CN103265450A - Method for photocatalytic synthesis of azoxybenzene and azobenzene compounds - Google Patents
Method for photocatalytic synthesis of azoxybenzene and azobenzene compounds Download PDFInfo
- Publication number
- CN103265450A CN103265450A CN2013102170962A CN201310217096A CN103265450A CN 103265450 A CN103265450 A CN 103265450A CN 2013102170962 A CN2013102170962 A CN 2013102170962A CN 201310217096 A CN201310217096 A CN 201310217096A CN 103265450 A CN103265450 A CN 103265450A
- Authority
- CN
- China
- Prior art keywords
- alcohol
- zinin
- compound
- photochemical catalysis
- synthetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for photocatalytic synthesis of azoxybenzene and azobenzene compounds. The method comprises the following steps: uniformly mixing a nitrobenzene compound, alkali and alcohol by molar ratio of 1:(0.1-20):(40-1000) to form a liquor; adding a copper/graphene catalyst into the liquor for ultrasonic dispersion for 5-240 minutes by mass ratio of the nitrobenzene compound and the catalyst: 1:(0.001-2); irradiating the dispersed liquor protected by inert gas and stirred with intensity of 0.001-5W/cm<2>, and heating to 20-80 DEG C and reacting for 3-10 hours to obtain the azoxybenzene compound; and heating to over 80 DEG C but below 150 DEG C and reacting for 3-10 hours to obtain the azobenzene compound. The method provided by the invention has the advantages of environmental friendliness, low cost, mild operation condition and high yield.
Description
Technical field
The invention belongs to the synthetic method of a kind of azoxybenzene compound and azobenzene compound, be specifically related to the method for the synthetic azoxybenzene compound of a kind of photochemical catalysis and azobenzene compound.
Background technology
Azoxybenzene compound and azobenzene compound are important organic synthesis intermediate and fine chemical materials, their application is very extensive, include aspects such as organic dye, medicine intermediate, sensitive materials, liquid-crystal display and photoswitch control material, at aspects such as constructing natural compounds and functional materials important application is arranged also simultaneously.
At present, the preparation of azoxybenzene compound mainly realizes by the reduction nitrobenzene compounds, for example hydrogenation method reduction nitrobenzene compounds, glucose reduction nitrobenzene compounds (concentrated base condition), formaldehyde reduction nitrobenzene compounds (concentrated base condition), in organic solvent with metal or metallic compound reduction nitrobenzene compounds etc., but problem such as these methods mostly exist that cost is higher, complex operation, disposal of three wastes difficulty and environmental pollution are serious.Chinese patent (application number: 20101036406.4) disclose a kind of synthetic method of zinin.This method is reaction medium with the water-ethanol mixed solvent, is catalyzer with polyoxyethylene glycol-1000, uses KBH in the presence of KOH
4The reduction nitrobenzene compound obtains azobenzene oxide compound.Though this method is short reaction time, a large amount of KBH that adopt
4As reductive agent, cost is higher, exists problems such as disposal of three wastes difficulty and environmental pollution be serious.
The common method of synthetic azobenzene compound is earlier synthetic diazonium salt, then carries out coupling, forms azo-compound.Reaction equation is as follows:
This reaction was generally for two steps, but because there is huge potential safety hazard in process of production in dangerous difficult preservation of diazonium salt.Therefore people begin to develop other synthetic method, for example, the nitrobenzene reduction method, the zinin reduction is sent out, the aniline oxidation style, the hydrazobenzene oxidation style, but these method reaction conditionss are harsh, as High Temperature High Pressure etc., the metal-salt consumption is big simultaneously, causes serious environmental to pollute.Big in order to solve in the azobenzene compound process amount of metal salts, problem such as environmental pollution is serious, people have developed different preparation process.Chinese patent (application number: 201210183645.4) announced that a kind of aromatic amine prepares the method for aromatic azo compound under metallic nano crystal catalysis.This method is to be substrate with the aromatic amine, is catalyzer with the metallic nano crystal, and after substrate, catalyzer and alkali dissolution were in the organic solvent, reaction prepared aromatic azo compound in autoclave.Advantages such as technology is easy though method has, but environmental friendliness, catalyzer reuse and metal catalyst versatility are good, reaction still needs carry out under condition of high voltage.
Recently, Australian scientist (Angew. Chem. Int. Ed., 2010,122,9851 – 9855) finds nanometer gold is loaded on the Zirconia carrier, can utilize ultraviolet and visible light to drive, and nitrobenzene reduction is become nitrogen benzide.This technology has environment simple to operate, energy-conservation and good selective, but price of gold lattice costliness is not suitable for commercial catalysts and uses.
Summary of the invention
The purpose of this invention is to provide a kind of environmental protection, with low cost, operational condition gentleness, the method for the synthetic azoxybenzene compound of the photochemical catalysis that product yield is high and azobenzene compound.
Detailed process is as follows:
(1) nitrobenzene compounds, alkali and alcohol are evenly formed solution according to the 1:0.1-20:40-1000 mixed in molar ratio after, mass ratio by nitrobenzene compounds and catalyzer is 1:0.001-2, adds copper/graphen catalyst, ultra-sonic dispersion 5-240min in solution;
(2) with scattered solution at inert atmosphere protection, under the agitation condition, at 0.001-5W/cm
2Illumination under the intensity is heated to 20-80
oReaction 3-10h can obtain azoxybenzene compound during C; Be heated to 80
oC is above, 150
oReaction 3-10h can obtain the azobenzene compound when C was following.
Synthetic method of the present invention is a kind of universal method, be applicable to synthetic various azo compounds and derivative thereof, therefore multiple functional group on the aromatic ring is had higher tolerance, and there is no particular restriction to the substituent number in azo compound and the derivative and kind.Correspondingly, the substituent number in the p-nitrophenyl compounds and kind do not have special restriction yet.
The structural formula of aforesaid nitrobenzene compounds is:
Wherein, R represents to be connected 1,2 or 3 substituting group on the phenyl ring, substituting group be selected from hydrogen atom, halogen atom, C1-C10 alkyl, C2-C10 thiazolinyl, C2-C10 alkynyl, C6-C20 aryl ,-OR ' ,-OCF3 ,-NHR ' ,-C (=O) OR ' ,-NHC (=O) R ' and-(=O) any one among the R ', described R ' is H, C1-C6 alkyl, C2-C6 thiazolinyl, C2-C6 alkynyl, phenyl or benzyl to C.
Described nitrobenzene compounds can adopt one or both nitrobenzene compounds.
Azoxybenzene compound of the present invention (formula A).
Wherein, R1 and R2 represent to be connected 1,2 or 3 substituting group on the phenyl ring, each substituting group be selected from independently of one another hydrogen atom, halogen atom, C1-C10 alkyl, C2-C10 thiazolinyl, C2-C10 alkynyl, C6-C20 aryl ,-OR ' ,-OCF3 ,-NHR ' ,-C (=O) OR ' ,-NHC (=O) R ' and-(=O) any one among the R ', described R ' is H, C1-C6 alkyl, C2-C6 thiazolinyl, C2-C6 alkynyl, phenyl or benzyl to C.
Azobenzene compound of the present invention (formula B)
The definition cotype A of substituent R 1 among the formula B and R2.
Aforesaid alkali is potassium hydroxide, sodium hydroxide, potassium tert.-butoxide and sodium tert-butoxide.
Aforesaid alcohol is saturated monohydroxy alcohol or the dibasic alcohol of C1-C10, concrete as methyl alcohol, ethanol, Virahol, n-propyl alcohol, the trimethyl carbinol, propyl carbinol, isopropylcarbinol, ethylene glycol, sec-butyl alcohol, primary isoamyl alcohol, Pentyl alcohol, n-Octanol, nonylcarbinol, tertiary amyl alcohol, n-hexyl alcohol, secondary octanol, 1,4-butyleneglycol, 2,3-butyleneglycol, 1,2-propylene glycol, 1, ammediol, n-Heptyl alcohol, isooctyl alcohol, sec.-amyl alcohol, nonanol-, 1,3-butyleneglycol, 3-amylalcohol, 1,2-pentanediol, 1,2-ethohexadiol, 2, any alcohol in 2-dimethyl propyl alcohol, the 2-enanthol.
Aforesaid catalyzer is metallic copper/graphen catalyst, and wherein the charge capacity of metallic copper is 0.5-50wt%.
Aforesaid ultrasonic power is 10-300W.
Aforesaid illumination is the xenon lamp irradiation of direct irradiation of sunlight or simulated solar irradiation.
Be reflected at as mentioned above under the protection of inert gas and carry out, described rare gas element is Ne, Ar or N for example
2
Characteristics of the present invention are: environmental protection, with low cost, simple to operate, reaction time is short, the product yield height.Wherein outstanding feature is effectively to utilize sun power, and by synthesizing azoxybenzene compound and azobenzene compound in the same system of being adjusted in of temperature respectively, the product selectivity height.
Embodiment
Embodiment 1
After oil of mirbane, potassium hydroxide and ethanolic soln mixed according to mol ratio 1:0.12:200; adding copper content by mass ratio 1:0.001 is copper/graphen catalyst of 2wt%; after ultrasonic (electric power 60W) disperses 30min; scattered suspension under xenon lamp photograph and argon shield, is heated to 40
oC stirring reaction 6h can obtain zinin, and wherein the oil of mirbane transformation efficiency is 90%, and the azoxy benzene selective is 94%; Be heated to 100
oC stirring reaction 5h reaction can obtain nitrogen benzide, and wherein the oil of mirbane transformation efficiency is 95%, and the nitrogen benzide selectivity is 98%.
Embodiment 2
After parachloronitrobenzene, potassium tert.-butoxide and 2-enanthol solution mixed according to mol ratio 1:0.3:500; adding copper content by mass ratio 1:0.01 is copper/graphen catalyst of 7wt.%; after ultrasonic (electric power 80W) disperses 90min; scattered suspension under xenon lamp photograph and neon protection, is heated to 80
oC stirring reaction 3h can obtain the oxychlorination nitrogen benzide, and wherein the parachloronitrobenzene transformation efficiency is 91%, is 89% to oxychlorination nitrogen benzide selectivity; Be heated to 100
oC stirring reaction 3h reaction can obtain the chlorine nitrogen benzide, and wherein the parachloronitrobenzene transformation efficiency is 94%, is 85% to chlorine nitrogen benzide selectivity.
Embodiment 3
After para-methylnitrobenzene, sodium tert-butoxide and aqueous isopropanol mixed according to mol ratio 1:0.24:240; adding copper content by mass ratio 1:0.04 is copper/graphen catalyst of 5wt%; after ultrasonic (electric power 150W) disperses 30min; scattered suspension under xenon lamp photograph and nitrogen protection, is heated to 60
oC stirring reaction 5h can obtain the methyl oxidation nitrogen benzide, and wherein the para-methylnitrobenzene transformation efficiency is 91%, is 90% to methyl oxidation nitrogen benzide selectivity; Be heated to 110
oC stirring reaction 5h reaction can obtain methyl-benzene, and wherein the para-methylnitrobenzene transformation efficiency is 95%, is 97% to the methyl-benzene selective.
Embodiment 4
After M-NITROBENZOIC ACID, potassium hydroxide and tertiary amyl alcohol solution mixed according to mol ratio 1:10:700; adding copper content by mass ratio 1:0.06 is copper/graphen catalyst of 40wt%; after ultrasonic (electric power 200W) disperses 200min; scattered suspension under xenon lamp photograph and argon shield, is heated to 70
oC stirring reaction 8h can obtain zinin-3, the 3'-dioctyl phthalate, and wherein the M-NITROBENZOIC ACID transformation efficiency is 84%, zinin-3,3'-dioctyl phthalate selectivity is 92%; Be heated to 100
oC stirring reaction 8h reaction can obtain nitrogen benzide-3, the 3'-dioctyl phthalate, and wherein the M-NITROBENZOIC ACID transformation efficiency is 87%, nitrogen benzide-3,3'-dioctyl phthalate selectivity is 91%.
Embodiment 5
With 3-methyl-5-nitro phenylformic acid, sodium hydroxide and 2; after the 3-butanediol solution mixes according to mol ratio 1:4:350; adding copper content by mass ratio 1:0.1 is copper/graphen catalyst of 15wt.%; after ultrasonic (electric power 90W) disperses 130min; scattered suspension under xenon lamp photograph and argon shield, is heated to 80
oC stirring reaction 6h can obtain zinin-3,3'-dimethyl-5, and the 5'-dioctyl phthalate, wherein 3-methyl-5-nitro phenylformic acid transformation efficiency is 81%, zinin-3,3'-dimethyl-5,5'-dioctyl phthalate selectivity is 84%; Be heated to 100
oC stirring reaction 6h reaction can obtain nitrogen benzide-3,3'-dimethyl-5, and the 5'-dioctyl phthalate, wherein 3-methyl-5-nitro phenylformic acid transformation efficiency is 83%, zinin-3,3'-dimethyl-5,5'-dioctyl phthalate selectivity is 80%.
Embodiment 6
Will be to methoxy nitrobenzene, potassium hydroxide and 2; after 2-dimethyl propylene alcoholic solution mixes according to mol ratio 1:1.2:260; adding copper content by mass ratio 1:0.5 is copper/graphen catalyst of 6wt%; after ultrasonic (electric power 220W) disperses 40min; scattered suspension under xenon lamp photograph and nitrogen protection, is heated to 40
oC stirring reaction 4h can obtain the methoxyl group zinin, is 90% to the methoxy nitrobenzene transformation efficiency wherein, is 93% to methoxyl group azoxy benzene selective; Be heated to 80
oC stirring reaction 4h reaction can obtain mab, is 94% to methoxy nitrobenzene wherein, and the mab selectivity is 93%.
Embodiment 7
With N; after N-dimethyl-4-N-methyl-p-nitroaniline, 4-nitrobiphenyl, sodium hydroxide and sec-butyl alcohol solution mix according to mol ratio 1:1:260; adding copper content by mass ratio 1:0.005 is copper/graphen catalyst of 10wt%; after ultrasonic (electric power 120W) disperses 50min; scattered suspension under sun exposure and nitrogen protection, is heated to 60
oC stirring reaction 10h can obtain zinin-4-N, N-dimethyl-4 '-phenyl, and N wherein, the transformation efficiency of N-dimethyl-4-N-methyl-p-nitroaniline and 4-nitrobiphenyl is respectively 85% and 81%, zinin-4-N, N-dimethyl-4 '-phenyl selectivity is 92%; Be heated to 120
oC stirring reaction 10h reaction can obtain nitrogen benzide-4-N, N-dimethyl-4 '-phenyl, and N wherein, the transformation efficiency of N-dimethyl-4-N-methyl-p-nitroaniline and 4-nitrobiphenyl is respectively 90% and 86%, nitrogen benzide-4-N, N-dimethyl-4 '-phenyl selectivity is 95%.
Embodiment 8
After methyl p-nitrobenzoate, p-nitrobenzoic acid propylene ester, potassium tert.-butoxide and ethylene glycol solution mixed according to mol ratio 1:5:300; adding copper content by mass ratio 1:0.02 is copper/graphen catalyst of 20wt%; after ultrasonic (electric power 160W) disperses 120min; scattered suspension under sun exposure and neon protection, is heated to 70
oC stirring reaction 8h can obtain zinin-4-methyl-formiate-4 ' formic acid propylene ester, wherein the transformation efficiency of methyl p-nitrobenzoate and p-nitrobenzoic acid propylene ester is respectively 82% and 86%, and zinin-4-methyl-formiate-4 ' formic acid propylene ester selectivity is 93%; Be heated to 110
oC stirring reaction 3h reaction can obtain nitrogen benzide-4-methyl-formiate-4 ' formic acid propylene ester, wherein the transformation efficiency of methyl p-nitrobenzoate and p-nitrobenzoic acid propylene ester is respectively 89% and 91%, and nitrogen benzide-4-methyl-formiate-4 ' formic acid propylene ester selectivity is 90%.
Embodiment 9
With adjacent trifluoromethoxy oil of mirbane, 4-nitro-3 '; after 5 '-dihydroxybiphenyl, potassium hydroxide and isobutanol solution mix according to mol ratio 1:1:8:600; adding copper content by mass ratio 1:1 is copper/Graphene of 30wt%; after ultrasonic (electric power 260W) disperses 240min; scattered suspension under xenon lamp photograph and nitrogen protection, is heated to 80
oC stirring reaction 9h can obtain zinin-6-trifluoromethoxy-3', the 5'-dihydroxyl, wherein adjacent trifluoromethoxy oil of mirbane and 4-nitro-3 ', the transformation efficiency of 5 '-dihydroxybiphenyl is respectively 82% and 86%, zinin-6-trifluoromethoxy-3', 5'-dihydroxyl selectivity is 76%; Be heated to 140
oC stirring reaction 9h reaction can obtain nitrogen benzide-6-trifluoromethoxy-3', the 5'-dihydroxyl, adjacent trifluoromethoxy oil of mirbane and 4-nitro-3 ', the transformation efficiency of 5 '-dihydroxybiphenyl is respectively 85% and 90%, nitrogen benzide-6-trifluoromethoxy-3', 5'-dihydroxyl selectivity is 83%.
Embodiment 10
With 3; 5-dimethyl nitrobenzene, 3-methoxyl group-5-nitrophenols, potassium hydroxide and 1; after ammediol solution mixes according to mol ratio 1:1:4.5:800; adding copper content by mass ratio 1:2 is copper/graphen catalyst of 50wt%; after ultrasonic (electric power 150W) disperses 200min; scattered solution under sun exposure and nitrogen protection, is heated to 60
oC stirring reaction 10h can obtain zinin-3,5-dimethyl-3 '-methoxyl group-5 '-hydroxyl, wherein 3, the transformation efficiency of 5-dimethyl nitrobenzene and 3-methoxyl group-5-nitrophenols is respectively 87% and 91%, zinin-3,5-dimethyl-3 '-methoxyl group-5 '-hydroxyl selectivity is 93%; Be heated to 110
oC stirring reaction 10h reaction can obtain nitrogen benzide-3,5-dimethyl-3 '-methoxyl group-5 '-hydroxyl, wherein 3, the transformation efficiency of 5-dimethyl nitrobenzene, 3-methoxyl group-5-nitrophenols is respectively 90% and 91%, nitrogen benzide-3,5-dimethyl-3 '-methoxyl group-5 '-hydroxyl selectivity is 94%.
Claims (13)
1. the method that zinin and azobenzene compound are synthesized in photochemical catalysis is characterized in that comprising the steps:
(1) nitrobenzene compounds, alkali and alcohol are evenly formed solution according to the 1:0.1-20:40-1000 mixed in molar ratio after, mass ratio by nitrobenzene compounds and catalyzer is 1:0.001-2, adds copper/graphen catalyst, ultra-sonic dispersion 5-240min in solution;
(2) with scattered solution at inert atmosphere protection, under the agitation condition, at 0.001-5W/cm
2Illumination under the intensity is heated to 20-80
oReaction 3-10h can obtain azoxybenzene compound during C; Be heated to 80
oC is above, 150
oReaction 3-10h can obtain the azobenzene compound when C was following.
2. the method for zinin and azobenzene compound is synthesized in a kind of photochemical catalysis as claimed in claim 1, it is characterized in that the structural formula of described nitrobenzene compounds is:
Wherein, R represents to be connected 1,2 or 3 substituting group on the phenyl ring, substituting group be selected from hydrogen atom, halogen atom, C1-C10 alkyl, C2-C10 thiazolinyl, C2-C10 alkynyl, C6-C20 aryl ,-OR ' ,-OCF3 ,-NHR ' ,-C (=O) OR ' ,-NHC (=O) R ' and-(=O) any one among the R ', described R ' is H, C1-C6 alkyl, C2-C6 thiazolinyl, C2-C6 alkynyl, phenyl or benzyl to C.
3. the method for the synthetic zinin of a kind of photochemical catalysis as claimed in claim 2 and azobenzene compound is characterized in that described nitrobenzene compounds adopts one or both nitrobenzene compounds.
4. the method for the synthetic zinin of a kind of photochemical catalysis as claimed in claim 1 and azobenzene compound is characterized in that described alkali is potassium hydroxide, sodium hydroxide, potassium tert.-butoxide or sodium tert-butoxide.
5. the method for the synthetic zinin of a kind of photochemical catalysis as claimed in claim 1 and azobenzene compound is characterized in that described alcohol is saturated monohydroxy alcohol or the dibasic alcohol of C1-C10.
6. the method for zinin and azobenzene compound is synthesized in a kind of photochemical catalysis as claimed in claim 5, it is characterized in that described monohydroxy-alcohol is methyl alcohol, ethanol, Virahol, n-propyl alcohol, the trimethyl carbinol, propyl carbinol, isopropylcarbinol, ethylene glycol, sec-butyl alcohol, primary isoamyl alcohol, Pentyl alcohol, n-Octanol, nonylcarbinol, tertiary amyl alcohol, n-hexyl alcohol, secondary octanol, n-Heptyl alcohol, isooctyl alcohol, sec.-amyl alcohol, nonanol-, 3-amylalcohol, 2,2-dimethyl propyl alcohol or 2-enanthol.
7. the method for the synthetic zinin of a kind of photochemical catalysis as claimed in claim 5 and azobenzene compound is characterized in that described dibasic alcohol is 1,4-butyleneglycol, 2,3-butyleneglycol, 1,2-propylene glycol, 1, ammediol, 1, the 3-butyleneglycol,, 1,2-pentanediol or 1,2-ethohexadiol.
8. the method for the synthetic zinin of a kind of photochemical catalysis as claimed in claim 1 and azobenzene compound is characterized in that described catalyzer is metallic copper/graphen catalyst, and wherein the charge capacity of metallic copper is 0.5-50wt%.
9. the method for the synthetic zinin of a kind of photochemical catalysis as claimed in claim 1 and azobenzene compound is characterized in that described ultrasonic power is 10-300W.
10. the method for the synthetic zinin of a kind of photochemical catalysis as claimed in claim 1 and azobenzene compound is characterized in that described illumination is the xenon lamp irradiation of direct irradiation of sunlight or simulated solar irradiation.
11. the method for the synthetic zinin of a kind of photochemical catalysis as claimed in claim 1 and azobenzene compound is characterized in that described rare gas element is Ne, Ar or N
2
12. as the method for the synthetic zinin of each described a kind of photochemical catalysis of claim 1-11 and azobenzene compound, the structural formula that it is characterized in that described azoxybenzene compound is formula A:
Wherein, R1 and R2 represent to be connected 1,2 or 3 substituting group on the phenyl ring, each substituting group be selected from independently of one another hydrogen atom, halogen atom, C1-C10 alkyl, C2-C10 thiazolinyl, C2-C10 alkynyl, C6-C20 aryl ,-OR ' ,-OCF3 ,-NHR ' ,-C (=O) OR ' ,-NHC (=O) R ' and-(=O) any one among the R ', described R ' is H, C1-C6 alkyl, C2-C6 thiazolinyl, C2-C6 alkynyl, phenyl or benzyl to C.
13. the method as the synthetic zinin of each described a kind of photochemical catalysis of claim 1-11 and azobenzene compound is characterized in that described azobenzene structural formula of compound is formula B:
Wherein, R1 and R2 represent to be connected 1,2 or 3 substituting group on the phenyl ring, each substituting group be selected from independently of one another hydrogen atom, halogen atom, C1-C10 alkyl, C2-C10 thiazolinyl, C2-C10 alkynyl, C6-C20 aryl ,-OR ' ,-OCF3 ,-NHR ' ,-C (=O) OR ' ,-NHC (=O) R ' and-(=O) any one among the R ', described R ' is H, C1-C6 alkyl, C2-C6 thiazolinyl, C2-C6 alkynyl, phenyl or benzyl to C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310217096.2A CN103265450B (en) | 2013-06-04 | 2013-06-04 | Method for photocatalytic synthesis of azoxybenzene and azobenzene compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310217096.2A CN103265450B (en) | 2013-06-04 | 2013-06-04 | Method for photocatalytic synthesis of azoxybenzene and azobenzene compounds |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103265450A true CN103265450A (en) | 2013-08-28 |
CN103265450B CN103265450B (en) | 2014-07-09 |
Family
ID=49009129
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310217096.2A Active CN103265450B (en) | 2013-06-04 | 2013-06-04 | Method for photocatalytic synthesis of azoxybenzene and azobenzene compounds |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103265450B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104447842A (en) * | 2014-11-07 | 2015-03-25 | 河北联合大学 | Azo indole double-charge organic hole transport material for all-solid-state quantum dot sensitized solar cell |
CN104447840A (en) * | 2014-11-07 | 2015-03-25 | 河北联合大学 | Azopyrazine/azopyridazine double-charge organic hole transport material used for all-solid-state quantum dot sensitized solar cells |
CN104447841A (en) * | 2014-11-07 | 2015-03-25 | 河北联合大学 | Azo condensed ring double-charge organic hole-transport materials for all-solid-state quantum dot sensitized solar cells |
CN106496063A (en) * | 2016-10-21 | 2017-03-15 | 福州大学 | A kind of method for preparing hydrodiazo benzene-like compounds |
CN106824996A (en) * | 2017-02-16 | 2017-06-13 | 广东工业大学 | A kind of method of smooth thermal coupling degradation biological matter discarded object |
CN107253920A (en) * | 2017-07-11 | 2017-10-17 | 苏州大学 | A kind of fragrant azobenzene oxide compound and preparation method thereof |
CN110803998A (en) * | 2019-11-12 | 2020-02-18 | 苏州大学 | Method for preparing asymmetric azobenzene and azoxybenzene compounds by photocatalysis |
CN114315653A (en) * | 2022-01-05 | 2022-04-12 | 重庆第二师范学院 | Method for synthesizing azoxybenzene by photocatalysis |
CN115337919A (en) * | 2021-05-14 | 2022-11-15 | 兰州大学 | Application of zirconium hydroxide as catalyst for catalyzing aniline or derivative thereof to prepare diphenyldiazene or derivative thereof |
CN115959997A (en) * | 2021-10-13 | 2023-04-14 | 中国科学院大连化学物理研究所 | Method for reducing nitro-substituted aromatic compound |
CN116393127A (en) * | 2023-03-03 | 2023-07-07 | 安徽大学 | Defect copper-based catalyst for synthesizing azobenzene compound and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101792406A (en) * | 2010-03-26 | 2010-08-04 | 山西大学 | Synthetic method of azobenzene oxide compound |
CN101851175A (en) * | 2010-06-09 | 2010-10-06 | 山西大学 | Preparation method of azoxybenzene compound |
CN102718680A (en) * | 2012-06-05 | 2012-10-10 | 清华大学 | Method for preparing aromatic azoic compound by catalyzing aromatic amine with metal nanocrystals |
-
2013
- 2013-06-04 CN CN201310217096.2A patent/CN103265450B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101792406A (en) * | 2010-03-26 | 2010-08-04 | 山西大学 | Synthetic method of azobenzene oxide compound |
CN101851175A (en) * | 2010-06-09 | 2010-10-06 | 山西大学 | Preparation method of azoxybenzene compound |
CN102718680A (en) * | 2012-06-05 | 2012-10-10 | 清华大学 | Method for preparing aromatic azoic compound by catalyzing aromatic amine with metal nanocrystals |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104447840A (en) * | 2014-11-07 | 2015-03-25 | 河北联合大学 | Azopyrazine/azopyridazine double-charge organic hole transport material used for all-solid-state quantum dot sensitized solar cells |
CN104447841A (en) * | 2014-11-07 | 2015-03-25 | 河北联合大学 | Azo condensed ring double-charge organic hole-transport materials for all-solid-state quantum dot sensitized solar cells |
CN104447840B (en) * | 2014-11-07 | 2017-05-17 | 河北联合大学 | Azopyrazine/azopyridazine double-charge organic hole transport material used for all-solid-state quantum dot sensitized solar cells |
CN104447841B (en) * | 2014-11-07 | 2017-05-24 | 河北联合大学 | Azo condensed ring double-charge organic hole-transport materials for all-solid-state quantum dot sensitized solar cells |
CN104447842B (en) * | 2014-11-07 | 2017-05-24 | 河北联合大学 | Azo indole double-charge organic hole transport material for all-solid-state quantum dot sensitized solar cell |
CN104447842A (en) * | 2014-11-07 | 2015-03-25 | 河北联合大学 | Azo indole double-charge organic hole transport material for all-solid-state quantum dot sensitized solar cell |
CN106496063B (en) * | 2016-10-21 | 2018-07-20 | 福州大学 | A method of preparing hydrodiazo benzene-like compounds |
CN106496063A (en) * | 2016-10-21 | 2017-03-15 | 福州大学 | A kind of method for preparing hydrodiazo benzene-like compounds |
CN106824996A (en) * | 2017-02-16 | 2017-06-13 | 广东工业大学 | A kind of method of smooth thermal coupling degradation biological matter discarded object |
CN107253920A (en) * | 2017-07-11 | 2017-10-17 | 苏州大学 | A kind of fragrant azobenzene oxide compound and preparation method thereof |
CN107253920B (en) * | 2017-07-11 | 2019-06-21 | 苏州大学 | A kind of fragrance azobenzene oxide compound and preparation method thereof |
CN110803998A (en) * | 2019-11-12 | 2020-02-18 | 苏州大学 | Method for preparing asymmetric azobenzene and azoxybenzene compounds by photocatalysis |
CN110803998B (en) * | 2019-11-12 | 2022-05-03 | 苏州大学 | Method for preparing asymmetric azobenzene and azoxybenzene compounds by photocatalysis |
CN115337919A (en) * | 2021-05-14 | 2022-11-15 | 兰州大学 | Application of zirconium hydroxide as catalyst for catalyzing aniline or derivative thereof to prepare diphenyldiazene or derivative thereof |
CN115337919B (en) * | 2021-05-14 | 2023-11-28 | 兰州大学 | Application of zirconium hydroxide as catalyst in catalyzing aniline or derivative thereof to prepare diphenyldiazene or derivative thereof |
CN115959997A (en) * | 2021-10-13 | 2023-04-14 | 中国科学院大连化学物理研究所 | Method for reducing nitro-substituted aromatic compound |
CN114315653A (en) * | 2022-01-05 | 2022-04-12 | 重庆第二师范学院 | Method for synthesizing azoxybenzene by photocatalysis |
CN116393127A (en) * | 2023-03-03 | 2023-07-07 | 安徽大学 | Defect copper-based catalyst for synthesizing azobenzene compound and preparation method thereof |
CN116393127B (en) * | 2023-03-03 | 2024-05-24 | 安徽大学 | Defect copper-based catalyst for synthesizing azobenzene compound and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN103265450B (en) | 2014-07-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103265450B (en) | Method for photocatalytic synthesis of azoxybenzene and azobenzene compounds | |
Gusak et al. | New potential of the reductive alkylation of amines | |
WO2022032879A1 (en) | Photochemical synthesis method for heteroaryl amine compound | |
CN104725251A (en) | Method for preparing solvent blue 78 | |
CN101914036B (en) | Method for preparing azobenzene derivatives | |
Yan et al. | Catalyst-free reductive hydrogenation or deuteration of aryl–heteroatom bonds induced by light | |
CN109529880A (en) | A kind of regeneration method of catalyst | |
CN106187657B (en) | A kind of method of palladium magnesia-alumina hydrotalcite catalysis Suzuki cross-coupling reaction | |
CN110668987B (en) | Synthesis method and application of visible light-promoted dithiocarbamate compound | |
An et al. | An Efficient and Solvent‐Free Reaction for Synthesis of Bis (indol‐3‐yl) methanes Catalyzed by Sulfamic Acid | |
CN104311527A (en) | Acidic bifunctional ionic liquid catalysis method for synthesis of benzoxanthene derivative | |
CN103130621B (en) | Fluorene derivatives having multi-photon absorption characteristic, synthesis method and applications thereof | |
CN103011094B (en) | Preparation method of water-soluble zinc selenide quantum dot | |
Reza Kiasat et al. | Silica‐Bound 3‐{2‐[Poly (ethylene Glycol)] ethyl}‐Substituted 1‐Methyl‐1H‐imidazol‐3‐ium Bromide: A Recoverable Phase‐Transfer Catalyst for Smooth and Regioselective Conversion of Oxiranes to β‐Hydroxynitriles in Water | |
CN104557661A (en) | Preparation method for synthesizing indoline through idodine catalysis of amide compound | |
Shaabani et al. | Pyridine-functionalized MCM-41 as an efficient and recoverable catalyst for the synthesis of pyran annulated heterocyclic systems | |
CN102976881B (en) | Method for preparing biphenyl | |
CN111362796B (en) | Method for reducing and hydrogenating tertiary alkyl alcohol | |
CN102351773B (en) | Synthesis method of indole type compounds | |
CN101704757B (en) | Method for preparing arylamine by reducing aromatic nitro compound under radiation of visible light | |
CN108424377A (en) | A kind of synthetic method of asymmetric oxidation azobenzene compound | |
CN115594684B (en) | Organic photocatalyst based on isoaza-trimeric indene skeleton, and preparation method and application thereof | |
CN100413844C (en) | Multi-photon absorption phenylfluorene derivative and preparation method thereof | |
CN106632067A (en) | Method for preparing triclabendazole serving as medicine for animal distomiasis | |
CN107629090B (en) | N, N-coordinated rhodium complex, synthetic method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |