CN114014868A - Preparation method of spiropyran compound for light conversion agent - Google Patents
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- FLHJIAFUWHPJRT-UHFFFAOYSA-N 2,3,3-trimethylindole Chemical compound C1=CC=C2C(C)(C)C(C)=NC2=C1 FLHJIAFUWHPJRT-UHFFFAOYSA-N 0.000 claims abstract description 19
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- OKIOOZNPLPIPQD-UHFFFAOYSA-N 3-(2,3,3-trimethyl-1,2-dihydroindol-1-ium-1-yl)propanoic acid;bromide Chemical compound [Br-].C1=CC=C2C(C)(C)C(C)[NH+](CCC(O)=O)C2=C1 OKIOOZNPLPIPQD-UHFFFAOYSA-N 0.000 claims abstract description 6
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- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 238000010992 reflux Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- VGCALSXXWOIEGB-UHFFFAOYSA-N 2,3,3-trimethylindole;hydrobromide Chemical compound Br.C1=CC=C2C(C)(C)C(C)=NC2=C1 VGCALSXXWOIEGB-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- PFQRNEUIKXTAPK-UHFFFAOYSA-N 3-(2,3,3-trimethylindol-1-ium-1-yl)propanoic acid bromide Chemical compound [Br-].CC1=[N+](CCC(O)=O)C2=CC=CC=C2C1(C)C PFQRNEUIKXTAPK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NYKVUZZALLADOW-UHFFFAOYSA-N 2-(3,3-dimethyl-6-nitrospiro[indole-2,2'-pyran]-1-yl)ethanol Chemical compound OCCN1C2=CC(=CC=C2C(C11OC=CC=C1)(C)C)[N+](=O)[O-] NYKVUZZALLADOW-UHFFFAOYSA-N 0.000 description 1
- FDVITFMRUUGIBF-UHFFFAOYSA-N 2-methylidene-1,3-dihydroindole Chemical compound C1=CC=C2NC(=C)CC2=C1 FDVITFMRUUGIBF-UHFFFAOYSA-N 0.000 description 1
- YBWXCCCUPTUVPQ-UHFFFAOYSA-N 3-(3,3-dimethyl-6-nitrospiro[indole-2,2'-pyran]-1-yl)propanoic acid Chemical compound C(=O)(O)CCN1C2=CC(=CC=C2C(C12OC=CC=C2)(C)C)[N+](=O)[O-] YBWXCCCUPTUVPQ-UHFFFAOYSA-N 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- RFQIWHDNNZFRBL-UHFFFAOYSA-N acetic acid;ethanol;hydrate Chemical compound O.CCO.CC(O)=O RFQIWHDNNZFRBL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- LALYXZGJXHIQMB-UHFFFAOYSA-N benzene 2H-pyran Chemical group C1=CC=CC=C1.O1CC=CC=C1 LALYXZGJXHIQMB-UHFFFAOYSA-N 0.000 description 1
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- 125000001041 indolyl group Chemical group 0.000 description 1
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- UKXKGTGQIITIAB-UHFFFAOYSA-N spiro[1,3-dihydroindole-2,2'-pyran] Chemical compound C1C2=CC=CC=C2NC11OC=CC=C1 UKXKGTGQIITIAB-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a preparation method of a spiropyran compound used for a light conversion agent, which comprises the following steps: (1) synthesizing 2,3, 3-trimethyl-3H-indole from phenylhydrazine and methyl isopropyl ketone in a mixed solvent of ethanol, acetic acid and water; (2) synthesizing 1- (3-hydroxyethyl) 2,3, 3-trimethyl-3H-indole bromide or 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide by reacting the 2,3, 3-trimethyl-3H-indole synthesized in the step (1) with bromoethanol or 3-bromopropionic acid in an organic solvent; (3) and (3) synthesizing hydroxy spiropyran from the 1- (3-hydroxyethyl) 2,3, 3-trimethyl-3H-indole bromide obtained in the step (2) and 5-nitro salicylaldehyde or synthesizing carboxy spiropyran from the 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide and 5-nitro salicylaldehyde. The invention provides a novel spiropyran serving as a ligand of a light conversion agent, and the light aging phenomenon of the light conversion agent is reduced and the weather resistance is improved by utilizing the light-induced isomerization principle.
Description
Technical Field
The invention relates to an agricultural functional material, in particular to a preparation method of a spiropyran compound used for a light conversion agent.
Background
China is a big agricultural country, the yield and consumption of agricultural films are in the forefront of the world, along with the development of modern agriculture, people have higher and higher requirements on the performance of the agricultural films, and various functional films are developed. The light conversion agent is a novel plastic additive developed according to the needs of modern high-efficiency high-quality agriculture. The light conversion film prepared by adding a certain light conversion agent into the resin can convert harmful or useless ultraviolet light and green light in sunlight into red orange light and blue light required by plant photosynthesis, improve plant illumination conditions, improve the light energy utilization rate, strengthen the plant photosynthesis and improve the yield and the quality of crops.
The light conversion agent is mainly divided into an organic light conversion agent and an inorganic light conversion agent, wherein the inorganic light conversion agent is mainly prepared by doping rare earth luminescent ions or other metal activated ions by taking metal sulfide or oxide as a matrix. Since the rare earth inorganic light conversion agent has the characteristic of simultaneously converting blue light and red light, the rare earth inorganic light conversion agent becomes one of the research hotspots of the current light conversion agent. Usually, a complex formed by rare earth ions and organic ligands is taken as a main functional unit.
After the light conversion agent is added into resin to form a light conversion film, the light conversion film is exposed to wind and sunlight for a long time, the luminous intensity is reduced to a certain extent, and the fluorescence attenuation degree of the light conversion agent determines the practical value of the light conversion film, so that the light conversion agent needs to have good weather resistance. The weather resistance of the light conversion agent is closely related to the organic ligand in the light conversion agent.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a preparation method of a spiropyran compound used for a light conversion agent. The spiropyran synthesized by the novel preparation method is used as a ligand of the light conversion agent, and the light aging phenomenon of the light conversion agent is reduced and the weather resistance is improved by utilizing the light isomerization principle.
The technical scheme is as follows: as shown in FIG. 1, the spiropyran is composed of an aromatic heterocycle (Ar)1) And a pyran benzene ring (Ar)2) The organic compound with photochromic property is a general name of a class connected by a sp3 hybridized carbon atom. Currently, the spiropyran molecule, in which Ar1 is an indole ring structure, has been most widely studied and is often referred to as indoline spiropyran or spiropyran.
The conventional synthesis method of the spiropyran compound is to generate the spiropyran compound by condensing and adding 2-methylene isoindole derivatives and salicylaldehyde derivatives. Therefore, the structural design thought of the spiropyran compound is correspondingly divided into two. Firstly, different substituents are modified on 2-methylene indoline, and secondly, the molecular structure of the salicylaldehyde derivative is designed, and a typical synthetic route is shown in figure 2.
In order to solve the problems of the prior art, the invention provides a new synthetic route of a spiropyran compound, and as shown in fig. 3, the invention provides a preparation method of the spiropyran compound for a light conversion agent, which comprises the following steps:
(1) heating and refluxing phenylhydrazine and methyl isopropyl ketone in a mixed solvent of ethanol, acetic acid and water for 3-4H to synthesize 2,3, 3-trimethyl-3H-indole;
(2) synthesizing 1- (3-hydroxyethyl) 2,3, 3-trimethyl-3H-indole bromide or 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide by reacting the 2,3, 3-trimethyl-3H-indole synthesized in the step (1) with bromoethanol or 3-bromopropionic acid in an organic solvent;
(3) and (3) synthesizing hydroxy spiropyran from the 1- (3-hydroxyethyl) 2,3, 3-trimethyl-3H-indole bromide obtained in the step (2) and 5-nitro salicylaldehyde or synthesizing carboxy spiropyran from the 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide and 5-nitro salicylaldehyde.
In a preferred embodiment of the present invention, in step (1), the reaction solvent is a mixed solvent of acetic acid, ethanol and water in a volume ratio of 4:1: 1.
In a preferred embodiment of the present invention, in the step (1), the temperature of the heating reflux is 105 to 110 ℃.
In a preferred embodiment of the present invention, in step (1), the heating reflux time is 3.5 h.
In a preferred embodiment of the present invention, in the step (1), the temperature of the heating reflux is 106 ℃.
As a preferred embodiment of the present invention, in step (1), the 2,3, 3-trimethyl-3H-indole is extracted with ethyl acetate for 2-3 times, the extracts are combined, and the fraction at 120 ℃ is collected by reduced pressure distillation to obtain 2,3, 3-trimethyl-3H-indole.
In a preferred embodiment of the present invention, in the step (2), the reaction solvent is acetonitrile or chloroform.
As a preferred embodiment of the present invention, in step (2), the reaction is carried out in N2Heating and refluxing for 40-60h under protection.
In a preferred embodiment of the present invention, in the step (2), the temperature of the heating reflux is 75 to 85 ℃.
As a preferred embodiment of the present invention, in step (2), the reaction is carried out in N2Heating and refluxing at 80 ℃ for 48h under protection.
In a preferred embodiment of the present invention, in the step (3), the reaction is performed under the condition of heating and refluxing at 75-85 ℃ for 3-20 h.
As a preferred embodiment of the present invention, in the step (3), the reaction is carried out under the condition of heating and refluxing at 75-85 ℃ for 3-20 hours.
In a preferred embodiment of the present invention, in step (1), the molar ratio of phenylhydrazine to methyl isopropyl ketone is 1: 0.98-1.02.
In a preferred embodiment of the invention, in the step (2), the molar ratio of the 2,3, 3-trimethyl-3H-indole to the bromoethanol is 1: 1.2-1.5; the molar ratio of the 2,3, 3-trimethyl-3H-indole to the 3-bromopropionic acid is 1: 1-1.2.
In a preferred embodiment of the present invention, in the step (3), the molar ratio of 1- (3-hydroxyethyl) 2,3, 3-trimethyl-3H-indole bromide to 5-nitro salicylaldehyde is 1:1 to 1.5.
Has the advantages that: the spiropyran synthesized by the method is used as a ligand of the light conversion agent, and the photo-induced isomerization principle of the spiropyran is utilized to reduce the photo-aging phenomenon of the light conversion agent and improve the weather resistance.
Drawings
FIG. 1 is a skeletal structure of a spiropyran of the prior art;
FIG. 2 is a synthetic pathway of a prior art spiropyran;
FIG. 3 is a synthetic pathway for spiropyrans according to the invention;
FIG. 4 is a nuclear magnetic spectrum of the spiropyran prepared in example 1;
FIG. 5 is a mass spectrum of the spiropyran prepared in example 1;
FIG. 6 is a mass spectrum of the spiropyran prepared in example 2.
Detailed Description
Example 1: synthesis of N-hydroxyethyl-3, 3-dimethyl-6-nitroindoline spiropyran (hydroxy spiropyran)
(1) Synthesis of 2,3, 3-trimethyl-3H-indole (1)
A500 mL round-bottom flask was charged with phenylhydrazine 10.8g (100mmol), methyl isopropyl ketone 8.8g (102mmol) and 240mL of a mixed solvent of acetic acid-ethanol-water (4:1:1), heated at 106 ℃ under reflux for 3.5 hours, and the end of the reaction was monitored by TLC. After the reaction is finished, the reaction solution is cooled to room temperature, saturated NaOH aqueous solution is used for adjusting the reaction solution to be alkalescent, then ethyl acetate is used for extracting twice, the extraction solutions are combined, and the fraction with the temperature of 116 ℃ and 120 ℃ is collected by reduced pressure distillation, so that 9.10g of light yellow oily liquid is obtained, and the yield is 57%.1HNMR(400MHz,CDCl3,δ)7.54(d,1H,ArH),7.29(m,2H,ArH),7.20(dd,1H,ArH),2.28(s,3H,CH3),1.29(d,6H,CH3)。
(2) Synthesis of 1- (3-hydroxyethyl) 2,3, 3-trimethyl-3H-indolium bromide (2)
A250 mL round bottom flask was charged with 6mL (37.38mmol) of intermediate (1), 3.5mL (49.38mmol) of 2-bromoethanol and 50mL (957mmol) of acetonitrile, N2Refluxing is carried out for 48h at 80 ℃ under protection, and the end point of the reaction is monitored by TLC. After the reaction, the reaction mixture was cooled to room temperature, and diethyl ether was added to precipitate the product, which was then filtered off with suction to obtain 7.54g of a crude product with a yield of 71%. The reaction mixture was used in the next reaction without further purification.1HNMR(400MHz,CDCl3,δ)7.92(ddd,2H,ArH),7.63(m,2H,ArH),4.61(t,2H,CH2),3.89(t,2H,CH2),2.84(s,3H,CH3),1.56(s,6H,CH3)。
(3) Synthesis of hydroxy spiropyrans (4)
A250 mL round bottom flask was charged with 7.54g (603mmol) of the crude product obtained in step (2) as a solid, 5.6g (33.5mmol) of 5-nitrosalicylaldehyde and 50mL (856mmol) of ethanol, heated at 80 ℃ under reflux for 3h, and monitored by TLC for the end of the reaction. After the reaction is finished, the mixture is continuously stirred for 12 hours at room temperature, then is filtered, and filter cakes are washed three times by ethanol to obtain 3.54g of purple solid with the yield of 30 percent.1HNMR(400MHz,D6MSO,δ)8.20(s,1H,OH),7.99(d,1H,ArH),7.14(m,3H,ArH),6.81(m,3H,ArH),6.01(d,1H,CH),4.70(t,1H,CH),4.32(t.1H,CH),3.17(m,3H,CH3),1.11(m,6H,CH3)。
Example 2: synthesis of N-carboxyethyl-3, 3-dimethyl-6-nitroindoline spiropyran (carboxyspiropyran)
(1) Synthesis of 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indolium bromide (3)
4.445g (28mmol) of intermediate (1),4.305g (28mmol) of 3-bromopropionic acid and 40mL (mmol) of chloroform were added to a 100mL round-bottomed flask, the reaction was refluxed at 65 ℃ for 20 hours, and the reaction end point was monitored by TLC. After the reaction was completed, it was cooled to room temperature, and extracted with water to obtain a red viscous substance, which was used in the next reaction without further purification, and 7.885g of a crude product was obtained in a yield of 90.12%.
(2) Synthesis of carboxyspiropyrans (5)
A250 mL round bottom flask was charged with 3.12g (10mmol) of intermediate (4), 2.51g (15mmol) of 5-nitrosalicylaldehyde, a few milliliters of triethylamine and 50mL (856mmol) of ethanol, heated at 80 ℃ to reflux for 20h, and the end of the reaction was monitored by TLC. Column chromatography purification was used to obtain 1.68g of pale yellow oily liquid with a yield of 44.2%.1HNMR(400MHz,D6MSO,δ)8.20(s,1H,OH),7.99(d,1H,ArH),7.14(m,3H,ArH),6.81(m,3H,ArH),6.01(d,1H,CH),4.70(t,1H,CH),4.32(t.1H,CH),3.17(m,3H,CH3),1.11(m,6H,CH3)。
Claims (8)
1. A method for preparing a spiropyran compound for light conversion agents, comprising the steps of:
(1) heating and refluxing phenylhydrazine and methyl isopropyl ketone in a mixed solvent of ethanol, acetic acid and water for 3-4H to synthesize 2,3, 3-trimethyl-3H-indole;
(2) synthesizing 1- (3-hydroxyethyl) 2,3, 3-trimethyl-3H-indole bromide or 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide by reacting the 2,3, 3-trimethyl-3H-indole synthesized in the step (1) with bromoethanol or 3-bromopropionic acid in an organic solvent;
(3) and (3) synthesizing hydroxy spiropyran from the 1- (3-hydroxyethyl) 2,3, 3-trimethyl-3H-indole bromide obtained in the step (2) and 5-nitro salicylaldehyde or synthesizing carboxy spiropyran from the 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide and 5-nitro salicylaldehyde.
2. The method for producing a spiropyran compound for light-converting agents according to claim 1, wherein in the step (1), said reaction solvent is a mixed solvent of acetic acid, ethanol and water in a volume ratio of 4:1: 1.
3. The method as claimed in claim 1, wherein the 2,3, 3-trimethyl-3H-indole is extracted with ethyl acetate 2-3 times in step (1), the combined extracts are vacuum distilled to collect the fraction at 120 ℃ 116-.
4. The method for producing a spiropyran compound for light-converting agents according to claim 1, wherein, in the step (2), said reaction solvent is acetonitrile or chloroform.
5. The method for preparing a spiropyran compound for light converting agents according to claim 1, wherein in the step (3), the reaction condition is heating reflux at 75-85 ℃ for 3-20 hours.
6. A process for preparing a spiropyran compound for light conversion agents according to claim 1, wherein in step (1), said molar ratio of phenylhydrazine to methyl isopropyl ketone is 1: 0.98-1.02.
7. The method for preparing a spiropyran compound for light conversion agent according to claim 1, wherein in the step (2), the molar ratio of 2,3, 3-trimethyl-3H-indole to bromoethanol is 1: 1.2-1.5; the molar ratio of the 2,3, 3-trimethyl-3H-indole to the 3-bromopropionic acid is 1: 1-1.2.
8. The method for producing a spiropyran compound for a light conversion agent according to claim 1, wherein in the step (3), the molar ratio of 1- (3-hydroxyethyl) 2,3, 3-trimethyl-3H-indolium bromide to 5-nitrosalicylaldehyde is 1:1 to 1.5.
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| CN108424482A (en) * | 2018-02-27 | 2018-08-21 | 同济大学 | A kind of dendritic of multiple response and preparation method thereof containing spiro-pyrans |
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