A method for preparing mononitrated derivatives of 1,8-disubstituted naphthalene-based condensed ring aromatic hydrocarbons

Abstract

A method for preparing a mononitrated derivative of a 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon is characterized by comprising the following steps: S1, dissolving a 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon and a subgroup metal nitrate in an organic solvent, performing a nitration reaction at 10 to 60°C, and performing TLC monitoring to determine the end point of the reaction after 4 to 10 hours, until the raw material point disappears; S2, cooling the product obtained in S1 to room temperature, filtering with suction, washing the filter cake with 5 to 10 mL of H2O and anhydrous C2H5OH, respectively, and vacuum drying to obtain a mononitrated derivative of a 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon. The product yield of this method is 93% to 96%, and the product purity is 98% to 99.5%. Compared with the prior art, the present invention has the characteristics of high product yield and purity, low cost, simple process, and ease of industrialization.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemicals, and particularly relates to a method for preparing a mononitrated derivative of 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbons. Background Art

[0002] 1,8-Disubstituted naphthalene-based polycyclic aromatic hydrocarbons are important fine chemical raw materials, primarily derived from byproducts of petroleum refining and coal tar. Their nitration products are widely used in various industries, including dyes, pharmaceuticals, pesticides, explosives, and daily necessities, possessing significant practical and economic value. Currently, the industrial preparation method still relies on traditional mixed acid nitration, but this process suffers from significant drawbacks such as poor selectivity, high levels of waste, high corrosion rates, and severe environmental pollution. Clean, green, efficient, highly selective, and atom-economical nitration technologies are gaining increasing attention.

[0003] Among the reported green nitration technologies, such as solid acid catalysis and Lewis acid catalysis, certain results have been achieved in replacing sulfuric acid to reduce corrosion and three waste emissions, and in catalyst recovery and recycling. However, these processes still have some shortcomings, such as the difficulty in industrial promotion and application, the poor universality of the substrates, and how to solve the relationship between function, cost and greenness. Summary of the Invention

[0004] The present invention addresses the deficiencies of existing green nitration technologies and provides a method for preparing mononitrated derivatives of 1,8-disubstituted naphthalene-based fused-ring aromatic hydrocarbons with simple operation, safe and reliable production, low environmental pollution, low cost, high yield and good quality.

[0005] The present invention provides a method for preparing a mononitrated derivative of a 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon, characterized in that the method comprises the following steps:

[0006] S1. Dissolve 1,8-disubstituted naphthalene-based condensed ring aromatic hydrocarbons and a subgroup metal nitrate in an organic solvent, and carry out a nitration reaction at 10-60° C. After 4-10 hours, the reaction is terminated when the raw material point disappears as monitored by TLC;

[0007] S2. The product obtained in S1 was cooled to room temperature, filtered, and the filter cake was washed with 5-10 mL of H2O and anhydrous C2H5OH, respectively, and dried under vacuum to obtain a mononitrated derivative of 1,8-disubstituted naphthalene-based condensed ring aromatic hydrocarbons.

[0008] Furthermore, the mononitrated derivative of 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon refers to a derivative in which a nitro group is introduced at the 3-position or 4-position of the naphthalene ring.

[0009] The chemical reaction formula is as follows:

[0010]

[0011] The reactant (I) is a 1,8-disubstituted naphthalene series condensed ring aromatic hydrocarbon, and the product (II) is a mononitrated derivative of a 1,8-disubstituted naphthalene series condensed ring aromatic hydrocarbon.

[0012] Furthermore, the 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon is one of the following: 1,8-dimethylnaphthalene, 1,8-dihydroxynaphthalene, 1,8-diaminonaphthalene, 1,8-dimethoxynaphthalene, 1,8-dimethylaminonaphthalene, acenaphthene, acenaphthene, acenaphthenequinone, 1,8-naphthalene anhydride, 1,8-naphthalene imide, N-hydroxy-1,8-naphthalene imide, N-(2-morpholinylethyl)-1,8-naphthalene imide, 1,8-naphthalene lactam, 1,8-naphthalene sultone;

[0013] The subgroup metal nitrate is one of the following or any combination of more than one: Cr(NO3)3, Mn(NO3)2·, Fe(NO3)3, Co(NO3)2, Ni(NO3)2, Cu(NO3)2, Zn(NO3)2, RuNO(NO3)3, Rh(NO3)3, Pd(NO3)2, AgNO3, Cd(NO3)2, Hg(NO3)2, La(NO3)3, Ce(NH4)2(NO3)6, Eu(NO3)3, Tb(NO3)3, Er(NO3)3, Yb(NO3)3;

[0014] The ratio of the amount of the 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon to the sub-group metal nitrate substance is 1:1.1-1.3.

[0015] Furthermore, the subgroup metal nitrates are Fe(NO3)3, Cu(NO3)2 and Ce(NH4)2(NO3)6.

[0016] Furthermore, the ratio of the amount of the 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon to the sub-group metal nitrate substance is 1:1.15.

[0017] Furthermore, the solvent for the nitration reaction is one of the following or any combination of more than one: methanol, ethanol, isopropanol, tert-butanol, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, benzene, toluene, xylene, cyclopentane, n-hexane, ethyl ether, isopropyl ether, butyl ether, petroleum ether, acetone, cyclopentanone, acetic acid, acetic anhydride, ethyl acetate, tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide; the amount of the organic solvent is 1.0 to 3.0 mL / mmol 1,8-disubstituted naphthalene condensed ring aromatic hydrocarbons.

[0018] Furthermore, the solvent for the nitration reaction is acetic acid and acetic acid / acetic anhydride.

[0019] Furthermore, the amount of the organic solvent used is 1.3 to 1.6 mL / mmol of 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon.

[0020] Furthermore, in step S1, the reaction time of the nitration reaction is 5 hours.

[0021] Furthermore, in step S1, the reaction temperature of the nitration reaction is 25-40°C.

[0022] Furthermore, the product yield of the 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon mononitration derivative is 93% to 96%, and the product purity is 98% to 99.5%.

[0023] The present invention has the beneficial effects of: under certain reaction conditions, the method for preparing a mononitrated derivative of a 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon has a product yield of 93% to 96% and a product purity of 98% to 99.5%. Compared with the prior art, the present invention has the advantages of high product yield and purity, low cost, simple process, and ease of industrialization. DETAILED DESCRIPTION

[0024] To make the objectives, technical solutions, and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessary confusion of the concepts of the present invention.

[0025] Example 1

[0026]

[0027] 3.12 g (20 mmol, M = 156.23) of 1,8-dimethylnaphthalene (I-1) and 9.29 g (23 mmol, M = 404.00) of Fe(NO3)3·9H2O were added to 26 mL of CH3COOH and reacted at 40°C for 5 h. The reaction was terminated by TLC monitoring until the starting material disappeared. The mixture was cooled to room temperature and filtered. The filter cake was washed with a small amount of H2O and anhydrous C2H5OH, respectively, and vacuum dried to obtain the pale yellow product 4-nitro-1,8-dimethylnaphthalene (II-1) in a yield of 92%. HPLC purity was 98.6%. HRMS (ES+) C 12 H 12 NO2([M+H]) + Theoretical value is 202.0868, measured value is 202.0866.

[0028] Example 2

[0029]

[0030] 3.20 g (20 mmol, M = 160.17) of 1,8-dihydroxynaphthalene (I-2) and 5.35 g (23 mmol, M = 232.59) of Cu(NO3)2·2.5H2O were added to 13 mL of CH3COOH + 13 mL of (CH3CO)2O, and the reaction was controlled at 25°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain an orange-yellow product, 4-nitro-1,8-naphthalenediol (II-2), in a yield of 91%. HPLC purity was 99.2%. HRMS (ES+) C 10 H8NO4([M+H]) + Theoretical value 206.0453, measured value 206.0453.

[0031] Example 3

[0032]

[0033] 3.16 g (20 mmol, M = 158.20) of 1,8-diaminonaphthalene (I-3) and 9.29 g (23 mmol, M = 404.00) of Fe(NO3)3·9H2O were added to 13 mL of CH3COOH + 13 mL of (CH3CO)2O, and the reaction was controlled at 25°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain the orange-red product 4-nitro-1,8-naphthalenediamine (II-3) in a yield of 94%. HPLC purity was 99.0%. HRMS (ES+) C 10 H 10 N3O2([M+H]) + Theoretical value is 204.0773, measured value is 204.0774.

[0034] Example 4

[0035]

[0036] 3.76 g (20 mmol, M = 188.23) of 1,8-dimethoxynaphthalene (I-4) and 12.61 g (23 mmol, M = 548.22) of Ce(NH4)2(NO3)6 were added to 30 mL of CH3COOH and the reaction was controlled at 35°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain the orange-red product 4-nitro-1,8-dimethoxynaphthalene (II-4) in a yield of 94%. HPLC purity was 98.5%. HRMS (ES+) C 12 H 12 NO4([M+H]) + Theoretical value 234.0766, measured value 234.0766.

[0037] Example 5

[0038]

[0039] 4.29 g (20 mmol, M = 214.31) 1,8-dimethylaminonaphthalene (I-5) and 5.35 g (23 mmol, M = 232.59) Cu(NO3)2·2.5H2O were added to 13 mL CH3COOH + 13 mL (CH3CO)2O, and the reaction was controlled at 25°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain the orange-red product 4-nitro-1,8-dimethylaminonaphthalene (II-5) in a yield of 93%. HPLC purity was 99.5%. HRMS (ES+) C 14 H 18 N3O2([M+H]) + Theoretical value is 260.1399, measured value is 260.1398.

[0040] Example 6

[0041]

[0042] 3.08 g (20 mmol, M = 154.21) of acenaphthene (I-6) and 9.29 g (23 mmol, M = 404.00) of Fe(NO3)3·9H2O were added to 30 mL of CH3COOH and the reaction was controlled at 35°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a light yellow product, 5-nitroacenaphthene (II-6), in a yield of 96%. HPLC purity was 99.5%. HRMS (ES+) C 12 H 10 NO2([M+H]) + Theoretical value is 200.0712, measured value is 200.0712.

[0043] Example 7

[0044]

[0045] 3.08 g (20 mmol, M = 154.21) of acenaphthene (I-6) and 5.35 g (23 mmol, M = 232.59) of Cu(NO3)2·2.5H2O were added to 30 mL of CH3COOH and the reaction was controlled at 40°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a light yellow product, 5-nitroacenaphthene (II-6), in a yield of 96%. HPLC purity was 99.2%. HRMS (ES+) C 12 H 10 NO2([M+H]) + Theoretical value is 200.0712, measured value is 200.0711.

[0046] Example 8

[0047]

[0048] 3.08 g (20 mmol, M = 154.21) of acenaphthene (I-6) and 5.35 g (23 mmol, M = 232.59) of Cu(NO3)2·2.5H2O were added to 14 mL of CH3COOH + 14 mL of (CH3CO)2O, and the reaction was controlled at 25°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a light yellow product, 5-nitroacenaphthene (II-6), in a yield of 95.0%. HPLC purity was 99.5%. HRMS (ES+) C 12 H 10 NO2([M+H]) + Theoretical value is 200.0712, measured value is 200.0710.

[0049] Example 9

[0050]

[0051] 3.08 g (20 mmol, M = 154.21) of acenaphthene (I-6) and 12.61 g (23 mmol, M = 548.22) of Ce(NH4)2(NO3)6 were added to 14 mL of CH3COOH + 14 mL of (CH3CO)2O, and the reaction was controlled at 25°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a light yellow product, 5-nitroacenaphthene (II-6), in a yield of 94.5%. HPLC purity was 99.0%. HRMS (ES+) C 12 H 10 NO2([M+H]) + Theoretical value is 200.0712, measured value is 200.0710.

[0052] Example 10

[0053]

[0054] 3.04 g (20 mmol, M = 152.20) of acenaphthylene (I-7) and 9.29 g (23 mmol, M = 404.00) of Fe(NO3)3·9H2O were added to 35 mL of CH3COOH and the reaction was controlled at 40°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a yellow product, 4-nitroacenaphthylene (II-7), in a yield of 93.5%. HPLC purity was 98.5%. HRMS (ES+) C 12 H8NO2([M+H]) + Theoretical value is 198.0555, measured value is 198.0557.

[0055] Example 11

[0056]

[0057] 3.64 g (20 mmol, M = 182.19) of acenaphthenequinone (I-8) and 12.61 g (23 mmol, M = 548.22) of Ce(NH4)2(NO3)6 were added to 18 mL of CH3COOH + 18 mL of (CH3CO)2O, and the reaction was controlled at 35°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a yellow product, 3-nitroacenaphthenequinone (II-8), in a yield of 94%. HPLC purity was 99.0%. HRMS (ES+) C 12 H6NO4([M+H]) + Theoretical value is 228.0297, measured value is 228.0297.

[0058] Example 12

[0059]

[0060] 3.96 g (20 mmol, M = 198.18) of 1,8-naphthoic anhydride (I-9) and 5.35 g (23 mmol, M = 232.59) of Cu(NO3)2·2.5H2O were added to 18 mL of CH3COOH + 18 mL of (CH3CO)2O, and the reaction was controlled at 40°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a yellow product, 3-nitro-1,8-naphthoic anhydride (II-9), in a yield of 94%. HPLC purity was 98.2%. HRMS (ES+) C 12 H6NO5([M+H]) + Theoretical value is 244.0246, measured value is 244.0246.

[0061] Example 13

[0062]

[0063] 3.94 g (20 mmol, M = 197.19) of 1,8-naphthaleneimide (I-10) and 9.29 g (23 mmol, M = 404.00) of Fe(NO3)3·9H2O were added to 18 mL of CH3COOH + 18 mL of (CH3CO)2O, and the reaction was controlled at 35°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a yellow product, 3-nitro-1,8-naphthaleneimide (II-10), in a yield of 93.8%. HPLC purity was 99.0%. HRMS (ES+) C 12 H7N2O4([M+H]) + Theoretical value is 243.0406, measured value is 243.0406.

[0064] Example 14

[0065]

[0066] 4.26 g (20 mmol, M = 213.19) of N-hydroxy-1,8-naphthalimide (I-11) and 9.29 g (23 mmol, M = 404.00) of Fe(NO3)3·9H2O were added to 18 mL of CH3COOH + 18 mL of (CH3CO)2O, and the reaction was controlled at 35°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a yellow product, 3-nitro-N-hydroxy-1,8-naphthalimide (II-11), in a yield of 94%. HPLC purity was 98.7%. HRMS (ES+) C 12 H7N2O5([M+H]) + Theoretical value is 259.0355, measured value is 259.0355.

[0067] Example 15

[0068]

[0069] 6.21 g (20 mmol, M = 310.35) of N-(2-morpholinoethyl)-1,8-naphthalimide (I-12) and 5.35 g (23 mmol, M = 232.59) of Cu(NO3)2·2.5H2O were added to 36 mL of CH3COOH and the reaction was controlled at 40°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a yellow product, 3-nitro-N-(2-morpholinoethyl)-1,8-naphthalimide (II-12), in a yield of 96.5%. HPLC purity was 99.5%. HRMS (ES+) C 18 H 18 N3O5([M+H]) + Theoretical value is 356.1246, measured value is 356.1245.

[0070] Example 16

[0071]

[0072] 3.38 g (20 mmol, M = 169.18) of 1,8-naphtholactam (I-13), 4.65 g (11.5 mmol, M = 404.00) of Fe(NO3)3·9H2O, and 2.67 g (11.5 mmol, M = 232.59) of Cu(NO3)2·2.5H2O were added to 18 mL of CH3COOH + 18 mL of (CH3CO)2O, and the reaction was controlled at 35°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a yellow product, 5-nitro-1,8-naphtholactam (II-13), in a yield of 95.0%. HPLC purity was 99.5%. HRMS (ES+) C 11 H7N2O3([M+H]) + Theoretical value 215.0457, measured value 215.0457.

[0073] Example 17

[0074]

[0075] 4.12 g (20 mmol, M = 206.22) of 1,8-naphthalene sultone (I-14), 4.65 g (11.5 mmol, M = 404.00) of Fe(NO3)3·9H2O, and 6.30 g (11.5 mmol, M = 548.22) of Ce(NH4)2(NO3)6 were added to 18 mL of CH3COOH + 18 mL of (CH3CO)2O. The reaction was controlled at 35°C for 5 h. Other conditions and preparation steps were the same as in Example 1 to obtain a yellow product, 5-nitro-1,8-naphthalene sultone (II-14), in a yield of 95.6%. HPLC purity was 99.2%. HRMS (ES+) C 10 H6NO5S([M+H]) + Theoretical value is 251.9967, measured value is 251.9967.

[0076] Among them, in Examples 6, 7, 8 and 9, 5-nitroacenaphthene is synthesized by nitration of acenaphthene. Compared with the methods reported in the literature, there are improvements in process simplification, improved yield, shortened reaction cycle, reduced reactants and reduced energy consumption. In the methods reported in the literature, the yield is 69.6% to 83%, the reaction temperature is 40°C to 225°C, the reaction time is 3.5 to 15h, the ratio of the amount of nitrating agent to the raw material is 1:1.6 to 1:3.5, and some methods use The organic solvent dichloroethane is prone to environmental pollution (nitration reaction of acenaphthene, Chen Mingqiang, Hu Yingyu, Shen Yongjia, "Dye Industry", Vol. 38, No. 1, pp. 21-23, February 2001; a new method for the synthesis of 5-nitroacenaphthene, Zhu Huiqin, "Chemical Reagents", Vol. 24, No. 1, pp. 45-46, January 2002; synthesis of 5-nitroacenaphthene by phase transfer method, Zhu Huiqin, "Chemical World", No. 5, pp. 259-260, May 2002).

[0077] Example 12 utilizes 1,8-naphthalene anhydride to nitrate and synthesize 3-nitro-1,8-naphthalene anhydride. Compared with the method reported in the literature (Synthesis of 3-nitro-1,8-naphthalene anhydride, Wang Sheng, Jiang Xuliang, "Fine Chemical Intermediates", Vol. 43, No. 2, pp. 49-50, April 2013), Example 12 has improvements in terms of increased yield, reduced reactants, shortened reaction cycle, reduced pollution, and reduced energy consumption. The yield in the literature is 65-71%, the ratio of the amount of nitrating agent to the raw material is 1:2, the reaction temperature is 60°C, the reaction time is 6-10 h, and the solvent used is dichloroethane.

[0078] It should be understood that the above-described specific embodiments of the present invention are merely illustrative or illustrative of the principles of the present invention and do not constitute limitations of the present invention. Therefore, any modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and scope of the present invention should be included within the scope of protection of the present invention. In addition, the appended claims are intended to cover all variations and modifications that fall within the scope and metes and bounds of the appended claims, or equivalents thereof.

Claims

1. A method for preparing a mononitrated derivative of a 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon, characterized in that: The method comprises the following steps: S1. Dissolve 1,8-disubstituted naphthalene-based condensed ring aromatic hydrocarbons and a subgroup metal nitrate in an organic solvent, and carry out a nitration reaction at 10-60° C. After 4-10 hours, the reaction is terminated when the raw material point disappears as monitored by TLC; S2. Cool the product obtained in S1 to room temperature, filter it with suction, wash the filter cake with 5-10 mL of H2O and anhydrous C2H5OH, respectively, and dry it in vacuo to obtain a mononitrated derivative of a 1,8-disubstituted naphthalene-based fused-ring aromatic hydrocarbon; The 1,8-disubstituted naphthalene-based condensed ring aromatic hydrocarbon mononitrated derivative refers to a derivative in which a nitro group is introduced at the 3-position or 4-position of the naphthalene ring; The 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon is one of the following: 1,8-dimethylnaphthalene, 1,8-dihydroxynaphthalene, 1,8-diaminonaphthalene, 1,8-dimethoxynaphthalene, 1,8-dimethylaminonaphthalene, acenaphthene, acenaphthene, acenaphthenequinone, 1,8-naphthalene anhydride, 1,8-naphthalene imide, N-hydroxy-1,8-naphthalene imide, N-(2-morpholinylethyl)-1,8-naphthalene imide, 1,8-naphthalene lactam, 1,8-naphthalene sultone; The subgroup metal nitrate is one or more of the following: Fe(NO3)3, Cu(NO3)2, Ce(NH4)2(NO3)6; The amount of the organic solvent is 1.0 to 3.0 mL / mmol of 1,8-disubstituted naphthalene condensed ring aromatic hydrocarbon; The ratio of the amount of the 1,8-disubstituted naphthalene-based condensed ring aromatic hydrocarbon to the sub-group metal nitrate substance is 1:1.15; The solvent for the nitration reaction is acetic acid or acetic acid / acetic anhydride.

2. The method for preparing a mononitrated derivative of a 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon according to claim 1, characterized in that: The amount of the organic solvent used is 1.3-1.6 mL / mmol of 1,8-disubstituted naphthalene condensed ring aromatic hydrocarbon.

3. The method for preparing a mononitrated derivative of a 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon according to claim 1, characterized in that: In step S1, the reaction time of the nitration reaction is 5 hours.

4. The method for preparing a mononitrated derivative of a 1,8-disubstituted naphthalene-based condensed-ring aromatic hydrocarbon according to claim 3, characterized in that: In step S1, the reaction temperature of the nitration reaction is 25-40°C.

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