CN104557560A - Ultrasonic radiation synthetic method of paranitrobenzoyl chloride - Google Patents
Ultrasonic radiation synthetic method of paranitrobenzoyl chloride Download PDFInfo
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- CN104557560A CN104557560A CN201410764909.4A CN201410764909A CN104557560A CN 104557560 A CN104557560 A CN 104557560A CN 201410764909 A CN201410764909 A CN 201410764909A CN 104557560 A CN104557560 A CN 104557560A
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- paranitrobenzoyl chloride
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Abstract
The invention relates to an ultrasonic radiation synthetic method of paranitrobenzoyl chloride and belongs to the technical field of synthesis of the paranitrobenzoyl chloride. The ultrasonic radiation synthetic method of the paranitrobenzoyl chloride comprises the following steps: under the actions of ultrasonic radiation and a catalyst, carrying out reaction on p-nitrobenzoyl acid and thionyl chloride to prepare the paranitrobenzoyl chloride. The ultrasonic radiation synthetic method is simple in operation, short in reaction period, low in energy consumption and production cost and high in yield of product and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of ultrasonic radiation synthetic method of paranitrobenzoyl chloride, belong to the synthesis technical field of paranitrobenzoyl chloride.
Background technology
Paranitrobenzoyl chloride is a kind of medical raw material, is commonly used to prepare vovocan, NSC 71042 and folic acid etc.; As dye material, substantive dyestuff palm fibre 100 can be prepared for leather and paper; Can also be used to manufacture matching stain, foodstuff additive (milk powder conditioning agent), color developer and organic synthesis intermediate, discriminating alcohol, phenol reagent etc.Particularly in recent years, along with the rise of fodder industry and the development of information industry, the consumption of paranitrobenzoyl chloride is increasing.
The existing production technique of paranitrobenzoyl chloride is roughly following several: 1. carry out reacting with p-nitrobenzoic acid and phosgene and obtain; 2. be raw material with p-nitrobenzoic acid, react with phosphorus oxychloride (or phosphorus pentachloride) and prepare; 3. be raw material with p-nitrobenzoic acid, with sulfur oxychloride Reactive Synthesis under catalyst action.All exist certain not enough in existing several preparation method: if phosgene and phosphorus oxychloride are violent in toxicity, personal security and environment are easily worked the mischief; Phosphorus pentachloride is solid, need add solvent and just can add fast response, easily increases impurity and lock out operation; When taking sulfur oxychloride as chlorizating agent, the reaction times is longer, and needs strutting to distill removal of impurities, increases energy consumption etc.
Summary of the invention
The object of the present invention is to provide a kind of ultrasonic radiation synthetic method of paranitrobenzoyl chloride, it is simple to operate, and reaction time is short, and energy consumption is low, and product yield is high, and production cost is low, is applicable to suitability for industrialized production.
The ultrasonic radiation synthetic method of paranitrobenzoyl chloride of the present invention, be under ultrasonic radiation and catalyst action, p-nitrobenzoic acid and sulfur oxychloride react, obtained paranitrobenzoyl chloride.
Reaction equation is as follows:
Described ultrasonic radiation frequency is 20 ~ 30KHz.
Described catalyzer is DMF (DMF), and consumption is 0.01 ~ 0.05% of p-nitrobenzoic acid quality.DMF is conventional solvent, is used for making catalyzer by DMF in the present invention, not only cheap, stable in properties, and catalytic effect is good.
The mol ratio of described p-nitrobenzoic acid and sulfur oxychloride is 1:1.1 ~ 1.5.
Described temperature of reaction is 75 ~ 80 DEG C, and the reaction times is 4 ~ 6h.
Reaction terminates the excessive sulfur oxychloride of rear underpressure distillation, and vacuum tightness during underpressure distillation is 10 ~ 30mmHg, and temperature is 115 ~ 125 DEG C, and the time is 1 ~ 2h.
Described obtained paranitrobenzoyl chloride chromatographic content >=99.5%, reaction yield >=99%.
Ultrasonic radiation is used in organic synthesis as a kind of new form of energy, a kind of convenience, rapid, effective, safe synthetic technology are become, it is superior to the thermodynamics means such as traditional stirring heating, mainly utilize hyperacoustic cavitation effect, in the microcell of medium, produce the high-energy environment of High Temperature High Pressure instantaneously, strong shock wave and microjet, facilitate the collision between molecule, accelerate speed of response, improve productive rate and the purity of reaction product simultaneously.
The present invention utilizes " cavatition " of ultrasonic radiation, can accelerate the heat and mass transfer effect that reactant two is alternate, increases molecular impact probability, accelerates reaction.The present invention, under the effect of ultrasonic radiation, shortens the reaction times, shortens to 4 ~ 6h from about the 10h of prior art; In prior art, the mol ratio of p-nitrobenzoic acid and sulfur oxychloride is more than 1:2, and the present invention effectively reduces the ratio consumption of sulfur oxychloride; Invention further reduces catalyst levels in addition, is that 0.5% of p-nitrobenzoic acid quality drops to 0.01 ~ 0.05% from existing consumption; Last negative pressure is steamed except a small amount of remaining sulfur oxychloride, need not can obtain high purity paranitrobenzoyl chloride by strutting distillation procedure.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention uses ultrasonic radiation to react as promoting the energy carried out, and not only effectively accelerates speed of reaction, reduces the addition of catalyzer, more decrease the consumption of sulfur oxychloride, saved cost, decrease the existence of impurity in product;
(2) sulfur oxychloride that the present invention is used, in the reaction not only as chlorizating agent but also as solvent use, without the need to adding other solvents, improves product purity;
(3) the present invention's reaction only needs negative pressure to steam except unnecessary sulfur oxychloride after terminating, and can obtain high purity product, decreases distilation operation, reduce energy consumption, and steaming the condensable recycling of sulfur oxychloride removed, the tail gas that reaction is released also can absorb with buck, has fewer environmental impacts.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but do not limit enforcement of the present invention.
Raw materials usedly be commercially available prod.
Embodiment 1
In reaction flask, add 83.5g p-nitrobenzoic acid, 0.01gDMF, then add 90g sulfur oxychloride, put into ultrasonic radiation instrument and carry out ultrasonic radiation, ultrasonic frequency is 20KHz, and temperature of reaction is 75 DEG C, ultrasonic time is 4h, emission-free releasing, and reaction terminates, heat up 120 DEG C, negative pressure 740mm mercury column steams except remaining sulfur oxychloride, and negative pressure is steamed except time 1h, obtains product 91.8g, chromatographic content is 99.8%, and yield is 99%.
Embodiment 2
In reaction flask, add 100g p-nitrobenzoic acid, 0.05gDMF, then add 100g sulfur oxychloride, put into ultrasonic radiation instrument and carry out ultrasonic radiation, radiation frequency is 30KHz, and temperature of reaction is 80 DEG C, ultrasonic time 5h, emission-free releasing, reaction terminates, heat up 115 DEG C, 15mm mercury column steams except remaining sulfur oxychloride, and negative pressure is steamed except time 2h, obtains product 109.4g, chromatographic content is 99.6%, and yield is 99.1%.
Embodiment 3
In reaction flask, add 50g p-nitrobenzoic acid, 0.015gDMF, then add 46g sulfur oxychloride, put into ultrasonic radiation instrument and carry out ultrasonic radiation, radiation frequency is 25KHz, temperature of reaction 79 DEG C, ultrasonic time 4h, emission-free releasing, reaction terminates, heat up 125 DEG C, 20mm mercury column steams except remaining sulfur oxychloride, and negative pressure is steamed except the time is 1h, obtains product 55g, chromatographic content is 99.7%, and yield is 99.1%.
Embodiment 4
In reaction flask, add 120g p-nitrobenzoic acid, 0.05gDMF, then add 153g sulfur oxychloride, put into ultrasonic radiation instrument and carry out ultrasonic radiation, radiation frequency is 30KHz, and temperature of reaction is 80 DEG C, ultrasonic time 6h, emission-free releasing, reaction terminates, heat up 120 DEG C, 30mm mercury column steams except remaining sulfur oxychloride, and negative pressure is steamed except the time is 1.5h, obtains product 132.2g, chromatographic content 99.5%, yield 99.2%.
Claims (8)
1. a ultrasonic radiation synthetic method for paranitrobenzoyl chloride, it is characterized in that: under ultrasonic radiation and catalyst action, p-nitrobenzoic acid and sulfur oxychloride react, obtained paranitrobenzoyl chloride.
2. the ultrasonic radiation synthetic method of paranitrobenzoyl chloride according to claim 1, is characterized in that: ultrasonic radiation frequency is 20 ~ 30KHz.
3. the ultrasonic radiation synthetic method of paranitrobenzoyl chloride according to claim 1, is characterized in that: catalyzer is DMF.
4. the ultrasonic radiation synthetic method of the paranitrobenzoyl chloride according to claim 1 or 3, is characterized in that: catalyst levels is 0.01 ~ 0.05% of p-nitrobenzoic acid quality.
5. the ultrasonic radiation synthetic method of paranitrobenzoyl chloride according to claim 1, is characterized in that: the mol ratio of p-nitrobenzoic acid and sulfur oxychloride is 1:1.1 ~ 1.5.
6. the ultrasonic radiation synthetic method of paranitrobenzoyl chloride according to claim 1, is characterized in that: temperature of reaction is 75 ~ 80 DEG C, and the reaction times is 4 ~ 6h.
7. the ultrasonic radiation synthetic method of the paranitrobenzoyl chloride according to claim 1 or 6, is characterized in that: reaction terminates the excessive sulfur oxychloride of rear underpressure distillation.
8. the ultrasonic radiation synthetic method of paranitrobenzoyl chloride according to claim 7, is characterized in that: vacuum tightness during underpressure distillation is 10 ~ 30mmHg, and temperature is 115 ~ 125 DEG C, and the time is 1 ~ 2h.
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| CN201410764909.4A CN104557560A (en) | 2014-12-12 | 2014-12-12 | Ultrasonic radiation synthetic method of paranitrobenzoyl chloride |
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| CN201410764909.4A CN104557560A (en) | 2014-12-12 | 2014-12-12 | Ultrasonic radiation synthetic method of paranitrobenzoyl chloride |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560146A (en) * | 2009-04-08 | 2009-10-21 | 淄博达隆制药科技有限公司 | Preparation method of paraphthaloyl chloride with high purity |
| US20110087013A1 (en) * | 2009-10-13 | 2011-04-14 | Bernhard Knipp | Friedel-Crafts acylation for the synthesis of aryl- and heteroaryl-(3-ethyl-4-nitrophenyl)-methanones |
| CN102796004A (en) * | 2012-08-28 | 2012-11-28 | 山东凯盛新材料股份有限公司 | Synthesis method for paranitrobenzoyl chloride |
| CN104193646A (en) * | 2014-08-05 | 2014-12-10 | 吴江梅堰三友染料化工有限公司 | Preparation method of p-aminobenzamide |
-
2014
- 2014-12-12 CN CN201410764909.4A patent/CN104557560A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560146A (en) * | 2009-04-08 | 2009-10-21 | 淄博达隆制药科技有限公司 | Preparation method of paraphthaloyl chloride with high purity |
| US20110087013A1 (en) * | 2009-10-13 | 2011-04-14 | Bernhard Knipp | Friedel-Crafts acylation for the synthesis of aryl- and heteroaryl-(3-ethyl-4-nitrophenyl)-methanones |
| CN102796004A (en) * | 2012-08-28 | 2012-11-28 | 山东凯盛新材料股份有限公司 | Synthesis method for paranitrobenzoyl chloride |
| CN104193646A (en) * | 2014-08-05 | 2014-12-10 | 吴江梅堰三友染料化工有限公司 | Preparation method of p-aminobenzamide |
Non-Patent Citations (1)
| Title |
|---|
| 贾庆超等: "超声辐射合成对苯二甲酰氯", 《精细石油化工进展》, 30 September 2010 (2010-09-30), pages 37 - 39 * |
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