N 4 Nanoparticle 1 mother liquor (g-C) 3 N 4 Is 1mg/20 mL).
Example 4, ionic g-C 3 N 4 Preparation of nanoparticle 2:
will g-C 3 N 4 50nm (1 mg) in ethanol/sodium hydroxide solution (1 mL, naOH mass 50 mg) and heating to 50 o C promoting dispersion to prepare g-C 3 N 4 Dispersing liquid, dissolving P2 (10 mg) in DMF (1 mL) to prepare a polymer solution, and mixing the above g-C 3 N 4 The dispersion was mixed with the polymer solution in a volume ratio of 1:1 (i.e., 1mLg-C 3 N 4 Dispersing liquid+1 mL polymer solution) and stirring uniformly to obtain g-C 3 N 4 P1 mixture (2 mL), dropwise adding the mixture (2 mL) into deionized water (18 mL) at a rate of 50 μL per minute, and stirring overnight to obtain ionic g-C 3 N 4 The nanoparticle 2 aqueous solution is freeze-dried and the solvent is sufficiently removed to obtain the ionic g-C 3 N 4 Nanoparticle 2, and redissolved in deionized water (20 mL) to give ionic g-C 3 N 4 Nanoparticle 2 mother liquor (g-C) 3 N 4 Is 1mg/20 mL).
Example 5 preparation of azobenzene:
diphenylhydrazine 1a (18.4 mg,0.1 mmol), ion g-C 3 N 4 Nanoparticle 1 aqueous mother liquor (368. Mu.L, g-C) 3 N 4 Is 0.0184mg, g-C 3 N 4 1a mass ratio of 1:1000) and H 2 O (632. Mu.L) was added to an open vial containing a magneton and stirred at room temperature under illumination of a white LED (20W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give orange solid 2a (17.0 mg, 93% yield).
The structure of the obtained compound 2a was:
Figure SMS_14
the characterization of the compound 2a obtained is as follows:
1 H NMR (400 MHz, CDCl 3 ) δ 7.93 (d, J = 7.5 Hz, 4H), 7.46-7.55 (m, 6H)。
compound 2a is a known compound whose spectrum is in complete agreement with literature reports (tetrahedron, 2007, 63, 11822-11827).
Example 6, cyclic experiment for photosensitizer for preparation of compound 2 a:
in the preparation of compound 2a, the extracted ionic g-C is obtained by freeze-drying in the aqueous phase 3 N 4 Nanoparticle 1, dissolved in deionized water (368. Mu.L) as photosensitizer and added again to the reaction, diphenylhydrazine 1a (18.4 mg,0.1 mmol) and H 2 O (1.0 mL) was added to an open vial containing magnetons and solid precipitate and stirred at room temperature under illumination of a white LED (20W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give orange solid 2a (16.5 mg, 91% yield). The above operation is repeated, and the yield of the final 2a is stabilized between 88% and 91%.
Example 7,4,4 preparation of dimethyl azobenzene:
4,4' -Dimethyldiphenylhydrazine 1b (21.2 mg,0.1 mmol), ionic g-C 3 N 4 Nanoparticle 1 aqueous mother liquor (42.4. Mu.L, g-C containing) 3 N 4 The mass of (C) is 0.00212 mg, g-C 3 N 4 1b mass ratio of 1:10000) and H 2 O (1.0 mL) was added to an open vial containing a magneton and stirred at room temperature under illumination of a white LED (10W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give 2b (18.9, mg, 90% yield) as a yellow solid.
The structure of the obtained compound 2b was:
Figure SMS_15
the characterization of the compound 2b obtained is as follows:
1 H NMR (600 MHz, CDCl 3 ) δ 7.82 (d, J = 8.3 Hz, 4H), 7.30 (d, J = 8.1 Hz, 4H), 2.43 (s, 6H)。
compound 2b is a known compound whose spectrum is in complete agreement with literature reports (chem. Commun. 2010, 46, 3173-3175.).
Example 8,4,4 preparation of diethyl azobenzene:
4,4' -diethyldiphenylhydrazine 1C (24.0 mg,0.1 mmol), ionic g-C 3 N 4 Nanoparticle 1 aqueous mother liquor (96. Mu.L, g-C containing) 3 N 4 Is 0.0048 mg, g-C 3 N 4 1:5000) and H 2 O (904. Mu.L) was added to an open vial containing magnetons and stirred at room temperature under illumination of a white LED (30W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give 2c (23.6 mg, 99% yield) as a yellow solid.
The structure of the obtained compound 2c was:
Figure SMS_16
the characterization of the compound 2c obtained is as follows:
1 H NMR (600 MHz, CDCl 3 ) δ 7.85 (d, J = 8.4 Hz, 4H), 7.34 (d, J = 8.3 Hz, 4H), 2.74 (q, J = 7.6 Hz, 4H), 1.30 (t, J = 7.6 Hz, 6H)。
compound 3c is a known compound whose spectrum is in complete agreement with literature reports (Green chem. 2019, 21, 4189-4193).
Example 9,4,4 preparation of dichloroazobenzene:
4,4' -dichloro-diphenyl-hydrazine 1d (25.2 mg,0.1 mmol), ionic g-C 3 N 4 Nanoparticle 1 aqueous mother liquor (200. Mu.L, g-C containing) 3 N 4 Is 0.01 mg, g-C 3 N 4 1d mass ratio of 1:2520) and H 2 O (800. Mu.L) was added to an open vial containing magnetons and stirred at room temperature under illumination of a white LED (20W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give 2d (18.3 mg, 73% yield) as a yellow solid.
The structure of the obtained compound 2d is:
Figure SMS_17
the characterization of the compound 2d obtained is as follows:
1 H NMR (600 MHz, CDCl 3 ) δ 7.87 (d, J = 8.3 Hz, 4H), 7.64 (d, J = 8.5 Hz, 4H)。
compound 3d is a known compound whose spectrum is completely consistent with literature reports (chem. Commun. 2010, 46, 3173-3175).
Example 10,4,4 preparation of diiodoazobenzene:
4,4' -Diiodiphenylhydrazine 1e (43.5 mg,0.1 mmol), ion g-C 3 N 4 Nanoparticle 1 aqueous mother liquor (1.74 mL, g-C containing) 3 N 4 Is 0.087 mg g-C 3 N 4 1:500) and H 2 O (260. Mu.L) was added to an open vial containing magnetons and stirred at room temperature under illumination of a white LED (20W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give 2e (35.5, mg, 82% yield) as a yellow solid.
The structure of the obtained compound 2e is:
Figure SMS_18
the characterization of the compound 2e obtained is as follows:
1 H NMR (600 MHz, CDCl 3 ) δ 7.86 (d, J = 8.7 Hz, 4H), 7.49 (d, J = 8.7 Hz, 4H)。
compound 2e is a known compound whose spectrum is in complete agreement with literature reports (RSC adv 2021, 11, 7251-7256).
Example 11,3,3', preparation of 4,4' -tetramethylazobenzene:
3,3', 4' -Tetramethylbenzyldihydrazide 1f (24.0 mg,0.1 mmol) and ionic g-C 3 N 4 Nanoparticle 1 aqueous mother liquor (2 mL, g-C containing) 3 N 4 Is 0.1 mg g-C 3 N 4 1f mass ratio 1:240) was added to an open vial containing magnetons and stirred at room temperature under irradiation of a white LED (20W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give yellow liquid 2f (23.3 mg, 98% yield).
The structure of the obtained compound 2f is:
Figure SMS_19
the characterization of the compound 2f obtained is as follows:
1 H NMR (400 MHz, CDCl 3 ) δ 7.66-7.76 (m, 4H), 7.29 (d, J = 8.1 Hz, 2H), 2.39 (s, 6H), 2.37 (s, 6H)。
compound 2f is a known compound whose spectrum is in complete agreement with literature reports (Green chem. 2019, 21, 4189-4193).
Example 12 preparation of 2-methylazobenzene:
1g (19.8 mg,0.1 mmol) of 2-methyldiphenylhydrazine and g-C 3 N 4 Ionic g-C 3 N 4 Nanoparticle 2 aqueous solution motherLiquid (39.6. Mu.L, containing g-C) 3 N 4 Is 0.00198 mg, g-C 3 N 4 1g mass ratio of 1:10000) and H 2 O (960.4. Mu.L mL) was added to an open vial containing a magneton and stirred at room temperature under illumination of a white LED (20W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give 2g (18.2. 18.2 mg, yield 93%) of a yellow liquid.
The structure of the resulting compound 2g was:
Figure SMS_20
the characterization result of 2g of the obtained compound is as follows:
1 H NMR (400 MHz, CDCl 3 ) δ 7.94 (d, J = 7.1 Hz, 2H), 7.64 (s, 1H), 7.53 (t, J = 7.5 Hz, 2H), 7.48 (t, J = 7.3 Hz, 1H), 7.41-7.32 (m, 2H), 7.28 (t, J = 7.4 Hz, 1H), 2.74 (s, 3H)。
compound 2g is a known compound whose spectrum is completely in accordance with literature reports (Green chem. 2019, 21, 4189-4193).
Example 13 preparation of 4-methoxyazobenzene:
4-Methoxydiphenyl hydrazine (21.4 mg,0.1 mmol) was added to the mixture for 1h, followed by ion g-C 3 N 4 Nanoparticle 2 aqueous mother liquor (1.78 mL, g-C content) 3 N 4 Is 0.0892 mg, g-C 3 N 4 1:240) and H 2 O (220. Mu.L mL) was added to an open vial containing a magneton and stirred at room temperature under illumination of a white LED (20W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give a brown solid for 2h (19.3 mg, 91% yield).
The structure of the obtained compound 2h is:
Figure SMS_21
the characterization result of the obtained compound 2h is as follows:
1 H NMR (400 MHz, CDCl 3 ) δ 7.41 – 7.31 (m, 4H), 7.30 – 7.23 (m, 4H), 7.20 – 7.13 (m, 4H), 6.94 (t, J = 7.2 Hz, 1H), 5.68 (s, 1H), 3.84 – 3.62 (m, 2H), 3.26 – 2.95 (m, 2H)。
compound 2h is a known compound whose spectrum is fully consistent with literature reports (j. Am. chem. Soc. 2007, 129, 13784-13785.).
Example 14 preparation of 4-bromoazobenzene:
4-Bromobiphenyl hydrazine 1i (26.2 mg,0.1 mmol), ion g-C 3 N 4 Nanoparticle 2 aqueous mother liquor (200. Mu.L, g-C-containing) 3 N 4 Is 0.01 mg, g-C 3 N 4 1i mass ratio of 1:2620) and H 2 O (800. Mu.L) was added to an open vial containing magnetons and stirred at room temperature under illumination of a white LED (20W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give yellow solid 2i (24.7, mg, 95% yield).
The structure of the obtained compound 2i is:
Figure SMS_22
the characterization of the compound 2i obtained is as follows:
1 H NMR (400 MHz, CDCl 3 ) δ 7.97 7.90 (m, 2H), 7.81 (d, J = 8.6 Hz, 2H), 7.65 (d, J = 8.6 Hz, 2H), 7.51 (m, 3H)。
compound 2i is a known compound whose spectrum is in complete agreement with literature reports (ACS catalyst 2013, 3, 478-486.).
Example 15,3,4 preparation of dimethyl azobenzene:
3, 4-Dimethyldiphenylhydrazine 1j (21.2 mg,0.1 mmol), ionic g-C 3 N 4 Nanoparticle 2 aqueous mother liquor (200. Mu.L, g-C-containing) 3 N 4 Is 0.01 mg, g-C 3 N 4 1:2120) and H 2 O (800. Mu.L) was added to an open vial containing magnetons and stirred at room temperature under illumination of a white LED (20W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give brown solid 2j (18.5, mg, 88% yield).
The structure of the obtained compound 2j is:
Figure SMS_23
the characterization of the compound 2j obtained is as follows:
1 H NMR (400 MHz, CDCl 3 ) δ 7.91 (d, J = 7.0 Hz, 2H), 7.64-7.78 (m, 2H), 7.42-7.58 (m, 3H), 7.28 (d, J = 7.9 Hz, 1H), 2.36 (d, J = 9.0 Hz, 6H)。
compound 2j is a known compound whose spectrum is in complete agreement with literature reports (Green chem.2019, 21, 4189-4193.).
Example 16,3,4 preparation of dimethyl azobenzene:
3,4, 5-trimethyldiphenylhydrazine 1k (22.6 mg,0.1 mmol), ion g-C 3 N 4 Nanoparticle 2 aqueous mother liquor (200. Mu.L, g-C-containing) 3 N 4 Is 0.01 mg, g-C 3 N 4 1k mass ratio of 1:2260) and H 2 O (800) was added to an open vial containing a magneton and stirred at room temperature under illumination of a white LED (20W). After 12 hours of reaction, the crude product was extracted with ethyl acetate (3×2.0 mL). The organic layers were combined with anhydrous Na 2 SO 4 Dried and then concentrated in vacuo. The residue was separated by column chromatography to give 2k (20.0. 20.0 mg, 89% yield) as a red solid。
The structure of the resulting compound 2k is:
Figure SMS_24
the characterization of the compound 2k obtained is as follows:
1 H NMR (400 MHz, CDCl 3 ) δ 7.87-7.94 (m, 2H), 7.60 (s, 2H), 7.42-7.55 (m, 3H), 2.39 (s, 6H), 2.26 (s, 3H)。
compound 2k is a known compound whose spectrum is in complete agreement with literature reports (Green chem.2019, 21, 4189-4193.).

Claims (2)

1. The preparation method of the azo compound is characterized in that the azo compound is prepared by adopting a photosensitizer for catalysis, and under the condition of 10-30W visible light, the hydrazine compound and air are subjected to dehydrogenation oxidation reaction at room temperature in water, and after the reaction is carried out for 6-24 h, the azo compound is obtained, wherein the reaction formula is as follows:
Figure QLYQS_1
the structural general formula of the hydrazine compound is as follows: />
Figure QLYQS_2
The structural general formula of the azo compound is as follows:
Figure QLYQS_3
wherein R is 1 And R is 2 Hydrogen, alkyl or halogen;
the preparation method of the photosensitizer comprises the following steps: polymer P1 or P2 was dissolved in DMF solvent, g-C 3 N 4 Dispersing in ethanol/sodium hydroxide solution, mixing P1 or P2 solution with g-C 3 N 4 Mixing the dispersion liquid of (2) to obtain a mixed liquid, slowly dripping deionized water into the mixed liquid, stirring overnight, and freeze-drying to obtain ionic g-C 3 N 4 Nanoparticles 1 or 2, i.e. the photosensitizer;
the g-C 3 N 4 The grain size of the particles is 50nm; the g-C 3 N 4 The mass ratio of the P-type compound to P1 or P2 is 1:10;
mw= 37600 g/mol of P1 is as follows:
Figure QLYQS_4
mw=32800 g/mol of P2 has the following structural formula: />
Figure QLYQS_5
g-C in the photosensitizer 3 N 4 The mass ratio of the dosage of the hydrazine compound to the hydrazine compound is 1:10000-1:240.
2. The method for producing an azo compound of claim 1, further comprising a step of recycling a photosensitizer, the step of recycling a photosensitizer comprising: and extracting the azo compound obtained after the dehydrogenation oxidation reaction by ethyl acetate, layering, centrifuging solid insoluble matters in the water phase at a high speed, collecting precipitate, placing the precipitate in a vacuum oven, further pumping the solvent to obtain a recovered photosensitizer, and adding the recovered photosensitizer into the dehydrogenation oxidation reaction again.
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