CN109912424B - Method for hydrolyzing nitroanilines into phenol - Google Patents
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Abstract
本发明公开了一种硝基苯胺类物质水解成酚的方法,依次包括以下步骤:将作为原料的硝基苯胺类物质、催化剂、无机碱以及作为溶剂的水混合,加入至反应釜中密封后,升温至100~190℃反应2~8h;所得的反应液先降至室温,然后调节pH为1~2,所得的析出物经水洗、烘干,得作为产物的硝基酚类物质。采用本发明的方法合成硝基酚类物质,原料利用率高,避免了高昂催化剂的使用,不但减少了三废排放,降低了生产成本,同时产品纯度高,收率高,具有很好的工业应用价值。
The invention discloses a method for hydrolyzing nitroaniline substances into phenol, which comprises the following steps in sequence: mixing nitroaniline substances as raw materials, a catalyst, an inorganic base and water as a solvent, adding them into a reaction kettle and sealing them , heat up to 100~190℃ and react for 2~8h; the obtained reaction solution is first lowered to room temperature, and then adjusted to pH 1~2, the obtained precipitate is washed with water and dried to obtain nitrophenols as the product. The method of the invention for synthesizing nitrophenols has high utilization rate of raw materials, avoids the use of expensive catalysts, not only reduces the discharge of three wastes, but also reduces the production cost, and at the same time, the product has high purity and high yield, and has good industrial application. value.
Description
技术领域technical field
本发明属于化工领域,涉及一种硝基苯胺类物质水解成酚的方法。The invention belongs to the field of chemical industry, and relates to a method for hydrolyzing nitroanilines into phenol.
背景技术Background technique
2-氯-4-硝基苯酚是一种重要的精细化工中间体,在生物、医药等行业应用广泛,在酚羟基中引入含氟烷基可用作杀虫剂,在苯环上引入炔基可用作细胞毒素抑制剂。2-Chloro-4-nitrophenol is an important fine chemical intermediate, which is widely used in biology, medicine and other industries. The introduction of fluorine-containing alkyl groups into the phenolic hydroxyl group can be used as pesticides, and the introduction of alkynes into the benzene ring bases can be used as cytotoxic inhibitors.
目前2-氯-4-硝基苯酚合成方法主要有:At present, the synthesis methods of 2-chloro-4-nitrophenol mainly include:
1)、氯化法:1), chlorination method:
以对硝基苯酚为原料,经氯化后制得,反应式如下:Take p-nitrophenol as raw material, make after chlorination, the reaction formula is as follows:
CN103130657以氯气为氯源,在有机溶剂中与对硝基苯酚直接进行氯化反应,氯化反应结束脱除溶剂后,再进行重结晶得到2-氯-4-硝基苯酚。CN103130657 uses chlorine gas as a chlorine source, directly carries out a chlorination reaction with p-nitrophenol in an organic solvent, and after the chlorination reaction ends and removes the solvent, recrystallization is performed to obtain 2-chloro-4-nitrophenol.
DE3810381以甲酸为溶剂,一定温度下通入氯气合成2-氯-4-硝基苯酚。以氯气为氯源存在腐蚀性强、毒性大,对反应设备要求高等缺点。DE3810381 uses formic acid as a solvent to synthesize 2-chloro-4-nitrophenol by introducing chlorine gas at a certain temperature. Using chlorine gas as the chlorine source has the disadvantages of strong corrosiveness, high toxicity, and high requirements for reaction equipment.
RU2268877以盐酸为溶剂,在一定温度下向对硝基苯酚中滴加次氯酸钠,合成2-氯-4-硝基苯酚。该法存在二氯副产物多(2,6-二氯-4-硝基苯酚),产品纯度低等问题。RU2268877 uses hydrochloric acid as a solvent, and drops sodium hypochlorite into p-nitrophenol at a certain temperature to synthesize 2-chloro-4-nitrophenol. This method has many problems such as dichloro by-product (2,6-dichloro-4-nitrophenol) and low product purity.
CN1282730以盐酸为溶剂,在一定温度下滴加氯酸钾溶液,合成2-氯-4-硝基苯酚。该法所用氯酸钾成本高,同时氯化能力强,易发生多氯代副反应。CN1282730 uses hydrochloric acid as solvent, and drops potassium chlorate solution at a certain temperature to synthesize 2-chloro-4-nitrophenol. The potassium chlorate used in this method has high cost, strong chlorination ability, and is prone to polychlorination side reactions.
文献Pharmaceutical Chemistry Journal,2000,34(4):215-216则以对硝基苯酚为原料,在双氧水/盐酸体系中进行氯化,制得2-氯-4-硝基苯酚。该法存在收率较低、双氧水危险性较大等问题。The literature Pharmaceutical Chemistry Journal, 2000, 34(4): 215-216 uses p-nitrophenol as a raw material and is chlorinated in a hydrogen peroxide/hydrochloric acid system to obtain 2-chloro-4-nitrophenol. This method has problems such as low yield and high danger of hydrogen peroxide.
2)、水解法:2), hydrolysis method:
文献应用化工,2007,36(12),1249-1521以3,4-二氯硝基苯为原料,在高压条件下进行碱性水解,合成2-氯-4-硝基苯酚,反应式如下:Literature Application Chemical Industry, 2007, 36(12), 1249-1521 Using 3,4-dichloronitrobenzene as raw material, conduct alkaline hydrolysis under high pressure to synthesize 2-chloro-4-nitrophenol, the reaction formula is as follows :
该法存在产品收率低、纯度差等问题。This method has problems such as low product yield and poor purity.
3)、硝化法:3), nitrification method:
以2-氯苯酚为原料,经硝化后制得,反应式如下:Take 2-chlorophenol as raw material, make after nitration, the reaction formula is as follows:
文献Synthesis and Reactivity in Inorganic,Metal-Organic,and Nano-Metal Chemistry,2014,44(3):364-370以普鲁士蓝为硝化剂对2-氯苯酚进行硝化,收率92%。The literature Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 2014, 44(3): 364-370 uses Prussian blue as a nitrating agent to nitrate 2-chlorophenol with a yield of 92%.
文献Arabian Journal of Chemistry,2017,10(Supp1),509-513采用三聚氰胺三磺酸作为催化剂,硝酸钠作为硝化剂,2-氯-4-硝基苯酚收率为88%。Document Arabian Journal of Chemistry, 2017, 10 (Supp1), 509-513 uses melamine trisulfonic acid as a catalyst, sodium nitrate as a nitrating agent, and the yield of 2-chloro-4-nitrophenol is 88%.
传统硝化法往往存在较多的副反应(2-氯-6-二硝基苯酚以及2-氯-5-硝基苯酚),而上述文献报道的硝化剂、催化剂价格较贵,较难工业化应用。Traditional nitration method often has more side reactions (2-chloro-6-dinitrophenol and 2-chloro-5-nitrophenol), and the nitrifying agent and catalyzer reported in the above-mentioned literature are more expensive, and are more difficult to industrialized application .
文献J.Org.Chem.2011,76,6356–6361告知以4-硝基苯胺及其衍生物为原料,以氢氧化钠或N-叔丁基羟胺为碱,以水或环丁砜为溶剂来制备相应的酚,用于胺基/卤元素的直接水解成羟基,当苯环上同时存在卤元素及胺基时,选择性大大降低,反应时间大大增加。以底物4-硝基苯胺作为原料时,在150℃下与氢氧化钠水溶液反应0.1h后,4-硝基苯酚收率为100%,然而当衍生物中含有卤原子时,存在反应选择性差、反应时间长等问题,如3-氯-6-硝基苯胺在氢氧化钠水溶液中经50h的水解后,生成了多种水解产物,其中3-氯-6-硝基苯胺仅占68%,故该法适用性较窄。Document J.Org.Chem.2011,76,6356-6361 tells that 4-nitroaniline and its derivatives are used as raw materials, sodium hydroxide or N-tert-butylhydroxylamine is used as base, and water or sulfolane is used as solvent to prepare The corresponding phenol is used for the direct hydrolysis of amine group/halogen element into hydroxyl group. When both halogen element and amine group exist on the benzene ring, the selectivity is greatly reduced and the reaction time is greatly increased. When the substrate 4-nitroaniline was used as the raw material, the yield of 4-nitrophenol was 100% after reacting with aqueous sodium hydroxide solution at 150 °C for 0.1 h. However, when the derivatives contained halogen atoms, there were reaction options. Problems such as poor performance and long reaction time, such as 3-chloro-6-nitroaniline hydrolysis in aqueous sodium hydroxide solution for 50 hours, a variety of hydrolysis products are generated, of which 3-chloro-6-nitroaniline only accounts for 68 %, so the applicability of this method is narrow.
此外也有文献以苯胺类衍生物为底物,经重氮化、水解两步反应合成相应的酚。重氮化法存在操作复杂、副产物多、污染大等问题,目前尚未有以2-氯-4-硝基苯胺为原料经重氮化法合成2-氯-4-硝基苯酚。In addition, there are also literatures that use aniline derivatives as substrates to synthesize corresponding phenols through two-step reactions of diazotization and hydrolysis. The diazotization method has problems such as complicated operation, many by-products, and large pollution. At present, there is no synthesis of 2-chloro-4-nitrophenol by diazotization using 2-chloro-4-nitroaniline as a raw material.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是提供一种高效、经济、适宜工业化生产要求的硝基苯胺类物质水解成酚的方法。The technical problem to be solved by the present invention is to provide a method for hydrolyzing nitroanilines into phenol, which is efficient, economical and suitable for industrial production requirements.
为了解决上述技术问题,本发明提供一种硝基苯胺类物质水解成酚的方法,依次包括以下步骤:In order to solve the above-mentioned technical problems, the present invention provides a method for hydrolyzing nitroanilines into phenol, which comprises the following steps in turn:
1)、将作为原料的硝基苯胺类物质、催化剂、无机碱以及作为溶剂的水混合,加入至反应釜中密封后,升温至100~190℃反应2~8h,1), mix the nitroaniline substance, catalyst, inorganic base and water as solvent as raw material, add it to the reaction kettle and seal, then heat up to 100~190 ℃ and react for 2~8h,
碱:硝基苯胺类物质=1~1.5:1的摩尔比,催化剂为硝基苯胺类物质的5~20wt%;Alkali: nitroaniline substance=1~1.5:1 molar ratio, catalyst is 5~20wt% of nitroaniline substance;
所述催化剂是分子量为200~1000的聚乙二醇;The catalyst is polyethylene glycol with a molecular weight of 200-1000;
2)、步骤1)所得的反应液先降至室温,然后调节pH为1~2,所得的析出物(硝基酚类物质的粗品)经水洗、烘干,得作为产物的硝基酚类物质。2), the reaction solution obtained in step 1) is first lowered to room temperature, and then the pH is adjusted to be 1~2, and the obtained precipitate (the crude product of nitrophenols) is washed with water and dried to obtain the nitrophenols as the product. substance.
作为本发明的硝基苯胺类物质水解成酚的方法的改进:所述无机碱为氢氧化钾、氢氧化钠。As an improvement of the method for hydrolyzing nitroanilines into phenols of the present invention: the inorganic bases are potassium hydroxide and sodium hydroxide.
作为本发明的硝基苯胺类物质水解成酚的方法的进一步改进:所述步骤1)中,每1mol的硝基苯胺类物质配用200~400ml(优选300~400ml)的水。As a further improvement of the method for hydrolyzing nitroanilines into phenols of the present invention: in the step 1), 200-400 ml (preferably 300-400 ml) of water is used for every 1 mol of nitroanilines.
作为本发明的硝基苯胺类物质水解成酚的方法的进一步改进,步骤1)中:As a further improvement of the method for hydrolysis of nitroaniline substances of the present invention into phenol, in step 1):
反应温度为150~190℃,反应时间为4~6h,The reaction temperature is 150~190℃, and the reaction time is 4~6h,
碱:硝基苯胺类物质=1.2~1.5:1的摩尔比,Alkali: nitroaniline substances=1.2~1.5:1 molar ratio,
催化剂为硝基苯胺类物质的8~15wt%,The catalyst is 8-15wt% of nitroaniline substances,
所述聚乙二醇的分子量200~400。The molecular weight of the polyethylene glycol is 200-400.
作为本发明的硝基苯胺类物质水解成酚的方法的进一步改进,所述步骤2)中,调节pH所用酸为无机酸,例如为硫酸(优选20%硫酸溶液)、盐酸。As a further improvement of the method for hydrolyzing nitroanilines into phenols of the present invention, in the step 2), the acid used for pH adjustment is an inorganic acid, such as sulfuric acid (preferably 20% sulfuric acid solution) and hydrochloric acid.
作为本发明的硝基苯胺类物质水解成酚的方法的进一步改进,As a further improvement of the method for hydrolysis of nitroaniline substances of the present invention into phenol,
当原料为2-氯-4-硝基苯胺时,产物为2-氯-4-硝基苯酚;When the raw material is 2-chloro-4-nitroaniline, the product is 2-chloro-4-nitrophenol;
当原料为2-硝基-5-氯苯胺时,产物为2-硝基-5-氯苯酚;When the raw material is 2-nitro-5-chloroaniline, the product is 2-nitro-5-chlorophenol;
当原料为3-氯-4-硝基苯胺是,产物为3-氯-4-硝基苯酚。When the starting material is 3-chloro-4-nitroaniline, the product is 3-chloro-4-nitrophenol.
本发明中,In the present invention,
2-氯-4-硝基苯酚的反应方程式为:The reaction equation of 2-chloro-4-nitrophenol is:
2-硝基-5-氯苯酚的反应方程式为:The reaction equation of 2-nitro-5-chlorophenol is:
3-氯-4-硝基苯酚的反应方程式为:The reaction equation of 3-chloro-4-nitrophenol is:
本发明的硝基苯胺类物质水解成酚的方法,具有如下技术优势:The method for hydrolyzing nitroaniline substances into phenol of the present invention has the following technical advantages:
1)目前尚未有采用以2-氯-4-硝基苯胺为原料直接水解来制备2-氯-4-硝基苯酚的合成工艺报道。1) At present, there is no report on the synthesis process that adopts 2-chloro-4-nitroaniline as raw material to directly hydrolyze to prepare 2-chloro-4-nitrophenol.
2)原料、碱金属及催化剂廉价易得,反应溶剂为水,绿色环保;无需复杂催化剂的使用,工艺步骤简单,产物后处理方便。2) The raw materials, alkali metals and catalysts are cheap and easy to obtain, and the reaction solvent is water, which is green and environmentally friendly; the use of complex catalysts is not required, the process steps are simple, and the product post-processing is convenient.
3)采用本方法合成的硝基酚类物质产品纯度高、产率高。根据本发明方法所得到的2-氯-4-硝基苯酚,收率可达82.6%,纯度达99%。3) The nitrophenolic substances synthesized by this method have high purity and high yield. The 2-chloro-4-nitrophenol obtained by the method of the present invention has a yield of 82.6% and a purity of 99%.
综上所述,采用本发明的方法合成硝基酚类物质,原料利用率高,避免了高昂催化剂的使用,不但减少了三废排放,降低了生产成本,同时产品纯度高,收率高,具有很好的工业应用价值。To sum up, using the method of the present invention to synthesize nitrophenols has high utilization rate of raw materials, avoids the use of expensive catalysts, not only reduces the discharge of three wastes, but also reduces the production cost, and at the same time, the product has high purity and high yield, and has Very good industrial application value.
附图说明Description of drawings
下面结合附图对本发明的具体实施方式作进一步详细说明。The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.
图1为本发明所得的2-氯-4-硝基苯酚的质谱图;Fig. 1 is the mass spectrogram of the 2-chloro-4-nitrophenol gained by the present invention;
图2为本发明所得的2-氯-4-硝基苯酚的分子结构式。Fig. 2 is the molecular structural formula of 2-chloro-4-nitrophenol obtained by the present invention.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:The present invention is further described below in conjunction with specific embodiment, but the protection scope of the present invention is not limited to this:
实施例1、Embodiment 1,
取原料2-氯-4-硝基苯胺86.3g(0.5mol)、氢氧化钾33.7g(0.6mol)、去离子水150ml以及聚乙二醇(PEG400)10g混合,加入至反应釜中。反应釜经氮气多次置换空气后密封,升温至150℃保温4h。Take raw material 2-chloro-4-nitroaniline 86.3g (0.5mol), potassium hydroxide 33.7g (0.6mol), deionized water 150ml and polyethylene glycol (PEG400) 10g, mix, add to the reaction kettle. The reaction kettle was sealed after replacing the air with nitrogen several times, and the temperature was raised to 150 °C for 4 h.
反应结束后,将反应釜冷却至室温后打开,反应液用20%(体积%)硫酸调节pH=2,从而析出粗2-氯-4-硝基苯酚,过滤,滤饼用去离子水洗涤三次(每次洗涤去离子水的用量为30ml)后,烘干(80℃干燥至恒重),得2-氯-4-硝基苯酚(精品)71.7g,收率82.6%,纯度99%。After the reaction was completed, the reactor was cooled to room temperature and opened, and the reaction solution was adjusted to pH=2 with 20% (volume %) sulfuric acid, so that thick 2-chloro-4-nitrophenol was precipitated, filtered, and the filter cake was washed with deionized water After three times (the consumption of deionized water for each washing is 30ml), drying (80° C. to constant weight), 71.7g of 2-chloro-4-nitrophenol (fine product) was obtained, with a yield of 82.6% and a purity of 99%. .
注:当将上述pH改为=1时,收率为82.5%,纯度99%。Note: When the above pH was changed to =1, the yield was 82.5% and the purity was 99%.
实施例2、将实施例1中的“氢氧化钾33.7g(0.6mol)”改成“氢氧化钠24g(0.6mol)”,其余等同于实施例1。Example 2. Change "33.7 g (0.6 mol) of potassium hydroxide" in Example 1 to "24 g (0.6 mol) of sodium hydroxide", and the rest are identical to those of Example 1.
所得的2-氯-4-硝基苯酚收率80.6%,纯度99%。The yield of the obtained 2-chloro-4-nitrophenol was 80.6%, and the purity was 99%.
实施例3-1~实施例3-4、保持2-氯-4-硝基苯胺投料量不变,仅改变实施例1中反应温度,其余条件等同于实施例1;具体工艺参数与所得结果如下表1所示;所得2-氯-4-硝基苯酚的纯度均为99%。Example 3-1~Example 3-4, keep the 2-chloro-4-nitroaniline feeding amount unchanged, only change the reaction temperature in Example 1, and other conditions are equal to Example 1; the specific process parameters and the results obtained As shown in Table 1 below; the purity of the obtained 2-chloro-4-nitrophenol is all 99%.
表1Table 1
实施例4-1~实施例4-4、保持2-氯-4-硝基苯胺投料量不变,仅改变实施例1中碱的用量,从而相应改变碱与2-氯-4-硝基苯胺的摩尔比,其余条件等同于实施例1;具体工艺参数与所得结果如下表2所示;所得2-氯-4-硝基苯酚的纯度均为99%。Example 4-1~Example 4-4, keep the feeding amount of 2-chloro-4-nitroaniline unchanged, only change the consumption of alkali in Example 1, thereby changing the alkali and 2-chloro-4-nitro accordingly The molar ratio of aniline and the remaining conditions are identical to those of Example 1; the specific process parameters and the obtained results are shown in Table 2 below; the purity of the obtained 2-chloro-4-nitrophenol is all 99%.
表2Table 2
实施例5-1~实施例5-4、保持2-氯-4-硝基苯胺投料量不变,仅改变实施例1中聚乙二醇(PEG400)使用量,其余条件等同于实施例1。具体工艺参数与所得结果如下表3所示;所得2-氯-4-硝基苯酚的纯度均为99%。Example 5-1~Example 5-4, keep the feeding amount of 2-chloro-4-nitroaniline unchanged, only change the amount of polyethylene glycol (PEG400) used in Example 1, and the remaining conditions are equivalent to Example 1 . The specific process parameters and the obtained results are shown in Table 3 below; the purity of the obtained 2-chloro-4-nitrophenol is both 99%.
表3table 3
实施例6-1~实施例6-3、保持2-氯-4-硝基苯胺投料量不变,仅改变实施例1中聚乙二醇的种类,其余条件等同于实施例1;具体工艺参数与所得结果如下表4所示;所得2-氯-4-硝基苯酚的纯度均为99%。Example 6-1 to Example 6-3, keep the 2-chloro-4-nitroaniline feeding amount unchanged, only change the type of polyethylene glycol in Example 1, and the remaining conditions are equal to Example 1; the specific process The parameters and the obtained results are shown in Table 4 below; the purity of the obtained 2-chloro-4-nitrophenol is both 99%.
表4Table 4
实施例7-1~实施例7-4、保持2-氯-4-硝基苯胺投料量不变,仅改变实施例1中水的用量,其余条件等同于实施例1;具体工艺参数与所得结果如下表5所示;所得2-氯-4-硝基苯酚的纯度均为99%。Example 7-1 ~ Example 7-4, keep the 2-chloro-4-nitroaniline feeding amount unchanged, only change the amount of water in Example 1, and other conditions are equal to Example 1; specific process parameters and obtained The results are shown in Table 5 below; the purity of the obtained 2-chloro-4-nitrophenol is all 99%.
表5table 5
实施例8-1~实施例8-3、保持2-氯-4-硝基苯胺投料量不变,仅改变实施例1中反应时间,其余条件等同于实施例1;具体工艺参数与所得结果如下表6所示;所得2-氯-4-硝基苯酚的纯度均为99%。Example 8-1~Example 8-3, keep the 2-chloro-4-nitroaniline feeding amount unchanged, only change the reaction time in Example 1, and other conditions are equal to Example 1; the specific process parameters and the results obtained As shown in Table 6 below; the purity of the obtained 2-chloro-4-nitrophenol is all 99%.
表6Table 6
实施例9、Embodiment 9,
取原料2-硝基-5-氯苯胺0.5mol、氢氧化钾0.6mol、去离子水150ml以及聚乙二醇(PEG400)10g混合,加入至反应釜中。反应釜经氮气多次置换空气后密封,升温至150℃保温4h。Take raw material 2-nitro-5-chloroaniline 0.5mol, potassium hydroxide 0.6mol, deionized water 150ml and polyethylene glycol (PEG400) 10g, mix, add to the reaction kettle. The reaction kettle was sealed after replacing the air with nitrogen several times, and the temperature was raised to 150 °C for 4 h.
反应结束后,将反应釜冷却至室温后打开,反应液用20%硫酸调节pH=2,从而析出粗2-硝基-5-氯苯酚,过滤,滤饼用去离子水洗涤三次(每次洗涤去离子水的用量为30ml)后,烘干(80℃干燥至恒重),得2-硝基-5-氯苯酚(精品)70.2g,收率80.9%,纯度99%。After the reaction was completed, the reactor was cooled to room temperature and opened, and the reaction solution was adjusted to pH=2 with 20% sulfuric acid, thereby separating out thick 2-nitro-5-chlorophenol, filtered, and the filter cake was washed three times with deionized water (each time The amount of washing deionized water is 30ml), drying (80 ° C to constant weight), to obtain 2-nitro-5-chlorophenol (fine) 70.2g, yield 80.9%, purity 99%.
实施例10、
取原料3-氯-4-硝基苯胺0.5mol、氢氧化钾0.6mol、去离子水150ml以及聚乙二醇(PEG400)10g混合,加入至反应釜中。反应釜经氮气多次置换空气后密封,升温至150℃保温4h。Take raw material 3-chloro-4-nitroaniline 0.5mol, potassium hydroxide 0.6mol, deionized water 150ml and polyethylene glycol (PEG400) 10g, mix, add to the reaction kettle. The reaction kettle was sealed after replacing the air with nitrogen several times, and the temperature was raised to 150 °C for 4 h.
反应结束后,将反应釜冷却至室温后打开,反应液用20%硫酸调节pH=2,从而析出粗3-氯-4-硝基苯酚,过滤,滤饼用去离子水洗涤三次(每次洗涤去离子水的用量为30ml)后,烘干(80℃干燥至恒重),得3-氯-4-硝基苯酚(精品)71.2g,收率82.1%,纯度99%。After the reaction was completed, the reactor was cooled to room temperature and opened, and the reaction solution was adjusted to pH=2 with 20% sulfuric acid, thereby separating out thick 3-chloro-4-nitrophenol, filtered, and the filter cake was washed three times with deionized water (each time After washing, the amount of deionized water is 30ml), drying (80° C. to constant weight), to obtain 71.2g of 3-chloro-4-nitrophenol (fine product), with a yield of 82.1% and a purity of 99%.
对比例1、相对于实施例1而言,仅改变实施例1反应液调节的pH值,其余条件等同于实施例1;具体工艺参数与所得结果如下表7所示;Comparative Example 1, with respect to Example 1, only the pH value regulated by the reaction solution of Example 1 was changed, and the remaining conditions were identical to those of Example 1; the specific process parameters and the obtained results were shown in Table 7 below;
表7Table 7
对比例2、相对于实施例1而言,改变实施例1中的催化剂(或取消催化剂的使用),其余条件等同于实施例1;具体工艺参数与所得结果与实施例1的对比如下表8所示;Comparative example 2, with respect to Example 1, change the catalyst in Example 1 (or cancel the use of the catalyst), and the remaining conditions are equal to Example 1; the specific process parameters and the results obtained are compared with Example 1 as shown in Table 8 shown;
表8Table 8
对比例3、相对于实施例1而言,仅仅将溶剂由水分别改成环丁砜或甲醇;其余等同于实施例1。所得结果为:均无法进行有效反应,收率为0。Comparative Example 3. Compared with Example 1, only the solvent was changed from water to sulfolane or methanol; the rest were the same as those of Example 1. The obtained results are: no effective reaction can be carried out, and the yield is 0.
对比例4、相对于实施例9而言,改变实施例9中催化剂(或取消催化剂的使用),相应的改变/不改变反应时间,其余条件等同于实施例9;具体工艺参数与所得结果与实施例9的如下表9所示;Comparative Example 4, with respect to Example 9, change the catalyst in Example 9 (or cancel the use of the catalyst), correspondingly change/do not change the reaction time, and the remaining conditions are equal to Example 9; The following table 9 of embodiment 9 is shown;
表9Table 9
对比例5、相对于实施例10而言,改变实施例10中催化剂(或取消催化剂的使用),相应的改变/不改变反应时间,其余条件等同于实施例10;具体工艺参数与所得结果与实施例10的如下表10所示;Comparative example 5, with respect to Example 10, change the catalyst in Example 10 (or cancel the use of the catalyst), correspondingly change/do not change the reaction time, and the remaining conditions are equal to Example 10; the specific process parameters and the results obtained are the same as The following table 10 of
表10Table 10
最后,还需要注意的是,以上列举的仅是本发明的若干个具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形,均应认为是本发明的保护范围。Finally, it should also be noted that the above enumeration is only a few specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and many modifications are possible. All modifications that those of ordinary skill in the art can directly derive or associate from the disclosure of the present invention shall be considered as the protection scope of the present invention.
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