CN1634862A - Process for photo catalytic reduction preparation of p-chloroaniline - Google Patents
Process for photo catalytic reduction preparation of p-chloroaniline Download PDFInfo
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- CN1634862A CN1634862A CN 200410072383 CN200410072383A CN1634862A CN 1634862 A CN1634862 A CN 1634862A CN 200410072383 CN200410072383 CN 200410072383 CN 200410072383 A CN200410072383 A CN 200410072383A CN 1634862 A CN1634862 A CN 1634862A
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- acid amide
- catalytic reduction
- chlorobenzoic acid
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Abstract
The invention provides a method for reduction preparation of p-chloroaniline by photocatalysis. The process comprises the following steps: solving p-chloronitrobenzene with organic solvent in photocatalysis reactor allowing over 300nm ultraviolet light to pass with the mass ratio of p-chloronitrobenzene to solvent between 1:40 and 1:225, adding hole scavenger and photocatalyst with the volume ratio of hole scavenger to organic solvent between 1:3 and 1:18 with the concentration of photocatalyst in organic solvent between 0.5g/L and 10g/L, adding nitrogen for removing oxygen, and irradiating for 3 hours to 6 hours by ultraviolet light at normal pressure. The reduction reaction can be carried out at normal temperature without high temperature energy consumption device, initiation light can be ultraviolet light or sunlight, and nano photocatalyst can be titanium dioxide or zinc oxide, etc. The invention has higher reduction conversion and yield.
Description
Technical field
The invention belongs to the production method of organic compound, proposed a kind of method for preparing p-Chlorobenzoic acid amide by photo catalytic reduction especially.
Background technology
P-Chlorobenzoic acid amide is fine chemicals intermediates such as a kind of important medicine, dyestuff, pigment, agricultural chemicals, and is of many uses.
Existing synthetic method is to reduce preparation p-Chlorobenzoic acid amide or prepared p-Chlorobenzoic acid amide or prepare p-Chlorobenzoic acid amide through hydrogenating reduction by parachloronitrobenzene in the presence of catalyzer through sodium sulfide reducing by parachloronitrobenzene by parachloronitrobenzene through iron powder in acidic medium substantially.The iron powder method is difficult for stirring, corrodibility strong, the equipment abrasion is serious, the slag and effluent discharging is many, and yield is low; The sulfuration alkaline process need pressurize, waste water is many, the refractory reason; The hydrogenating reduction method needs high temperature, high-tension apparatus, operational hazards, is subjected to the restriction of high quality hydrogen source.
Summary of the invention
When the Nano semiconductor photocatalyst was subjected to wavelength X to be less than or equal to its forbidden band wavelength X g excitation light irradiation, the electronics on the semi-conductor valence band was excited and transits to conduction band, stays the hole on valence band.Conduction band electron can make the electron acceptor(EA) that is adsorbed on semiconductor surface such as aromatic nitro compound etc. obtain reduction.According to this principle, we have invented a kind of method for preparing p-Chlorobenzoic acid amide by photo catalytic reduction.
Concrete steps are as follows:
Can make the above UV-light of 300nm by in the photo catalysis reactor of reactor wall light transmissive material, with the parachloronitrobenzene organic solvent dissolution; The mass ratio of parachloronitrobenzene and solvent is 1: 40～1: 225; Add hole scavenging agent and photocatalyst, the hole scavenging agent is 1: 3～1: 18 with the volume of organic solvent ratio; The concentration of photocatalyst in organic solvent is 0.5g/L～10g/L.Stir and form suspension liquid, behind the logical nitrogen deoxygenation gas, under the normal pressure, use the ultra violet lamp certain hour, filter the Ex-all solid catalyst, distillation removes neat solvent, obtains p-Chlorobenzoic acid amide.
Described machine solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetonitrile or acetone;
Described hole scavenging agent is formic acid, oxalic acid or hydrazine hydrate;
Photocatalyst is nano semiconductor such as titanium dioxide, zinc oxide, Tungsten oxide 99.999, strontium titanate, Cadmium Sulfide, and wherein active high oxide semiconductor is better, as titanium dioxide.Catalyzer can be done powdered, particle shape, membranaceous.The averageparticle crystalline substance is preferably 0.01～10 μ m at 0.005～100 μ m.
Described photo catalysis reactor is Pyrex glass or silica glass.
Temperature of reaction can be from the boiling point of-20 ℃～solvent, but usually can fine carrying out in room temperature.
Reaction times can be 3～6 hours, and the time, too short p-Chlorobenzoic acid amide yield was low, overlong time, and yield increases little.
This method has tangible advantage than existing reduction mode: reduction reaction can take place in normal temperature, does not need the high temperature energy consumption equipment; Exciting light can be UV-light or sunlight, is cleaning and cheap reacting driving force; Chemical property such as nano-photocatalyst such as titanium dioxide, zinc oxide is stable, nontoxic and price is more cheap; Do not use hydrogen, operate safer; Reducing medium is mainly appropriate solvent, and solvent is recyclable, and three wastes discharge amount is few; Normal pressure can reduce smoothly, not need high-pressure reactor, and equipment is simple; Without hydrogen, reactor sealing, manufactured materials are easy to solve; Reduction transformation efficiency and yield are than higher; The photochemical catalysis operating procedure is more easily implemented, and is more suitable for the production of fine chemistry industry series products.
Embodiment
Embodiment 1
To pack in the chuck Pyrex reactor that has magnetic stir bar with 10mL formic acid and 90mL isopropanol solvent dissolved 630mg parachloronitrobenzene, add 640mg P25 type TiO
2(about 80% anatase titanium dioxide, 20% rutile-type, median size 30nm) catalyst fines forms suspension system.Behind the logical nitrogen deoxygenation, dark absorption 1.5h places irradiation high voltage mercury lamp (100W) under with suspension liquid under the magnetic agitation, in magnetic agitation, uninterruptedly lead under the nitrogen and react.Finish reaction behind the irradiation 4h, remove by filter TiO
2Particle, gained filtrate is carried out product analysis with high pressure liquid chromatography (HPLC), obtains p-Chlorobenzoic acid amide productive rate 98%.
Embodiment 2 is except using powders A 101 type TiO
2(being anatase titanium dioxide substantially, median size 210nm) catalyzer replaces P25 type TiO
2Outward, other condition is with embodiment 1, and the result obtains p-Chlorobenzoic acid amide productive rate 69%.
Embodiment 3 is except using powder R101 type TiO
2(being rutile-type substantially, median size 185nm) catalyzer replaces P25 type TiO
2Outward, other condition is with embodiment 1, and the result obtains p-Chlorobenzoic acid amide productive rate 15%.
Embodiment 4 is except the mixed solvent with 100mL isopropanol solvent replacement 10mL formic acid and 90mL Virahol, and other condition is with embodiment 2, and the result obtains p-Chlorobenzoic acid amide productive rate 21%.
Embodiment 5 is except the mixed solvent with 100mL formic acid replacement 10mL formic acid and 90mL Virahol, and other condition is with embodiment 2, and the result obtains p-Chlorobenzoic acid amide productive rate 19%.
Embodiment 6 is except replacing Pyrex reactor, illumination among the embodiment 1 to carry out the 1h with the identical quartz reactor of structure, and other reaction conditions is with embodiment 1, and it is 80% that the result obtains the p-Chlorobenzoic acid amide productive rate.
Embodiment 7 is except replacing the 630mg parachloronitrobenzene among the embodiment 1 with the 2560mg parachloronitrobenzene, other reaction conditions is with embodiment 6, and it is 78% that the result obtains the p-Chlorobenzoic acid amide productive rate.
Embodiment 8 is the 2h except the reaction times, and other is operated with embodiment 1, p-Chlorobenzoic acid amide yield 88%.
Embodiment 9 is except catalyzer TiO
2Change into outside 1g, median size 30 μ m granular, other is operated with embodiment 1, p-Chlorobenzoic acid amide yield 74%.
Embodiment 10 is except hole scavenging agent formic acid consumption changes 5mL into, Virahol changes into the 95mL, and other is operated with embodiment 1, p-Chlorobenzoic acid amide yield 82%.
Embodiment 11 is except replacing the 640mg TiO among the embodiment 1 with 800mg zinc oxide (median size 100nm)
2Outward, other reaction conditions is with embodiment 1, and it is 82% that the result obtains the p-Chlorobenzoic acid amide productive rate.
Embodiment 12 is except replacing the 640mg TiO among the embodiment 1 with 800mg Cadmium Sulfide (median size 50nm)
2Outward, other reaction conditions is with embodiment 1, and it is 89% that the result obtains the p-Chlorobenzoic acid amide productive rate.
Embodiment 13: except catalyzer being changed into the membranaceous anatase titanium dioxide TiO that is carried on the sheet glass
2(thickness 4 μ m, film surface-area 9cm outward
2, the TiO of component film
2Median size 48nm), irradiation time is outside the 7h, and other is operated with embodiment 1, obtains p-Chlorobenzoic acid amide productive rate 86%.
The present invention is not limited to the technology described in the embodiment; its description is illustrative; and it is nonrestrictive; authority of the present invention is limited by claim; based on present technique field personnel according to the present invention can change, technology related to the present invention that method such as reorganization obtains, all within protection scope of the present invention.
Claims (8)
1. a photo catalytic reduction prepares the method for p-Chlorobenzoic acid amide, concrete steps are as follows: can make the above UV-light of 300nm by in the photo catalysis reactor of reactor wall light transmissive material, with the parachloronitrobenzene organic solvent dissolution, the mass ratio of parachloronitrobenzene and solvent is 1: 40～1: 225; Add hole scavenging agent and photocatalyst, hole scavenging agent and volume of organic solvent ratio are 1: 3～1: 18, and the concentration of photocatalyst in organic solvent is 0.5g/L～10g/L; Behind the logical nitrogen deoxygenation gas, under the normal pressure, use ultra violet lamp 3～6 hours.
2. a kind of photo catalytic reduction as claimed in claim 1 prepares the method for p-Chlorobenzoic acid amide, it is characterized in that described machine solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetonitrile or acetone.
3. a kind of photo catalytic reduction as claimed in claim 1 prepares the method for p-Chlorobenzoic acid amide, it is characterized in that described hole scavenging agent is formic acid, oxalic acid or hydrazine hydrate.
4. a kind of photo catalytic reduction as claimed in claim 1 prepares the method for p-Chlorobenzoic acid amide, it is characterized in that described photocatalyst is a nano semiconductor.
5. a kind of photo catalytic reduction as claimed in claim 4 prepares the method for p-Chlorobenzoic acid amide, it is characterized in that described nano semiconductor is titanium dioxide, zinc oxide, Tungsten oxide 99.999, strontium titanate or Cadmium Sulfide.
6. a kind of photo catalytic reduction as claimed in claim 4 prepares the method for p-Chlorobenzoic acid amide, it is characterized in that described photocatalyst does powdered, particle shape or membranaceous; The averageparticle crystalline substance is at 0.005～100 μ m.
7. a kind of photo catalytic reduction as claimed in claim 6 prepares the method for p-Chlorobenzoic acid amide, it is characterized in that described photocatalyst averageparticle crystalline substance is being 0.01～10 μ m.
8. a kind of photo catalytic reduction as claimed in claim 1 prepares the method for p-Chlorobenzoic acid amide, it is characterized in that describedly it is characterized in that described photo catalysis reactor is Pyrex glass or silica glass.
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| CN 200410072383 CN1269796C (en) | 2004-10-25 | 2004-10-25 | Process for photo catalytic reduction preparation of p-chloroaniline |
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| CN 200410072383 CN1269796C (en) | 2004-10-25 | 2004-10-25 | Process for photo catalytic reduction preparation of p-chloroaniline |
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| CN1634862A true CN1634862A (en) | 2005-07-06 |
| CN1269796C CN1269796C (en) | 2006-08-16 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241595A (en) * | 2011-05-05 | 2011-11-16 | 天津城市建设学院 | Photocatalytic method for preparing 3,4-dichloroaniline |
| CN102574705A (en) * | 2009-08-25 | 2012-07-11 | 法斯-施塔格迈尔有限责任公司 | Processes and uses of dissociating molecules |
| CN103880621A (en) * | 2014-04-04 | 2014-06-25 | 南通柏盛化工有限公司 | Reduction method for preparing 7-methoxy-2-tetralone |
| WO2022032879A1 (en) * | 2020-08-10 | 2022-02-17 | 天津凯莱英制药有限公司 | Photochemical synthesis method for heteroaryl amine compound |
| CN115448843A (en) * | 2022-09-16 | 2022-12-09 | 中国科学技术大学 | Preparation method of aniline compound |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298407B (en) * | 2008-06-30 | 2010-06-02 | 南京工业大学 | Method for coupling hydrogen production reaction and hydrogenation reaction by photocatalysis |
-
2004
- 2004-10-25 CN CN 200410072383 patent/CN1269796C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574705A (en) * | 2009-08-25 | 2012-07-11 | 法斯-施塔格迈尔有限责任公司 | Processes and uses of dissociating molecules |
| CN102241595A (en) * | 2011-05-05 | 2011-11-16 | 天津城市建设学院 | Photocatalytic method for preparing 3,4-dichloroaniline |
| CN102241595B (en) * | 2011-05-05 | 2013-12-18 | 天津城市建设学院 | Photocatalytic method for preparing 3,4-dichloroaniline |
| CN103880621A (en) * | 2014-04-04 | 2014-06-25 | 南通柏盛化工有限公司 | Reduction method for preparing 7-methoxy-2-tetralone |
| CN103880621B (en) * | 2014-04-04 | 2015-08-12 | 南通柏盛化工有限公司 | The method of reducing of preparation 7-methoxy-2-tetralone |
| WO2022032879A1 (en) * | 2020-08-10 | 2022-02-17 | 天津凯莱英制药有限公司 | Photochemical synthesis method for heteroaryl amine compound |
| CN115448843A (en) * | 2022-09-16 | 2022-12-09 | 中国科学技术大学 | Preparation method of aniline compound |
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| CN1269796C (en) | 2006-08-16 |
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