CN107652267B - Synthesis and application of solid reversible pyrazolone photochromic compound - Google Patents

Synthesis and application of solid reversible pyrazolone photochromic compound Download PDF

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CN107652267B
CN107652267B CN201711033140.9A CN201711033140A CN107652267B CN 107652267 B CN107652267 B CN 107652267B CN 201711033140 A CN201711033140 A CN 201711033140A CN 107652267 B CN107652267 B CN 107652267B
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pyrazolone
diphenyl
bromo
thiosemicarbazide
solid
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CN107652267A (en
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刘岸杰
陈怡�
郭继玺
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Xinjiang University
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract

The invention belongs to the field of solid organic photochromism, and relates to synthesis and application of a solid reversible pyrazolone photochromic compound, which takes theoretical calculation as guidance to synthesize 1, 3-diphenyl-4- (5-bromo) pyridinoyl-5-pyrazolone (DP5Br3PyBP) and N (4) -methyl-thiosemicarbazide (MTSC)/N (4) -ethyl-thiosemicarbazide (ETSC)/N (4) -phenyl-semicarbazide (PSC) through condensation reaction in an ethanol solution to obtain 1, 3-diphenyl-4- (5-bromo) pyridinoyl-5-pyrazolone N (4) -methyl thiosemicarbazide (DP5Br3PyBP-MTSC) and 1, 3-diphenyl-4- (5-bromo) pyridinoyl-5-pyrazolone N (4) -ethyl thiosemicarbazide (DP5Br3PyBP) -ETSC) and 1, 3-diphenyl-4- (5-bromo) pyridionyl-5-pyrazolone-condensed N (4) -phenylthiosemicarbazide (DP5Br3 PyBP-PTSC). All three compounds have reversible photochromic properties in the solid state.

Description

Synthesis and application of solid reversible pyrazolone photochromic compound
Technical Field
The invention relates to synthesis and application of a solid reversible pyrazolone photochromic compound.
Background
The solid reversible photochromic material is a compound or a mixture A, under the radiation of a certain external excitation light source, the substance A generates obvious color change after absorbing external electromagnetic waves, and the color-changed substance B can generate the phenomenon of color return under the condition of another excitation light source. Organic photochromic materials are receiving more and more attention from researchers at home and abroad due to the potential application value of the organic photochromic materials in the fields of information storage, molecular switches, biotechnology and the like. However, the material with good photochromic performance in solid state is the basis of wide application, but at present, the material can not meet the requirement of high technical field, and the development of organic photochromic materials with various types, rich colors and high photosensitivity is urgently needed. Therefore, the synthesis of new solid-state organic photochromic materials remains the focus of current research. The pyrazolone derivative synthesized by the invention is a novel optical functional material with a unique structure and excellent optical performance in a solid state, and the compound shows reversible photochromic performance in the solid state, has good fluorescent modulation and fatigue resistance, and has potential application value in the fields of high-density information storage, fluorescent molecular switches and the like. At present, most of pyrazolones synthesized by the subject group are photochromic thermoreversible or photochromic but irreversible compounds, the type and the performance are single, and the requirements of people on the diversity of materials cannot be met. By combining with theoretical calculation results, the pyrazolone compound with reversible photochromic performance, which is synthesized by the method, fills the gap and enriches the system.
Disclosure of Invention
The invention relates to synthesis and application of a solid reversible pyrazolone photochromic compound.
The invention relates to synthesis and application of a solid reversible pyrazolone photochromic compound, and in combination with theoretical calculation results, 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone and N (4) -methyl-thiosemicarbazide (MTSC)/N (4) -ethyl-thiosemicarbazide (ETSC)/N (4) -phenyl-semicarbazide (PSC) are subjected to condensation reaction to prepare 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone N (4) -methyl thiosemicarbazide (DP5Br3PyBP-MTSC), 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone N (4) -ethyl thiosemicarbazide (DP5Br3 PyBP-ETSC) and 1 with photochromic performance, 3-Diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolinone condensed N (4) -phenylthiosemicarbazide (DP5Br3 PyBP-PTSC).
The invention adopts 1, 3-diphenyl-4- (5-bromine) pyridine acyl-5-pyrazolone and N (4) -methyl-thiosemicarbazide (MTSC)/N (4) -ethyl-thiosemicarbazide (ETSC)/N (4) -phenyl-semicarbazide (PSC) to carry out condensation reaction. The method comprises the following specific steps: 1) weighing 7.09 g of 1, 3-diphenyl-5-pyrazolone (DPP) (30 mmol) in a three-necked bottle, adding 20 mL of dioxane, and heating for dissolving; 2) under stirring in an oil bath at 80 ℃ 4.35 g Ca (OH) were added2Stirring the fine powder uniformly; 3) removing the oil bath condition, quickly dropwise adding 6.4 g of 5-bromopyridine acyl chloride (dissolved by dioxane) under strong stirring, instantly changing the color of the solution into dark green, gradually changing into reddish brown, and stirring for 5 min to gradually moderate the reaction; 4) continuously stirring for 50 min under the condition of 80 ℃ oil bath, removing the oil bath, and adding 50 mL of HCl solution with the concentration of 3 mol/L while the solution is hot; 5) cooling with a small amount of water after a large amount of oily substance appears, stirring to obtain a large amount of solid powder, vacuum filtering, washing with distilled water for 3 times at room temperatureDrying in the air to obtain brown yellow powder 1, 3-diphenyl-4- (5-bromo) pyridine acyl-5-pyrazolone (DP5Br3 PyBP); 6) weighing the same moles of DP5Br3PyBP and N (4) -methyl-thiosemicarbazide (MTSC)/N (4) -ethyl-thiosemicarbazide (ETSC)/N (4) -phenyl-semicarbazide (PSC) in a 25 mL round bottom flask; 7) adding a proper amount of ethanol and a small amount of glacial acetic acid (used as a catalyst) to react for 7 hours under the stirring of an oil bath at the temperature of 80 ℃; 8) filtering, and recrystallizing with ethanol to obtain dry solid powder.
The invention has the advantages that the pyrazolone compound with solid-state photo-reversible discoloration performance is prepared, and the invention has the following advantages: 1) the three compounds have the photochromic property of photo-reversible under solid state, and are a new characteristic of pyrazolone compounds. 2) The solid powders of the compounds DP5Br3PyBP-MTSC, DP5Br3PyBP-ETSC and DP5Br3PyBP-PTSC appeared light purple, purple red and white, respectively. The three compounds were irradiated with uv light and it was found that the color of the sample changed significantly with the increase of the uv irradiation time. After the discolored compound is irradiated by visible light, the color of the sample gradually returns, and the reversible photoisomerization reaction can be performed on the three compounds under the action of the light. The three compounds have high color change rate and good fatigue resistance, can be repeatedly used, are good photochromic materials, and can be applied to information storage, molecular switch, photosensitive switches and the like. 3) The fluorescence emission spectrum shows that the three compounds have blue fluorescence under ultraviolet light, the fluorescence emission intensity gradually decreases until the compounds disappear along with the extension of the ultraviolet illumination time, the fluorescence quenching rates of the three compounds are all more than 80%, and the DP5Br3PyBP-PTSC reaches 97.6%. They both show good fluorescence reversibility under the alternating action of ultraviolet light and visible light.
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FIG. 1 shows UV-VIS absorption spectra before and after discoloration of 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone N (4) -methylaminothiourea (DP5Br3PyBP-MTSC), 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone N (4) -ethylaminothiourea (DP5Br3 PyBP-ETSC) and 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone N (4) -phenylaminothiourea (DP5Br3 PyBP-PTSC) and fatigue resistance tests.
FIG. 2 shows fluorescence emission spectra before and after discoloration of 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone N (4) -methylaminothiourea (DP5Br3PyBP-MTSC), 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone N (4) -ethylaminothiourea (DP5Br3 PyBP-ETSC) and 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone N (4) -phenylaminothiourea (DP5Br3 PyBP-PTSC) and fatigue resistance tests.
FIG. 3 is an infrared spectrum of 1, 3-diphenyl-4- (5-bromo) pyridinoyl-5-pyrazolone N (4) -methylaminothiourea (DP5Br3PyBP-MTSC), 1, 3-diphenyl-4- (5-bromo) pyridinoyl-5-pyrazolone N (4) -ethylaminothiourea (DP5Br3 PyBP-ETSC) and 1, 3-diphenyl-4- (5-bromo) pyridinoyl-5-pyrazolone N (4) -phenylaminothiourea (DP5Br3 PyBP-PTSC) before and after discoloration.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Examples of the embodiments
7.09 g of 1, 3-diphenyl-5-pyrazolone (DPP) (30 mmol) was weighed into a three-necked flask, 20 mL of dioxane was added, and heated to dissolve. Under stirring in an oil bath at 80 ℃ 4.35 g Ca (OH) were added2Stirring the fine powder uniformly, removing the oil bath condition, quickly dropwise adding 6.4 g of 5-bromopyridine acyl chloride (dissolved by dioxane) under strong stirring, instantly changing the color of the solution into dark green, gradually changing into reddish brown, stirring for 5 min, gradually slowing down the reaction, continuously stirring for 50 min under the condition of 80 ℃ oil bath, removing the oil bath, adding 50 mL of HCl solution with the concentration of 3 mol/L while hot, cooling with a small amount of water after a large amount of oily substances appear, continuously stirring until a large amount of solid powder appears, performing suction filtration, washing with distilled water for 3 times, and drying at room temperature to obtain brown yellow powder 1, 3-diphenyl-4- (5-bromo) pyridine acyl-5-pyrazolone (DP5Br3 PyBP). The same molar amounts of DP5Br3PyBP and N (4) -methyl-thiosemicarbazide (MTSC)/N (4) -ethyl-thiosemicarbazide (ETSC)/N (4) -phenyl-semicarbazide (PSC) were weighed into a 25 mL round bottom flask and reacted with the appropriate amount of ethanol and a small amount of glacial acetic acid (as catalyst) in an 80 ℃ oil bath for 7 h with stirringLight red solid powder crystals are obtained, and dried solid powder is obtained after suction filtration and ethanol recrystallization. The synthesis methods of 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone N (4) -ethylthiosemicarbazide (DP5Br3 PyBP-ETSC) and 1, 3-diphenyl-4- (5-bromo) pyridinoacyl-5-pyrazolone N (4) -phenylthiosemicarbazide (DP5Br3 PyBP-PTSC) were the same as above. The three compounds have good reversible photochromic performance, fade under 365 nm ultraviolet light irradiation and return under visible light irradiation.
The material has good reversible photochromic performance, and as shown in figure 1, the three compounds have strong ultraviolet absorption intensity under the irradiation of a 365 nm ultraviolet lamp, and the fading phenomenon occurs. Under the irradiation of visible light, the ultraviolet absorption intensity becomes weak, and the color gradually recovers. Wherein the compound 1, 3-diphenyl-4- (5-bromo) pyridine acyl-5-pyrazolone N (4) -phenyl thiosemicarbazide (DP5Br3 PyBP-PTSC) shows better fatigue resistance. The material has reversible photochromic performance and can be applied to the aspect of light opening.
FIG. 2 is a fluorescence spectrum of three compounds, from which we can see that the fluorescence emission intensity of the compounds is reduced under 365 nm ultraviolet lamp irradiation, and gradually increased under visible light irradiation. As the three compounds have obvious contrast of fluorescence signals under the action of light and show good fluorescence modulation performance, the three compounds can exert the specific performance in the fields of photonic switches, biological cell identification and the like.
FIG. 3 is the infrared spectrum before and after UV irradiation of the material, and we can see that the three compounds are respectively 1663 cm-1、1661 cm-1And 1658 cm-1An obvious infrared absorption peak appears, and the peak can be assigned as a stretching vibration peak of carbonyl C = O, which indicates that the compound has a ketone structure after being irradiated by ultraviolet light. We speculate that the molecular structure of the compound is converted from an alcoholic structure before UV irradiation to a ketone structure after UV irradiation.

Claims (1)

1. The application of the solid reversible pyrazolone photochromic compound in the aspect of optical switches is characterized in that the solid reversible pyrazolone photochromic compound is 1, 3-diphenyl-4- (5-bromo) pyridinoyl-5-pyrazolone N (4) -phenylthiosemicarbazone.
CN201711033140.9A 2017-10-30 2017-10-30 Synthesis and application of solid reversible pyrazolone photochromic compound Expired - Fee Related CN107652267B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101624519A (en) * 2008-11-04 2010-01-13 新疆大学 Preparation and application of pyrazolone-shrinking phenyl semicarbazide photochromic compounds
CN101709054A (en) * 2009-09-16 2010-05-19 新疆大学 Preparation and application of pyrazolone methyl thiosemicarbazone photochromic compound

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101624519A (en) * 2008-11-04 2010-01-13 新疆大学 Preparation and application of pyrazolone-shrinking phenyl semicarbazide photochromic compounds
CN101709054A (en) * 2009-09-16 2010-05-19 新疆大学 Preparation and application of pyrazolone methyl thiosemicarbazone photochromic compound

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Design and synthesis of reversible solid-state photochromic pyrazolones by introducing a pyridine ring;Guo, Jixi等;《Photochemical & Photobiological Sciences》;20160829;第15卷(第10期);1222-1226 *

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