Preparation method of N-acylpyrene amine and preparation method of 1-hydroxypyrene

Abstract

The invention provides a preparation method of N-acylpyrene amine and a preparation method of 1-hydroxypyrene. The preparation method comprises the steps: reacting C2-C10 nitro compounds containing alpha-H with pyrene in solid superacid and a first solvent to obtain the N-acyl pyrene amine. According to the method, under the catalytic action of the solid superacid, the alpha-H of the C2-C10 nitro compound containing alpha-H is easier to pull out, so that the alpha-C of the C2-C10 nitro compound containing alpha-H is connected with the C on the 1 position of pyrene, and then the N-acetyl pyrene amine is obtained through one-step reaction; and the 1-hydroxypyrene is synthesized by taking the N-acetyl pyrene amine obtained by the preparation method as a raw material. According to the preparation method, the reaction steps are reduced, the reaction conditions are mild, the raw material source is wide, and the use of a polluting acylation reagent is avoided, so that the environmental pollution is reduced, and the production cost is reduced on the whole.

Description

technical field

[0001] The invention relates to the technical field of synthesis of 1-hydroxypyrene, in particular to a preparation method of N-acylpyreneamine and a preparation method of 1-hydroxypyrene. Background technique

[0002] At present, there are four main preparation routes of 1-hydroxypyrene:

[0003] 1. Heat up the sodium alkylate solution to reflux, add 1-bromopyrene to react for 10 to 15 hours, recover the solvent, cool down, and centrifugally dry to obtain 1-alkoxypyrene; then dissolve 1-alkoxypyrene in the solvent , and with an amino acid compound containing a terminal mercapto group under the condition of strong inorganic base, heat up to 120-170° C., react for 2-3 hours, and obtain 1-hydroxypyrene after solvent recovery, purification and drying. This route needs to use a large amount of mercapto amino acids, the reaction conditions are harsh, and the purity of 1-hydroxypyrene is relatively low.

[0004]

[0005] 2. Using pyrene as a raw material, sulf...

Examples

preparation example Construction

[0026] In a typical embodiment of the present application, a preparation method of N-acylpyreneamine is provided, the preparation method comprising: adding C 2 ~C 10 The nitro compound containing α-H reacts with pyrene in a solid superacid and a first solvent to obtain N-acylpyreneamine.

[0027] This application ends with C 2 ~C 10 The nitro compound containing α-H and pyrene are the reaction raw materials, wherein C 2 ~C 10 The α-H of the nitro compound containing α-H itself has a strong acidity, and under the catalysis of a solid superacid, C 2 ~C 10 The α-H of the α-H-containing nitro compound is more easily pulled out, so that the C 2 ~C 10 The α-C of the nitro compound containing α-H is connected to the C on the 1-position of pyrene, and then through a one-step reaction to obtain N-acetylpyreneamine, and then the N-acetylpyreneamine obtained by this preparation method As a raw material to synthesize 1-hydroxypyrene. Compared with the traditional method—by perfor...

preparation Embodiment 1

[0043] First, add 20.2g (0.1mol) of pyrene, 8.25g (0.11mol) of nitroethane, and 80mL of acetic acid to a 250mL glass three-necked flask, and finally add 3g of HNF-5W perfluorosulfonic acid resin. Under nitrogen protection, the temperature is raised to Stir at 80°C for 8 hours, cool down to room temperature after passing the TLC control, and obtain N-acetylpyreneamine. MS(m / z)259[M] of N-acetylpyreneamine + , and the H NMR spectrum data are 1 H NMR (DMSO-d 6 )δ2.28 (s, 3H), 8.0-8.4 (m, 9H), 10.35 (s, 1H).

preparation Embodiment 2

[0045] The difference between the preparation example 2 of N-acylpyreneamine and the preparation example 1 of N-acylpyreneamine is that 20.2g (0.1mol) pyrene and 7.88g (0.105mol) nitroethane are added to finally obtain N-acetyl base pyrenamine.

technical field

[0001] The invention relates to the technical field of synthesis of 1-hydroxypyrene, in particular to a preparation method of N-acylpyreneamine and a preparation method of 1-hydroxypyrene. Background technique

[0002] At present, there are four main preparation routes of 1-hydroxypyrene:

[0003] 1. Heat up the sodium alkylate solution to reflux, add 1-bromopyrene to react for 10 to 15 hours, recover the solvent, cool down, and centrifugally dry to obtain 1-alkoxypyrene; then dissolve 1-alkoxypyrene in the solvent , and with an amino acid compound containing a terminal mercapto group under the condition of strong inorganic base, heat up to 120-170° C., react for 2-3 hours, and obtain 1-hydroxypyrene after solvent recovery, purification and drying. This route needs to use a large amount of mercapto amino acids, the reaction conditions are harsh, and the purity of 1-hydroxypyrene is relatively low.

[0004]

[0005] 2. Using pyrene as a raw material, sulf...

Examples

preparation example Construction

[0026] In a typical embodiment of the present application, a preparation method of N-acylpyreneamine is provided, the preparation method comprising: adding C 2 ~C 10 The nitro compound containing α-H reacts with pyrene in a solid superacid and a first solvent to obtain N-acylpyreneamine.

[0027] This application ends with C 2 ~C 10 The nitro compound containing α-H and pyrene are the reaction raw materials, wherein C 2 ~C 10 The α-H of the nitro compound containing α-H itself has a strong acidity, and under the catalysis of a solid superacid, C 2 ~C 10 The α-H of the α-H-containing nitro compound is more easily pulled out, so that the C 2 ~C 10 The α-C of the nitro compound containing α-H is connected to the C on the 1-position of pyrene, and then through a one-step reaction to obtain N-acetylpyreneamine, and then the N-acetylpyreneamine obtained by this preparation method As a raw material to synthesize 1-hydroxypyrene. Compared with the traditional method—by perfor...

preparation Embodiment 1

[0043] First, add 20.2g (0.1mol) of pyrene, 8.25g (0.11mol) of nitroethane, and 80mL of acetic acid to a 250mL glass three-necked flask, and finally add 3g of HNF-5W perfluorosulfonic acid resin. Under nitrogen protection, the temperature is raised to Stir at 80°C for 8 hours, cool down to room temperature after passing the TLC control, and obtain N-acetylpyreneamine. MS(m / z)259[M] of N-acetylpyreneamine + , and the H NMR spectrum data are 1 H NMR (DMSO-d 6 )δ2.28 (s, 3H), 8.0-8.4 (m, 9H), 10.35 (s, 1H).

preparation Embodiment 2

[0045] The difference between the preparation example 2 of N-acylpyreneamine and the preparation example 1 of N-acylpyreneamine is that 20.2g (0.1mol) pyrene and 7.88g (0.105mol) nitroethane are added to finally obtain N-acetyl base pyrenamine.

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