CN111362899A - Preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride - Google Patents

Preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride Download PDF

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CN111362899A
CN111362899A CN201911325059.7A CN201911325059A CN111362899A CN 111362899 A CN111362899 A CN 111362899A CN 201911325059 A CN201911325059 A CN 201911325059A CN 111362899 A CN111362899 A CN 111362899A
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吴爱斌
胡艳雄
周五
师春甜
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Abstract

The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride. Taking acenaphthene as a raw material, adding acenaphthene, sodium bromide and a catalyst into a mixed solution of glacial acetic acid and water, dropwise adding hydrogen peroxide for temperature-controlled reaction to obtain 5-bromoacenaphthene; adding 5-bromoacenaphthene and metal nitrate into glacial acetic acid, and stirring at a controlled temperature to react to obtain 4-bromo-5-nitroacenaphthene; adding 4-bromo-5-nitro acenaphthene and a catalyst into glacial acetic acid, introducing oxygen, and heating to react to obtain 4-bromo-5-nitro-1, 8-naphthalic anhydride. The target product prepared by the method has the advantages of cheap and easily-obtained raw materials, low preparation cost, high product yield, mild preparation process conditions, good atom economy and industrial batch production.

Description

Preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride.
Background
4-bromo-5-nitro-1, 8-naphthalic anhydride is an important fine chemical and an important intermediate in the dye and pigment industry. At present, the industrial preparation method still adopts the traditional means of N-bromosuccinimide (NBS)/Dimethylformamide (DMF) bromination, mixed acid (sulfuric acid/nitric acid) nitration, sodium dichromate oxidation and the like. The process obviously has the defects of serious environmental pollution (more three wastes, large corrosion), high cost and the like, so that a new, green and economic synthesis process is urgently needed to be developed.
The existing green bromination, nitration and oxidation technologies are widely concerned due to the characteristics of high efficiency, high selectivity, atom economy and the like. Among the reported green bromination techniques, for example, Wanghaibo et al (research on the synthesis of 5-bromoacenaphthylene, the chemical world, 2012,3,160-162) employed H2O2The NBS is replaced by the HBr oxidation bromination process, so that the utilization rate of bromine is improved, the production cost is saved, and the environmental pollution is reduced; bukharkia etc. (Catalytic oxidation of acetic acid and its derivatives in acetic acid, Organic Process Research)&Development,2002,6,394-400) adopts cobalt acetate/manganese acetate/oxygen to replace sodium dichromate to prepare 4-nitro-1, 8-naphthalic anhydride, reduces environmental pollution and three-waste discharge, and achieves the achievements of catalyst recycling and the like. However, the processes still have some defects, such as difficult industrial popularization and application, narrow substrate universality, harmony among product functions, cost and environmental protection, and the like. Therefore, the research and discovery of the preparation method of the 4-bromo-5-nitro-1, 8-naphthalic anhydride, which has the advantages of stable reaction, high product yield, high purity, low cost, simple process and easy industrialization, has extremely important theoretical significance and application value.
Disclosure of Invention
Aiming at the defects of the prior preparation technology of the 4-bromo-5-nitro-1, 8-naphthalic anhydride, the invention provides the preparation method of the 4-bromo-5-nitro-1, 8-naphthalic anhydride, which has the advantages of simple operation, safe and reliable production, small environmental pollution, low cost, high yield and good quality.
The technical scheme adopted by the invention is as follows:
a preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride comprises the following reaction processes:
Figure BDA0002328166110000011
wherein: i is acenaphthene; II is 5-bromoacenaphthene; III is 4-bromo-5-nitro acenaphthene; IV is 4-bromo-5-nitro-1, 8-naphthalic anhydride.
The method comprises the following steps:
step one, bromination reaction
Adding acenaphthene, sodium bromide and a catalyst ① into a mixed solution of glacial acetic acid and water, dropwise adding hydrogen peroxide, setting the reaction temperature and time, cooling to room temperature after the reaction is finished, and carrying out suction filtration, washing and vacuum drying to obtain 5-bromoacenaphthene;
step two, nitration reaction
Adding 5-bromoacenaphthene and metal nitrate into glacial acetic acid, setting reaction temperature and time, cooling to room temperature after the reaction is finished, and obtaining 4-bromo-5-nitroacenaphthene after suction filtration, washing and vacuum drying;
step three, oxidation reaction
Adding 4-bromo-5-nitro acenaphthene and catalyst ② into glacial acetic acid, introducing oxygen, setting reaction temperature and time, cooling to room temperature after reaction, performing suction filtration, washing, vacuum drying, and recrystallizing with glacial acetic acid to obtain 4-bromo-5-nitro-1, 8-naphthalic anhydride.
In the step one, a bromination system adopted is sodium bromide/catalyst ①/hydrogen peroxide, and the catalyst ① is CeCl3·7H2O、AlCl3、ZnCl2、CuCl2·2H2O、MnCl2、NiCl2·6H2One or any combination of two or more of O, preferably CeCl3·7H2And O, the molar ratio of the acenaphthene to the catalyst ① is 10: 1-1.5, preferably 10: 1-1.2, the set reaction temperature is 15-30 ℃, preferably 20-25 ℃, and the set reaction time is 2-6 hours, preferably 3-4 hours.
In the second step, the adopted nitration system is metal nitrate/glacial acetic acid, and the metal nitrate is LiNO3、NaNO3、KNO3、Mg(NO3)2、Ca(NO3)2、Ba(NO3)2、Al(NO3)3·9H2O、 Cu(NO3)2·3H2O、Bi(NO3)3·5H2One or two or more of OAnd preferably Cu (NO)3)2·3H2O/Al(NO3)3·9H2A combination system of O, wherein the molar ratio is 1-1.3: 4, preferably 1-1.1: 4; the molar ratio of the 5-bromoacenaphthene to the metal nitrate is 1: 1-1.3, preferably 1: 1-1.2; the set reaction temperature is 35-80 ℃, and preferably 45-60 ℃; the set reaction time is 2-8 h, preferably 4-5 h.
In the third step, an oxidation system adopted is ②/oxygen, the catalyst ② is one or any combination of two or more of cobalt acetate, cobalt bromide, manganese sulfate, manganese acetate and N-hydroxyphthalimide (NHPI), preferably a combination system of cobalt acetate/NHPI, the molar ratio is 1: 1-1.5, preferably 1: 1-1.3, the molar ratio of 4-bromo-5-nitroaphthylene to the catalyst ② (cobalt acetate/NHPI) is 15: 1-1.3: 1-1.6, preferably 15: 1-1.2: 1-1.3, the set reaction temperature is 50-110 ℃, preferably 70-80 ℃, and the set reaction time is 2-8 hours, preferably 4-5 hours.
The invention has the beneficial effects that: the invention provides a preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride, which is simple to operate, cheap and easily available in raw materials, high in product yield, mild in conditions in the whole preparation process, good in atom economy, green and pollution-free in post-treatment and easy to industrialize, and the production cost is greatly reduced.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the present invention is not limited to the embodiments. The implementation conditions adopted in the case can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are those in routine experiments.
Example 1
Figure 4
15.4g (0.0998mol) of acenaphthene, 10.29g (0.1mol) of sodium bromide and 2.3759 g (0.01mol) of NiCl were added in this order to a round-bottomed flask2·6H2O (catalyst), 198mL of glacial acetic acid and 99mL of water, and then 204mL of hydrogen peroxide is added to 2Reacting for 3 hours at 0 ℃, then cooling the reaction liquid to room temperature, carrying out suction filtration, and respectively using 5-10 mL of H2Washing the filter cake with O and absolute ethyl alcohol, and drying in vacuum to obtain a yellow product 5-bromoacenaphthene with the yield of 92.4%. HRMS (ES +) C12H10Br([M+H])+Theoretical 232.9966, found 232.9964. The purity of the target compound was 98.5% by HPLC.
Example 2
Example 2 except that the catalyst was 1.7048g (0.01mol) of CuCl2·2H2O, the temperature is controlled to be 15 ℃ and the reaction is carried out for 4 hours, other conditions and preparation steps are the same as those of the example 1, and the yellow product 5-bromoacenaphthene is obtained, and the yield is 94.4%. HRMS (ES +) C12H10Br([M+H])+Theoretical 232.9966, found 232.9960. The purity of the target compound was 98.3% by HPLC.
Example 3
Example 3 except that the catalyst was 3.7258g (0.01mol) CeCl3·7H2O, the temperature is controlled to be 20 ℃ and the reaction lasts for 3 hours, other conditions and preparation steps are the same as those of the example 1, and the yellow product 5-bromoacenaphthene is obtained, and the yield is 97.5%. HRMS (ES +) C12H10Br([M+H]) + theoretical value 232.9966, found 232.9963. The purity of the target compound was 99.1% by HPLC.
Example 4
Example 4 except that the catalyst was 37.258g (0.1mol) CeCl3·7H2O, all reaction raw materials and corresponding conditions are enlarged by 9 times, and the reaction is carried out for 4 hours at the temperature of 15 ℃, other conditions and preparation steps are the same as those of the example 1, so that the yellow product 5-bromoacenaphthene is obtained, and the yield is 96.3%. HRMS (ES +) C12H10Br([M+H])+Theoretical 232.9966, found 232.9960. The purity of the target compound was 99.2% by HPLC.
Example 5
Example 5 except that the catalyst was 2.5572g (0.015mol) of CuCl2·2H2O, the temperature is controlled to be 20 ℃ and the reaction is carried out for 4 hours, other conditions and preparation steps are the same as those of the example 1, and the yellow product 5-bromoacenaphthene is obtained, and the yield is 93.4%. HRMS (ES +) C12H10Br([M+H])+Theoretical value 232.9966, found 232.9960. The purity of the target compound was 97.3% by HPLC.
Example 6
Figure 2
Adding 44g (0.197mol) of 5-bromoacenaphthene, 51.304g (0.212mol) of copper nitrate trihydrate (nitrating agent) and 95mL of glacial acetic acid into a round-bottom flask in sequence, stirring and reacting for 3 hours at the temperature of 50 ℃, then cooling the reaction liquid to room temperature, performing suction filtration, and respectively using 5-10 mL of H2Washing the filter cake with O and absolute ethyl alcohol, and vacuum drying to obtain 4-bromo-5-nitro acenaphthylene with a yield of 91.3%. HRMS (ES +) C12H9BrNO2([M+H])+Theoretical 277.9817, found 277.9815. The purity of the target compound was 99.3% by HPLC.
Example 7
Example 7 the same conditions and preparation procedures as in example 6 were repeated except that the nitrating agent was a mixture of 10.2608g (0.0424mol) of copper nitrate trihydrate and 63.622g (0.1696mol) of aluminum nitrate nonahydrate, and the reaction was carried out at 40 ℃ for 3 hours to obtain 4-bromo-5-nitroacenaphthylene with a yield of 91.5%. HRMS (ES +) C12H9BrNO2([M+H])+Theoretical 277.9817, found 277.9816. The purity of the target compound was 99.4% by HPLC.
Example 8
The conditions and preparation steps were the same as those of example 6 except that the nitrating agent in example 8 was a mixture of 102.608g (0.424mol) of copper nitrate trihydrate and 636.22g (1.696 mol) of aluminum nitrate nonahydrate, and all the reaction materials and the corresponding conditions were enlarged by 9 times, and the temperature was controlled at 50 ℃ to react for 4 hours, thereby obtaining 4-bromo-5-nitroaenaphthylene with a yield of 94.3%. HRMS (ES +) C12H9BrNO2([M+H])+Theoretical 277.9817, found 277.9812. The purity of the target compound was 99.6% by HPLC.
Example 9
Example 9 conditions and preparation were carried out except that the nitrating agent was a mixture of 11.0594g (0.0457mol) of copper nitrate trihydrate and 62.3625g (0.1663mol) of aluminum nitrate nonahydrate, and the reaction was carried out at 40 ℃ for 4 hoursThe procedure is as in example 6 to obtain 4-bromo-5-nitroaenaphthyl in 92.5% yield. HRMS (ES +) C12H9BrNO2([M+H])+Theoretical 277.9817, found 277.9813. The purity of the target compound was 99.1% by HPLC.
Example 10
Example 10 the same procedures used in example 6 were repeated except that the nitrating agent was 79.5g (0.212mol) of aluminum nitrate nonahydrate and the reaction was carried out at 60 ℃ for 4 hours to give 4-bromo-5-nitroacenaphthylene in 91.5% yield. HRMS (ES +) C12H9BrNO2([M+H])+Theoretical 277.9817, found 277.9813. The purity of the target compound was 99.2% by HPLC.
Example 11
Figure 3
720.9g (2.7mol) of 4-bromo-5-nitro acenaphthene, 4.98g (0.2mol) of cobalt acetate (catalyst) and 275g of glacial acetic acid are sequentially added into a round-bottom flask, oxygen is introduced, the mixture reacts for 3 hours at the temperature of 70 ℃, then the reaction liquid is cooled to room temperature, is filtered by suction, and is respectively added with 5-10 mL of H2O and anhydrous C2H5OH washes a filter cake, and the filter cake is dried in vacuum to obtain the 4-bromo-5-nitro-1, 8-naphthalic anhydride with the yield of 91.5 percent. HRMS (ES +) C12H5BrNO5([M+H])+Theoretical 321.9351, found 321.9350. The purity of the target compound was 98.3% by HPLC.
Example 12
Example 12 the same conditions and preparation procedure as in example 11 were repeated except that the catalyst was a mixture of 4.98g (0.2mol) of cobalt acetate and 40.7825g (0.25mol) of N-hydroxyphthalimide, and the reaction was carried out at 70 ℃ for 4 hours to obtain 4-bromo-5-nitro-1, 8-naphthalic anhydride with a yield of 98.5%. HRMS (ES +) C12H5BrNO5([M+H])+Theoretical 321.9351, found 321.9349. The purity of the target compound was 99.5% by HPLC.
Example 13
Example 13 with the exception that the catalyst was 0.498g (0.02mol) of cobalt acetate,4.07825g (0.025mol) of N-hydroxyphthalimide, and all the reaction raw materials and the corresponding conditions are reduced by 9 times, and the reaction is carried out for 3 hours at 50 ℃, and other conditions and preparation steps are the same as those of example 11, so as to obtain 4-bromo-5-nitro-1, 8-naphthalic anhydride with the yield of 98.5%. HRMS (ES +) C12H5BrNO5([M+H])+Theoretical 321.9351, found 321.9349. The purity of the target compound was 99.5% by HPLC.
Example 14
Example 14 the same conditions and preparation procedures as in example 11 were repeated except that the catalyst was 4.98g (0.2mol) of cobalt acetate and 40.7825g (0.25mol) of N-hydroxyphthalimide, and the reaction was carried out at 50 ℃ for 3 hours to obtain 4-bromo-5-nitro-1, 8-naphthalic anhydride with a yield of 94.5%. HRMS (ES +) C12H5BrNO5([M+H])+Theoretical 321.9351, found 321.9350. The purity of the target compound was 99.3% by HPLC.
Example 15
Example 15 the same conditions and preparation procedures as in example 11 were repeated except that the catalyst was 4.98g (0.2mol) of cobalt acetate and 44.0451g (0.27mol) of N-hydroxyphthalimide, and the reaction was carried out at 70 ℃ for 3 hours to obtain 4-bromo-5-nitro-1, 8-naphthalic anhydride with a yield of 98.3%. HRMS (ES +) C12H5BrNO5([M+H])+Theoretical 321.9351, found 321.9348. The purity of the target compound was 99.4% by HPLC.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (7)

1. A preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride is characterized by comprising the following preparation processes:
step one, bromination reaction
Adding acenaphthene, sodium bromide and a catalyst ① into a mixed solution of glacial acetic acid and water, dropwise adding hydrogen peroxide, setting the reaction temperature and time, cooling to room temperature after the reaction is finished, and carrying out suction filtration, washing and vacuum drying to obtain 5-bromoacenaphthene;
step two, nitration reaction
Adding 5-bromoacenaphthene and metal nitrate into glacial acetic acid, setting reaction temperature and time, cooling to room temperature after the reaction is finished, and obtaining 4-bromo-5-nitroacenaphthene after suction filtration, washing and vacuum drying;
step three, oxidation reaction
Adding 4-bromo-5-nitro acenaphthene and catalyst ② into glacial acetic acid, introducing oxygen, setting reaction temperature and time, cooling to room temperature after reaction, performing suction filtration, washing, vacuum drying, and recrystallizing with glacial acetic acid to obtain 4-bromo-5-nitro-1, 8-naphthalic anhydride.
2. The method for preparing 4-bromo-5-nitro-1, 8-naphthalic anhydride according to claim 1, wherein a bromination system adopted in the step one is sodium bromide/catalyst ①/hydrogen peroxide, and the catalyst ① is CeCl3·7H2O、AlCl3、ZnCl2、CuCl2·2H2O、MnCl2、NiCl2·6H2One or any combination of two or more of O.
3. The preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride according to claim 1, wherein in the first step, the molar ratio of acenaphthylene to the catalyst ① is 10: 1-1.5, and the reaction temperature and the reaction time are 15-30 ℃ and 2-6 hours respectively.
4. The method for preparing 4-bromo-5-nitro-1, 8-naphthalic anhydride according to claim 1, wherein: in the second step, the adopted nitration system is metal nitrate/glacial acetic acid, and the metal nitrate is LiNO3、NaNO3、KNO3、Mg(NO3)2、Ca(NO3)2、Ba(NO3)2、Al(NO3)3·9H2O、Cu(NO3)2·3H2O、Bi(NO3)3·5H2One or any combination of two or more of O, preferably Cu (NO)3)2·3H2O/Al(NO3)3·9H2And the molar ratio of the O in the combined system is 1-1.3: 4.
5. The method for preparing 4-bromo-5-nitro-1, 8-naphthalic anhydride according to claim 1, wherein: in the second step, the molar ratio of the 5-bromoacenaphthene to the metal nitrate is 1: 1-1.3, and the reaction temperature and the reaction time are respectively 35-80 ℃ and 2-8 hours.
6. The preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride according to claim 1, wherein an oxidation system adopted in the third step is catalyst ②/oxygen, the catalyst ② is one or any combination of two or more of cobalt acetate, cobalt bromide, manganese sulfate, manganese acetate and N-hydroxyphthalimide, preferably a combination system of cobalt acetate/N-hydroxyphthalimide, and the molar ratio is 1: 1-1.5.
7. The preparation method of 4-bromo-5-nitro-1, 8-naphthalic anhydride according to claim 1, wherein in the third step, the molar ratio of 4-bromo-5-nitroacenaphthylene to catalyst ② (cobalt acetate/N-hydroxyphthalimide) is 15: 1-1.3: 1-1.6, and the reaction temperature and time are 50-110 ℃ and 2-8 hours respectively.
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