Light conversion agent containing carbazole D-pi-A conjugated system for traditional Chinese medicine planting as well as synthesis method and application of light conversion agent

Abstract

The invention relates to a light conversion agent containing a carbazole D-pi-A conjugated system for traditional Chinese medicine planting as well as a synthesis method and application of the light conversion agent. The structure of the light conversion agent or pharmaceutically acceptable salts, tautomers, racemes, hydrates and solvates of the light conversion agent is shown as a formula (I): # imgabs0 #, and each A is independently selected from N or CR4; r1, R2 and R4 are respectively and independently selected from hydrogen,-F,-Cl,-Br,-I,-CN,-CHO,-B (OH) 2, hydroxyl,-COOH, alkyl-COOH,-SO3H, alkyl-SO3H, alkyl-C (= O)-, aryl-C (= O)-, amino, nitryl, alkoxy, alkylthio, cycloalkyl, heterocyclic radical, aryl, heteroaryl or alkyl; n and m are selected from 0, 1, 2, 3, 4 or 5; r is H, an alkyl group, an alkyl group-COOH, an alkyl group-COO alkyl group, an alkyl-SO3H, a cycloalkyl group, a heterocyclic group, an aryl group or a heteroaryl group. The light conversion agent prepared by the invention can reduce the cost of an organic light conversion material, improve the light conversion efficiency in the production and application process, and increase the content of effective components in large-scale traditional Chinese medicine planting products.

Description

Technical Field

[0001] The invention relates to the technical field of agricultural fluorescent light conversion materials, and specifically provides a light conversion agent containing a carbazole D-π-A conjugated system for traditional Chinese medicine planting, as well as a synthesis method and application thereof. Background Art

[0002] As a key component of modern agriculture, agricultural films were initially valued for their fundamental thermal and moisture-retaining properties, significantly improving agricultural production efficiency. Traditional agricultural films have played a positive role in improving crop yield and quality by regulating soil temperature, retaining moisture, and suppressing weeds, creating a favorable microenvironment for plant growth. However, despite initial success, these traditional films and more advanced alternatives still have significant limitations, urgently requiring further innovation.

[0003] With the development of functional modification technologies, spectral conversion materials, such as rare earth light-conversion films, can increase crop yields by 5% to 10% by converting ultraviolet light into red and blue wavelengths. However, the rapidly growing demand for rare earth elements in other sectors, coupled with the complex and costly extraction and processing of rare earth elements, has resulted in high costs for rare earth light-conversion films, hindering their widespread adoption in agricultural production.

[0004] In recent years, breakthroughs have been made in the field of organic optoelectronic materials. Organic small molecule optoelectronic materials hold great promise for developing next-generation agricultural films with customized functionality, particularly for photoconversion. This is primarily due to the inherent advantages of organic materials, such as biocompatibility, mechanical flexibility, and solution processability. Compared to inorganic materials, organic materials offer diverse structures and easily tunable properties. The successful application of organic optoelectronic materials in fields such as organic solar cells and organic light-emitting diodes has also opened up new possibilities in agriculture. For example, by designing organic materials that absorb specific wavelengths of light and convert them into red or near-infrared light, which is more readily absorbed by plants, it is possible to improve photosynthetic efficiency, thereby increasing crop yield and quality. Furthermore, the printability of organic materials makes it possible to produce agricultural films on a low-cost, large-scale basis. The application of organic light-conversion films, in particular, in the cultivation of traditional Chinese medicine plants, shows great potential. By precisely controlling light quality, it is possible to optimize the spectral requirements of different medicinal plants, for example, to increase the content of specific medicinal components. Furthermore, some studies have shown that irradiation with UV light of specific wavelengths can even increase the content of medicinal components in certain plants.

[0005] Different Chinese medicinal plants have significantly different light requirements, necessitating the design of tailored light-conversion materials. The application of organic light-conversion films in Chinese medicinal plant cultivation also faces several challenges. Furthermore, cost remains a key factor hindering large-scale application. Therefore, the development of low-cost, high-efficiency organic light-conversion materials and film preparation technologies is needed to meet production needs. Summary of the Invention

[0006] The purpose of the present invention is to provide a light conversion agent containing a carbazole D-π-A conjugated system for traditional Chinese medicine planting, as well as a synthesis method and application thereof, in order to reduce the cost of organic photoconversion materials, improve the light conversion efficiency of the production and application process, and increase the content of active ingredients in large-scale traditional Chinese medicine planting products during the application process.

[0007] To achieve the above object, the technical solution of the present invention is as follows:

[0008] In a first aspect, the present invention provides a light conversion agent containing a carbazole D-π-A conjugated system for use in traditional Chinese medicine planting, or a pharmaceutically acceptable salt, tautomer, racemate, hydrate, or solvate thereof, wherein the formula is shown in formula (I):

[0009]

[0010] wherein each A is independently selected from N or CR 4 ;

[0011] R 1 、R 2 and R 4 each independently selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxy, -COOH, alkyl-COOH, -SO3H, alkyl-SO3H, alkyl-C(=O)-, aryl-C(=O)-, amino, nitro, alkoxy, alkylthio, cycloalkyl, heterocyclyl, aryl, heteroaryl or alkyl;

[0012] n is selected from 0, 1, 2, 3, 4 or 5; m is selected from 0, 1, 2, 3, 4 or 5;

[0013] R is H, alkyl, alkyl-COOH, alkyl-COOalkyl, alkyl-SO3H, cycloalkyl, heterocyclyl, aryl or heteroaryl;

[0014] R 1 、R 2 、R 4 The alkoxy, alkylthio, alkyl, alkyl-COOH, alkyl-SO3H, cycloalkyl, cycloalkyl, heterocyclyl, aryl and heteroaryl groups in R are further optionally substituted independently by the same or different substituents R 3 Single or multiple substitutions; the substituent R 3It is hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxy, -COOH, alkyl-COOH, -SO3H, alkyl-SO3H, alkyl-C(=O)-, amide, alkyl-COOalkyl, haloalkyl, aryl-C(=O)-, amino, nitro, alkoxy, alkylthio, cycloalkyl, heterocyclyl, aryl, heteroaryl or alkyl.

[0015] Furthermore, the R 1 、R 2 、R 3 and R 4 Each independently selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxyl, -COOH, C 1-6 Alkyl-COOH, -SO3H, C 1-6 Alkyl-SO3H, C 1-6 Alkyl-C(=O)-, -CON(R 5 )2. -C 1-6 Alkyl-COOC 1-6 Alkyl, C 1-6 Halogenated alkyl, C 6-12 Aryl-C(=O)-, amino, nitro, C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkyl, C 2-6 Heterocyclic group, C 6-12 Aryl, C 1-6 Heteroaryl or C 1-6 alkyl.

[0016] Furthermore, R 5 Selected from hydrogen, or C 1-6 alkyl.

[0017] Furthermore, R 5 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, etc.

[0018] Furthermore, the R 1 、R 2 、R 3 and R 4 Each independently selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxyl, -COOH, C 1-4 Alkyl-COOH, -SO3H, -CON(R 5 )2, amino, nitro, -C 1-4 Alkyl-COOC 1-4 Alkyl, C 1-4Haloalkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclobutyl, cyclopropyl, cyclohexyl, cyclopentyl, phenyl, etc.

[0019] Furthermore, R is H, C 1-12 Alkyl, C 1-12 Alkyl-COOH, -C 1-12 Alkyl-COOC 1-12 Alkyl, C 1-12 Alkyl-SO3H, C 3-6 Cycloalkyl, C 2-6 Heterocyclic group, C 6-12 Aryl or C 1-6 The heteroaryl group may be further substituted or polysubstituted by the same or different substituents described in the present invention.

[0020] Furthermore, R is H, C 1-12 Alkyl, C 1-6 Alkyl-COOH, -C 1-6 Alkyl-COOC 1-6 Alkyl, C 1-12 Alkyl-SO3H, C 3-6 Cycloalkyl, C 2-6 Heterocyclic group, C 6-12 Aryl or C 1-6 The heteroaryl group may be further substituted or polysubstituted by the same or different substituents described in the present invention.

[0021] Furthermore, R is H, C 1-12 Alkyl, C 1-4 Alkyl-COOH, -C 1-4 Alkyl-COOC 1-4 Alkyl, C 1-4 Alkyl-SO3H, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, dioxolanyl, dioxanyl, dithianyl, piperazinyl, pyrrolidine, dihydropyranyl, oxathiolanyl, dithiolane, oxathiophenyl, thiomorpholino, oxiranyl, aziridinyl, oxetanyl, oxepanyl, azetidinyl, tetrahydrofuranyl, tetrahydrothiopyranyl, phenyl, naphthyl, pyrrolyl, pyridinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, or thiazolyl may be further substituted or polysubstituted by the same or different substituents described herein.

[0022] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0023]

[0024] R 1 、R2 , R has the meaning as described in the present invention.

[0025] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0026]

[0027] R 1 、R 2 , R has the meaning as described in the present invention.

[0028] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0029]

[0030] Each R 1 , each R 2 , R, n and m have the meanings as defined in the present invention.

[0031] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0032]

[0033] Each R 1 , each R 2 , R, n and m have the meanings as defined in the present invention.

[0034] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0035]

[0036] q is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.

[0037] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0038] q is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.

[0039] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0040]

[0041] R 3 has the meaning as described in the present invention.

[0042] In some embodiments, R 3 The position on the benzene ring can be ortho, meta, or para, with the para position being preferred.

[0043] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0044]

[0045] R 3 has the meaning as described in the present invention.

[0046] In some embodiments, R 3 The position on the benzene ring can be ortho, meta, or para, with the para position being preferred.

[0047] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0048]

[0049] X is selected from O, S, NR 5 or CHR 4 ; R 3 has the meaning as described in the present invention.

[0050] In some embodiments, R 3 The position on the heteroaromatic ring can be 3-, 4-, or 5-, with the 5-position being preferred.

[0051] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0052]

[0053] X is selected from O, S, NR 5 or CHR 4 ; R 5 、R 4 、R 3 has the meaning as described in the present invention.

[0054] In some embodiments, R 3 The position on the heteroaromatic ring can be 3-, 4-, or 5-, with the 5-position being preferred.

[0055] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0056]

[0057] Each R 1 , R, each A, and each n have the meanings as described in the present invention.

[0058] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0059]

[0060] Each R 1 , R, and each n have the meanings as described in the present invention.

[0061] Furthermore, the structure of the light conversion agent containing the carbazole D-π-A conjugated system for Chinese medicinal planting as shown in formula (I) of the present invention is:

[0062]

[0063] Each R 1 , R, and each n have the meanings as described in the present invention.

[0064] Further, q is each independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11;

[0065] Each X is independently selected from O, S, NR 5 or CHR 4 ;

[0066] Each R 1 , each R 2 、R 3 、R 4 、R 5 , R, A, n and m have the meanings as defined in the present invention.

[0067] Furthermore, the light conversion agent containing a carbazole D-π-A conjugated system for Chinese medicinal planting of the present invention is selected from one of the following structures:

[0068]

[0069] In a second aspect, the present invention provides a method for preparing a light conversion agent containing a carbazole D-π-A conjugated system for use in traditional Chinese medicine planting, the specific steps of which are as follows:

[0070]

[0071] S1: The compound of formula (A) and the compound of formula (B) are reacted in the presence of a first alkaline reagent and a first catalyst to produce a compound of formula (C);

[0072] S2: reacting the compound of formula (C) with HBF4 in the presence or absence of the compound of formula (D) to produce the compound of formula (E);

[0073] Wherein, Y and Q are each independently a leaving group, preferably -Cl, -Br, -I, -B(OH)2, hydroxyl, -COOH, -NH2, ester group, -SO3H, etc.; each R 1 , R, each A and each n have the meanings as described in the present invention.

[0074] Furthermore, in S2, when R is H, the compound of formula D does not exist; the compound of formula (C) reacts with HBF4 to produce the compound of formula (E).

[0075] Furthermore, in S2, when R is not H, the compound of formula D exists; the compound of formula (C) reacts with HBF4 in the presence of the compound of formula (D) to obtain the compound of formula (E).

[0076] Furthermore, in the method, S2 may include the following steps:

[0077]

[0078] The compound of formula (C) reacts with the compound of formula (H) to produce the compound of formula (J), which is further reacted with HBF4 in the presence of the compound of formula (D) to produce the compound of formula (E);

[0079] wherein Q has the definition as described in the present invention;

[0080] R 6 is selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxy, -COOH, alkyl-COOH, -SO3H, alkyl-SO3H, alkyl-C(=O)-, aryl-C(=O)-, amino, nitro, alkoxy, alkylthio, cycloalkyl, heterocyclyl, aryl, heteroaryl or alkyl;

[0081] x is selected from 0, 1, 2, 3, 4 or 5.

[0082] Furthermore, R 6 Selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxyl, -COOH, C 1-6 Alkyl-COOH, -SO3H, C 1-6 Alkyl-SO3H, C 1-6 Alkyl-C(=O)-, -CONH2, -C 1-6Alkyl-COOC 1-6 Alkyl, C 1-6 Halogenated alkyl, C 6-12 Aryl-C(=O)-, amino, nitro, C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkyl, C 2-6 Heterocyclic group, C 6-12 Aryl, C 1-6 Heteroaryl or C 1-6 Alkyl; each R 5 are independently selected from hydrogen, or C 1-6 alkyl.

[0083] Furthermore, R 6 Selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxyl, -COOH, C 1-4 Alkyl-COOH, -SO3H, -CONH2, amino, nitro, -C 1-4 Alkyl-COOC 1-4 Alkyl, C 1-4 Haloalkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclobutyl, cyclopropyl, cyclohexyl, cyclopentyl, phenyl.

[0084] Furthermore, the first alkaline agent includes one or more of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal phosphates, alkali metal carbonates, alkaline earth metal carbonates and organic amines.

[0085] Furthermore, the first alkaline reagent is preferably one or more of cesium carbonate, potassium carbonate, sodium hydride, sodium amide, butyl lithium, potassium tert-butoxide, lithium tert-butoxide, lithium diisopropylamide, sodium acetate, potassium acetate, sodium bicarbonate, potassium bicarbonate, diethylamine, ethylenediamine, potassium phosphate, sodium carbonate, sodium phosphate, potassium hydroxide, sodium hydroxide, lithium hydroxide, triethylamine and N,N-diisopropylethylamine.

[0086] Furthermore, the first catalyst includes at least one of a palladium catalyst, a ruthenium catalyst, a platinum catalyst, an Fe catalyst, and a Cu catalyst.

[0087] Furthermore, the palladium catalyst is selected from at least one of palladium carbon, Pd(PPh3)4, PdCl2(dppf), Pd(OAc)2, a combination of triphenylphosphine and Pd(OAc)2, Pd(dba)2 and Pd2(dba)3.

[0088] Furthermore, in the combination of triphenylphosphine and Pd(OAc)2, the molar ratio of the two is 4:1.

[0089] Furthermore, the compound of formula (A) is prepared by the following method:

[0090]

[0091] S1A: The compound of formula (F) and the compound of formula (G) are reacted with a second alkaline reagent and a second catalyst to produce a compound of formula (A);

[0092] Wherein, Y has the meaning as defined in the present invention.

[0093] Furthermore, the second alkaline agent includes one or more of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal phosphates, alkali metal carbonates, alkaline earth metal carbonates and organic amines.

[0094] Furthermore, the second alkaline reagent includes one or more of cesium carbonate, potassium carbonate, sodium hydride, sodium amide, butyl lithium, potassium tert-butoxide, lithium tert-butoxide, lithium diisopropylamide, sodium acetate, potassium acetate, sodium bicarbonate, potassium bicarbonate, diethylamine, ethylenediamine, potassium phosphate, sodium carbonate, sodium phosphate, potassium hydroxide, sodium hydroxide, lithium hydroxide, triethylamine and N,N-diisopropylethylamine.

[0095] Furthermore, the second catalyst includes at least one of a palladium catalyst, a ruthenium catalyst, a platinum catalyst, an Fe catalyst, and a Cu catalyst.

[0096] Furthermore, the palladium catalyst is selected from at least one of palladium carbon, Pd(PPh3)4, PdCl2(dppf), Pd(OAc)2, a combination of triphenylphosphine and Pd(OAc)2, Pd(dba)2 and Pd2(dba)3.

[0097] Furthermore, in the combination of triphenylphosphine and Pd(OAc)2, the molar ratio of the two is 4:1.

[0098] In a third aspect, the present invention provides a light-conversion material, a light-conversion base film, or an organic light-conversion material comprising the light-conversion agent containing a carbazole D-π-A conjugated system for use in traditional Chinese medicine cultivation. For example, such a light-conversion material, a light-conversion base film, or an organic light-conversion material may comprise any of the light-conversion agents containing a carbazole D-π-A conjugated system for use in traditional Chinese medicine cultivation of the present invention and a pharmaceutically acceptable carrier and / or excipient.

[0099] In a fourth aspect, the present invention provides a use of a light-converting agent or light-converting material or light-converting base film containing a carbazole D-π-A conjugated system for use in planting traditional Chinese medicine according to the present invention in the preparation of an organic light-converting film.

[0100] Furthermore, the organic light-conversion film is used for the cultivation of traditional Chinese medicine.

[0101] The term "alkyl" refers to a saturated, linear or branched, monovalent hydrocarbon radical containing 1 to 20 carbon atoms, wherein the alkyl radical may be optionally substituted with one or more substituents described herein. Unless otherwise specified, an alkyl radical contains 1-20 carbon atoms. In one embodiment, the alkyl radical contains 1-12 carbon atoms; in another embodiment, the alkyl radical contains 1-6 carbon atoms; in yet another embodiment, the alkyl radical contains 1-4 carbon atoms. Examples of alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, and sec-butyl. When alkyl is a linking group and "alkyl" is listed for the Markush group definition, "alkyl" refers to the linking alkylene radical. The term "alkylene" refers to a saturated, divalent hydrocarbon radical derived by removing two hydrogen atoms from a saturated, linear or branched hydrocarbon radical. Examples of alkylene radicals include, but are not limited to, -CH2-, -CH2CH2-, -CH(CH3)CH2-, and the like. The "alkyl" in "alkyl-COOH", "alkyl-COOalkyl", "alkyl-SO3H" and the like mentioned herein has the definition as described in the present invention, and the same applies to other groups.

[0102] As used herein, "alkoxy," "alkylthio," and "heteroalkyl" refer to groups in which some of the carbon atoms in an alkyl group are replaced by different heteroatoms (e.g., O, N, S, Si, or P), wherein the alkyl moiety has the meaning described herein. The heteroalkyl moiety may include four optionally different heteroatoms (e.g., O, N, S, Si, or P), such as alkoxy, alkylamino, and the like. Examples of alkoxy moieties include, but are not limited to, methoxy, ethoxy, isopropoxy, and the like.

[0103] The term "haloalkyl" refers to an alkyl group substituted with F, Cl, Br or I, wherein the alkyl portion has the meaning as defined herein, for example, -CH2Cl, -CF3, -CH2CF3, -CH2CCl3, etc.

[0104] The terms "heterocycle" or "heterocyclyl" are used interchangeably and refer to a monovalent, non-aromatic, saturated or partially unsaturated monocyclic, bicyclic or polycyclic ring system of 3 to 12 ring atoms, containing at least one carbon atom and one, two or three heteroatoms selected from O, N and S, including monoheterocyclyl, bridged heterocyclyl, paraheterocyclyl and spiroheterocyclyl. Unless otherwise specified, the heterocyclyl group may be a carbon group or a nitrogen group, and the -CH2- group may be optionally replaced by -C(=O)-. The sulfur atom of the ring may be optionally oxidized to an S-oxide, and the nitrogen atom of the ring may be optionally oxidized to an N-oxide. The heterocycle may be monocyclic or bicyclic; in particular, the bicyclic ring system may be a paraheterobicyclic, spiroheterobicyclic or bridged heterobicyclic. In some embodiments, the heterocyclyl group contains 4-7 ring atoms, that is, it represents a 4-7 membered heterocyclyl group; examples of heterocycloalkyl groups include, but are not limited to, 1-(1,2,5,6-tetrahydropyridinyl), 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, 1-piperazinyl, 2-piperazinyl, etc. Examples of heterocyclic groups include dihydrofuranyl, dioxolanyl, dioxanyl, dithianyl, piperazinyl, pyrrolidine, dihydropyranyl, oxathiolanyl, dithiolane, oxathiophenyl, thiomorpholino, oxiranyl, aziridinyl, oxetanyl, oxepanyl, azetidinyl, tetrahydrofuranyl, tetrahydrothiopyranyl, pyrrolidinyl, tetrahydropyranyl, piperidinyl, morpholinyl, piperazinyl, azepanyl, oxepanyl, oxazepanyl, oxepanyl, thiepanyl, azepanyl, dioxepanyl, and diazepanyl. "Cycloalkylene" and "heterocycloalkylene" alone or as part of another substituent refer to a divalent radical derived from cycloalkyl and heterocycloalkyl, respectively.

[0105] Aryl groups can be monocyclic, fused to form bicyclic or tricyclic groups, or linked by bonds to form biaryls. Representative aryl groups include phenyl, naphthyl, and biphenyl. Other aryl groups include benzyl with a methylene linker. The term "arylene" refers to a divalent aryl group, wherein aryl has the definition as described herein.

[0106] Heteroaryl groups may include groups such as pyrrole, pyridine, imidazole, pyrazole, thiazole, triazole, tetrazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4- and 1,3,5-isomers), benzopyrroles such as indole and isoindole, benzopyridines such as quinoline and isoquinoline, benzopyrazines (quinoxalines), benzopyrimidines (quinazolines), etc. The term "heteroarylene" refers to a divalent heteroaryl group, wherein heteroaryl has the definition as described herein.

[0107] Cycloalkyl refers to a monovalent or polyvalent monocyclic, bicyclic or tricyclic ring system containing carbon atoms (e.g., monocyclic, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or bicyclic, including spirocyclic, fused or bridged systems (such as bicyclo[1.1.1]pentyl, bicyclo[2.2.1]heptyl, bicyclo[3.2.1]octyl or bicyclo[5.2.0]nonyl, decalinyl, etc.), which may be fully saturated or contain one or more degrees of unsaturation, but may not have an aromatic ring. In one embodiment, the cycloalkyl group contains 3-6 carbon atoms, such as C 3-6 Saturated or partially unsaturated cycloalkyl. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, and the like. In one embodiment, the saturated or partially unsaturated cycloalkyl is selected from the group consisting of: saturated monocyclic cycloalkyl, saturated bicyclic cycloalkyl, saturated tricyclic cycloalkyl, partially unsaturated monocyclic cycloalkyl, partially unsaturated bicyclic cycloalkyl, and partially unsaturated tricyclic cycloalkyl. 4-7 Cycloalkyl refers to a cycloalkyl group having 4 to 7 ring atoms. 3-6 Cycloalkyl refers to a cycloalkyl group having 3 to 6 ring atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, and the like. The term "cycloalkylene" refers to a divalent saturated monocyclic carbon ring system. The -CH2- group in the cycloalkylene group may optionally be replaced by -C(=O)-. In some embodiments, the cycloalkylene group contains 3 to 7 ring carbon atoms, i.e., C 3-7 In one embodiment, the cycloalkylene group contains 3 to 6 carbon atoms, i.e., C 3-6 In another embodiment, the cycloalkyl group contains 3-5 carbon atoms, i.e., C 3-5 Examples of cycloalkylene include, but are not limited to, 1,1-cyclopropylene, 1,2-cyclopropylene, 1,1-cyclopentylene, 1,1-cyclohexylene, 1,3-cyclopentylene, etc. The cycloalkylene group may be independently optionally substituted with one or more substituents described herein.

[0108] In the present invention, the values ​​of A in the same structural formula may be the same or different and do not affect each other. For example In this article The positions of the bonds can be combined at any reasonable position on the ring, which can be expressed as Etc.; and so on.

[0109] The elements referred to in the structures of the present invention are elements including all isotopes thereof, and exemplary isotopes in the compounds of the present invention include isotopes of hydrogen (H), carbon (C), nitrogen (N), oxygen (O), phosphorus (P), sulfur (S), fluorine (F), chlorine (Cl) and bromine (Br), such as2 H, 3 H, 13 C, 14 C, 15 N, 16 O, 17 O, 31 P, 32 P, 36 S, 18 F, 37 Cl, Br 81 That is, hydrogen (H) includes 1 H. 2 H. 3 H; Carbon (C) includes 12 C. 13 C. 14 C; Nitrogen (N) includes 14 N. 15 N; oxygen (O) includes 16 O. 17 O; Phosphorus (P) includes 30 P. 31 P. 32 P; sulfur (S) includes 32 S. 33 S. 34 S. 36 S; Fluorine (F) includes 18 F. 17 F; Chlorine (Cl) includes 35 Cl, 37 Cl; bromine (Br) including Br 79 Br 81 .

[0110] The term "isotopically labeled compound" means a compound of the present invention that is labeled with an isotope. It is identical to those compounds described herein except that one or more atoms are replaced by an atom having an atomic mass or mass number different from the atomic mass or mass number usually found in nature. Exemplary isotopes that may also be incorporated into the compounds of the present invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, and chlorine, such as 2 H, 3 H, 13 C, 14 C, 15 N, 16 O, 17 O, 31 P, 32 P, 36 S, 18 F and 37 Cl.

[0111] Compounds of the present invention containing the aforementioned isotopic labels and / or other isotopic labels of other atoms and pharmaceutically acceptable salts of the compounds are all within the scope of the present invention. Isotope-labeled compounds of the present invention, such as radioisotope-labeled compounds, such as 3 H and 14 C is incorporated into the compounds of the present invention for drug and / or substrate tissue distribution analysis. Due to ease of preparation and detection, tritiated, i.e., 3 H, and carbon-14, i.e. 14 C, isotopes are particularly preferred. In addition, isotopes with larger mass numbers, such as deuterium, 2 H substitutions may offer therapeutic advantages of greater metabolic stability, such as increased in vivo half-life or reduced dosage requirements, and therefore may be preferred in some circumstances.

[0112] In the present invention, similar terms such as "jk pieces", "jk yuan" or "C j -C k "The j and k in it are each independently any non-zero natural number, and k>j; for example, "1-4" means 1, 2, 3 or 4, "4-6 yuan" means 4 yuan, 5 yuan or 6 yuan; "C3-C6" means C3, C4, C5 or C6. And so on.

[0113] The terms "optional", "optional" or "optionally" mean that the subsequently described event or circumstance may but need not occur. The term "and / or" should be understood to mean any one of the optional items or a combination of any two or more of the optional items.

[0114] In addition, it should be noted that, unless otherwise explicitly stated, the descriptions used throughout this document, “each ... and ... are independently,” “... and ... are each independently,” and “... and ... are respectively independently,” are interchangeable and should be understood in a broad sense. They may mean that in different groups, the specific options expressed by the same symbols do not affect each other, or that in the same group, the specific options expressed by the same symbols do not affect each other.

[0115] The beneficial effects of the present invention are as follows:

[0116] Compared to existing technologies, the light conversion agent containing a carbazole D-π-A conjugated system for use in traditional Chinese medicine cultivation provided by this invention exhibits excellent photoconversion performance and, through the use of a regulatory group, can achieve beneficial conversion of various wavelengths. Furthermore, this light conversion agent is an organic small molecule compound with low synthesis cost and a high degree of functional customization, making it suitable for large-scale commercial application in a variety of traditional Chinese medicinal plants and promising market prospects.

[0117] The present invention adopts a carbazole ring as an electron donor unit and a 4-nitrilephenyl group as a symmetrical electron acceptor unit. In addition, by introducing a pyridinium salt with a strong electron-pulling effect as an additional electron acceptor unit, the electron transfer efficiency is enhanced, the performance of the light converter is regulated to absorb and adapt to light waves of different wavelengths (such as ultraviolet, green, red, and blue light), and the photoluminescence wavelength of the light converter (such as red, blue, and infrared light) can be adjusted to meet the light wave requirements of different Chinese medicinal materials. DETAILED DESCRIPTION

[0118] The present invention will be further described below with reference to specific examples. These examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0119] Preparation Example 1: A preparation process of the compound of the present invention is as follows:

[0120]

[0121] S1A: The compound of formula (F) and the compound of formula (G) are reacted with a second alkaline reagent and a second catalyst to produce a compound of formula (A);

[0122] S1: The compound of formula (A) and the compound of formula (B) are reacted in the presence of a first alkaline reagent and a first catalyst to produce a compound of formula (C);

[0123] S2: reacting the compound of formula (C) with HBF4 in the presence or absence of the compound of formula (D) to produce the compound of formula (E);

[0124] Wherein, Y and Q are each independently a leaving group, and the leaving group is preferably -Cl, -Br, -I, -B(OH)2, hydroxyl, -COOH, -NH2, ester, -SO3H, etc.; each R 1 , R, each A and each n have the meanings as described in the present invention.

[0125] Preparation Example 2: A preparation process of the compound of the present invention is as follows:

[0126]

[0127]

[0128] S1A: The compound of formula (F) and the compound of formula (G) are reacted with a second alkaline reagent and a second catalyst to produce a compound of formula (A);

[0129] S1: The compound of formula (A) and the compound of formula (B) are reacted in the presence of a first alkaline reagent and a first catalyst to produce a compound of formula (C);

[0130] S2: The compound of formula (C) reacts with the compound of formula (H) to produce the compound of formula (J), which is further reacted with HBF4 in the presence of the compound of formula (D) to produce the compound of formula (E);

[0131] Wherein Q is a leaving group, and the leaving group is preferably -Cl, -Br, -I, -B(OH)2, hydroxyl, -COOH, -NH2, ester, -SO3H, etc.;

[0132] R 6 is selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxy, -COOH, alkyl-COOH, -SO3H, alkyl-SO3H, alkyl-C(=O)-, aryl-C(=O)-, amino, nitro, alkoxy, alkylthio, cycloalkyl, heterocyclyl, aryl, heteroaryl or alkyl;

[0133] x is selected from 0, 1, 2, 3, 4 or 5; each R 1 , R, each A and each n have the meanings as described in the present invention.

[0134] Sources of reagents: The reagents and APIs used in the present invention are commercially available.

[0135] Example 1

[0136] The preparation includes the following steps:

[0137]

[0138] In the first step, 2,7-dibromocarbazole (6.50 g, 20.0 mmol), 4-iodopyridine (6.15 g, 30.0 mmol), potassium tert-butoxide (3.37 g, 30.0 mmol), triphenylphosphine (1.05 g, 4.00 mmol), and palladium acetate (0.23 g, 1.00 mmol) were mixed with 50 mL of toluene. The reaction system was purged with nitrogen to remove all air from the reaction flask. The system was heated to 120°C and refluxed under nitrogen for 24 hours. After the reaction was completed, the temperature was cooled to room temperature and 50 mL of water was added to the reaction flask. The mixture was extracted three times with 50 mL of ethyl acetate. The organic phases were combined and concentrated to obtain a crude product. The crude product was separated and purified by silica gel column chromatography using a mixture of petroleum ether and ethyl acetate (volume ratio of 95:5 to 10:1, preferably 50:1) as the eluent to obtain a pale yellow solid, compound 3 (5.63 g, 70% yield).

[0139] 1H NMR (500MHz, Chloroform-d) δ8.58-8.52(m,2H),8.10(d,J=1.5Hz,2H),7.91(d,J=7.4Hz,2H),7.47(dd,J=7.5,1.5Hz,2H),7.42-7.37(m,2H).

[0140]

[0141] In the second step, all the pure compound 3 (5.63 g, 14.00 mmol) obtained in the first step, 4-cyanophenylboronic acid (6.17 g, 42.01 mmol), potassium carbonate (5.81 g, 42.01 mmol), and tetrakis(triphenylphosphine)palladium (1.62 g, 1.40 mmol) were mixed with 40 mL of tetrahydrofuran and 10 mL of water. The reaction system was purged with nitrogen to remove all air from the reaction flask. The system was heated to 60 degrees Celsius and refluxed under a nitrogen atmosphere for 24 hours. After the reaction was completed, the temperature was lowered and 50 mL of water was added to the reaction flask. The mixture was extracted three times with 50 mL of ethyl acetate. The organic phases were combined and concentrated to obtain a crude product. The crude product was separated and purified by silica gel column chromatography using a mixture of petroleum ether and ethyl acetate (volume ratio of 100:1 to 10:1, preferably 50:1) as the eluent to obtain compound 5 (4.13 g, 66% yield) as an off-white solid.

[0142] 1 H NMR(500MHz,Chloroform-d)δ8.60-8.55(m,2H),8.01(d,J=7.5Hz,2H),7.81(dd,J= 7.1,1.5Hz,2H),7.77-7.70(m,8H),7.67(dd,J=7.5,1.5Hz,2H),7.51-7.45(m,2H).

[0143]

[0144] In the third step, the entirety of the pure compound 5 (4.13 g, 9.25 mmol) obtained in the second step and a tetrafluoroboric acid aqueous solution (48 wt%, 3.61 g, 18.5 mmol) were mixed with 40 mL of ethanol. The reaction system was nitrogen-purged to remove all air from the reaction flask. The system was then heated to 80°C and refluxed under a nitrogen atmosphere for 24 hours. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. The crude product was then slurried with 20 mL of 95% ethanol at room temperature for 8 hours and filtered to yield pure compound 17 (2.87 g, 58%).

[0145] 1H NMR(500MHz,Chloroform-d)δ8.19(ddt,J=8.8,7.9,1.9Hz,2H),8.05(d,J=7.5Hz,2H),7.88-7. 82(m,6H),7.76-7.70(m,4H),7.59(dd,J=7.5,1.6Hz,2H),7.52-7.46(m,2H),6.60-6.53(m,1H).

[0146] Example 2

[0147] The preparation includes the following steps:

[0148]

[0149] In the first step, 3,6-dibromocarbazole (6.50 g, 20.0 mmol), 4-iodopyridine (6.15 g, 30.0 mmol), potassium tert-butoxide (3.37 g, 30.0 mmol), triphenylphosphine (1.05 g, 4.00 mmol), and palladium acetate (0.23 g, 1.00 mmol) were mixed with 60 mL of toluene. The reaction system was purged with nitrogen to remove all air from the reaction flask. The system was heated to 120 degrees Celsius and refluxed for 24 hours under a nitrogen atmosphere. After the reaction was completed, the temperature was lowered and 50 mL of water was added to the reaction flask. The mixture was extracted three times with 50 mL of ethyl acetate. The organic phases were combined and concentrated to obtain a crude product. The crude product was separated and purified by silica gel column chromatography using a mixture of petroleum ether and ethyl acetate (volume ratio of 95:5 to 10:1, preferably 50:1) as the eluent to obtain a pale yellow solid compound 8 (5.83 g, yield 72.8%).

[0150] 1H NMR (500MHz, Chloroform-d) δ8.58-8.52(m,2H),8.22-8.17(m,2H),7.61(d,J=7.5Hz,2H),7.46(dd,J=7.5,1.6Hz,2H),7.44-7.39(m,2H).

[0151]

[0152] In the second step, all the pure compound 8 (5.63 g, 14.00 mmol) obtained in the first step, 4-cyanophenylboronic acid (48 wt%, 6.17 g, 42.01 mmol), potassium carbonate (5.81 g, 42.01 mmol), and tetrakistriphenylphosphine palladium (1.62 g, 1.40 mmol) were mixed with 60 mL of tetrahydrofuran and 15 mL of water. The reaction system was purged with nitrogen to completely expel the air from the reaction flask. The system was heated to 60 degrees Celsius and refluxed under a nitrogen atmosphere for 24 hours. After the reaction was completed, the temperature was lowered and 50 mL of water was added to the reaction flask. The mixture was extracted three times with 50 mL of ethyl acetate. The organic phases were combined and concentrated to obtain a crude product. The crude product was separated and purified by silica gel column chromatography using a mixture of petroleum ether and ethyl acetate (volume ratio of 100:1 to 10:1, preferably 50:1) as the eluent to obtain compound 10 (4.32 g, 66% yield) as an off-white solid.

[0153] 1 H NMR(500MHz,Chloroform-d)δ8.59-8.54(m,2H),8.30(d,J=1.6Hz,2H),7.79-7. 70(m,8H),7.67(dd,J=7.6,1.5Hz,2H),7.62(d,J=7.5Hz,2H),7.47-7.41(m,2H).

[0154]

[0155] In the third step, the entirety of pure Compound 10 (4.32 g, 9.67 mmol) obtained in the second step was mixed with a tetrafluoroboric acid aqueous solution (48 wt%, 3.54 g, 19.35 mmol), and ethyl bromoacetate (2.42 g, 14.5 mmol) in 50 mL of ethanol. The reaction system was nitrogen-purged to remove all air from the reaction flask. The system was then heated to 80°C and refluxed for 24 hours under a nitrogen atmosphere. After the reaction was complete, the mixture was cooled to room temperature and the solvent removed under reduced pressure. The crude product was then slurried with 15 mL of 95% ethanol at room temperature for 8 hours and filtered to yield pure Compound 11 (3.24 g, 54%).

[0156] 1 H NMR(500MHz,Chloroform-d)δ9.23-9.16(m,2H),8.28(d,J=1.8Hz,2H),7.89-7.83(m,4H),7.82-7.74 (m,4H),7.67-7.60(m,4H),7.52-7.45(m,2H),5.88(s,2H),4.28(q,J=8.0Hz,2H),1.33-1.17(m,3H).

[0157] Example 3

[0158]

[0159] Compound 5 (4.13 g, 9.25 mmol), tetrafluoroboric acid aqueous solution (48 wt%, 3.38 g, 18.5 mmol), and iodomethane (2.63 g, 18.5 mmol) were mixed with 30 mL of ethanol. The reaction system was purged with nitrogen to remove all air from the reaction flask. The system was heated to 80°C and refluxed under nitrogen for 24 hours. After the reaction was completed, the reaction was cooled to room temperature and the solvent was removed under reduced pressure. The crude product was then slurried with 10 mL of 95% ethanol at room temperature for 8 hours and filtered to obtain pure compound 12 (2.54 g, 50%).

[0160] 1 H NMR(500MHz,Chloroform-d)δ8.88-8.80(m,2H),8.03(d,J=7.6Hz,2H),7.87-7.81(m,4H),7.77(dd,J=4.1,1.5H z,2H),7.75-7.71(m,4H),7.69(d,J=1.5Hz,1H),7.67(d,J=1.5Hz,1H),7.41-7.34(m,2H),4.39(d,J=0.9Hz,3H).

[0161] Example 4

[0162]

[0163] Compound 5 (4.13 g, 9.25 mmol), tetrafluoroboric acid aqueous solution (48 wt%, 4.23 g, 23.12 mmol), phenylboric acid (1.69 g, 13.87 mmol), copper acetate (0.17 g, 0.93 mmol), and ferric nitrate (0.22 g, 0.93 mmol) were mixed with 30 mL of N,N-dimethylformamide. The reaction system was heated to 80°C in an air atmosphere for 10 hours. After the reaction was completed, the mixture was cooled to room temperature and the N,N-dimethylformamide solvent was removed under reduced pressure. The crude product was then slurried with 15 mL of 95% ethanol at room temperature for 8 hours and filtered to obtain pure compound 13 (4.12 g, 73%).

[0164] 1H NMR(500MHz,Chloroform-d)δ9.01-8.96(m,2H),8.04(d,J=7.6Hz,2H),7.90(d,J=1.4Hz,1H),7.88-7.84(m, 5H),7.80-7.75(m,4H),7.71(dq,J=7.9,1.7Hz,2H),7.67-7.62(m,2H),7.62-7.56(m,3H),7.43-7.37(m,2H).

[0165] Example 5

[0166]

[0167] Compound 10 (4.32 g, 9.67 mmol) and 1-chloro-2,4-dinitrobenzene (2.06 g, 10.16 mmol) were mixed with 30 mL of acetone. The reaction system was purged with nitrogen to remove all air from the reaction flask. The system was heated and refluxed under a nitrogen atmosphere for 24 hours. After the reaction was complete, the reaction was cooled to room temperature and the solvent was removed under reduced pressure to obtain the crude product, which was used directly in the next reaction.

[0168] The crude product, p-trifluoromethylaniline (3.10 g, 19.26 mmol), and aqueous tetrafluoroboric acid (6.34 g, 34.68 mmol) were mixed with 20 mL of ethanol and 20 mL of water. The reaction system was purged with nitrogen to remove all air from the reaction flask. The system was sealed under a nitrogen atmosphere and microwave-heated at 130°C for 20 minutes. After the reaction, the mixture was cooled to room temperature and concentrated to remove the solvent. The crude product was then slurried with 15 mL of 95% ethanol at room temperature for 8 hours and filtered to obtain pure compound 15 (2.29 g, 38% total yield over two steps).

[0169] 1 H NMR(500MHz,Chloroform-d)δ9.05-8.99(m,2H),8.30-8.24(m,2H),7.88-7.83(m ,4H),7.82-7.80(m,2H),7.79-7.74(m,4H),7.66-7.61(m,6H),7.60-7.56(m,2H).

[0170] Example 6

[0171]

[0172] Compound 5 (4.13 g, 9.25 mmol) and 1-chloro-2,4-dinitrobenzene (2.81 g, 13.87 mmol) were mixed with 50 mL of acetone. The reaction system was purged with nitrogen to remove all air from the reaction flask. The system was heated and refluxed under nitrogen for 24 hours. After the reaction was complete, the reaction was cooled to room temperature and the solvent was removed under reduced pressure to obtain the crude product, which was used directly in the next reaction.

[0173] The crude product, ethyl 5-aminothiophene-2-carboxylate (3.17 g, 18.49 mmol), and aqueous tetrafluoroboric acid (3.38 g, 18.49 mmol) were mixed with 40 mL of ethanol and 40 mL of water. The reaction system was purged with nitrogen to remove all air from the reaction flask. The system was sealed under a nitrogen atmosphere and microwave-heated at 130°C for 20 minutes. After the reaction, the mixture was cooled to room temperature and concentrated to remove the solvent. The crude product was then slurried with 10 mL of 95% ethanol at room temperature for 8 hours and filtered to obtain pure compound 16 (1.91 g, 30% total yield over two steps).

[0174] 1 H NMR(500MHz,Chloroform-d)δ8.63-8.59(m,2H),8.18(d,J=7.5Hz,1H),8.04(d,J=7.5Hz,2H),7.89(dd,J=16.9,1.6Hz,2H) ,7.86-7.83(m,4H),7.80-7.76(m,4H),7.68(d,J=7.5Hz,1H),7.65-7.61(m,2H),7.59(dd,J=7.5,1.5Hz,2H),3.88(s,3H).

[0175] Preparation Example 1 of Organic Film:

[0176] The light conversion agent prepared in the embodiment of the present invention is mixed with a polymer material (such as at least one of PVC and PVDF, PVDF is selected in this embodiment) at a mass ratio of 3:99. After high-speed stirring and melt extrusion, it is extruded through an annular die into a tubular film blank, and then inflated with compressed air and cooled to form a final organic film with a thickness of 100 μm. The corresponding numbers of the organic films are shown in Table 1 below:

[0177]

[0178] Effect Example 1 Optical Performance Test

[0179] The prepared organic films I-II were tested to determine their characteristic spectra. The absorption and transmission spectra of the organic films were analyzed using an ultraviolet spectrophotometer. The test wavelength range was 200-800 nm. The excitation and emission spectra of the organic films were measured, and the results are shown in Table 2 below:

[0180] Organic film number Organic Film I Organic Film II Emission wavelength 458nm 503nm Absorption wavelength 390nm 378nm

[0181] Test results: The organic film prepared by adding the light conversion agent of the present invention mainly absorbs light with a wavelength of 365nm to 410nm.

[0182] Effect Example 2 Chinese medicine planting test

[0183] The organic film prepared by the present invention was applied to the cultivation of Guangxi Curcuma zedoaria in the open air and the conventional organic film without adding the light conversion agent of the present invention was used as a control. The organic film was dug out two years after planting. The average value of the test data is shown in Table 3 below.

[0184] (1) According to the relevant operating standards of the alcohol-soluble extract determination method in the Chinese Pharmacopoeia, the extract of Guangxi Curcuma was extracted by cold soaking method. Specifically, the medicinal material was soaked in ethanol for 24 hours to dissolve the components, and then the extract was evaporated to dryness. The residue was weighed to obtain the mass and percentage of the extract.

[0185] (2) Mix zedoary turmeric and water in a weight ratio of 1:10, reflux and extract for 30 h, and collect zedoary turmeric oil.

[0186] (3) The contents of curcumol, germacrone, and curdion in zedoary turmeric oil were determined by gas chromatography (GC). An HP-5 quartz elastic capillary column was used, with an injection port temperature of 250°C, a detector temperature of 280°C, an injection volume of 4 μL, and a temperature program of 200°C.

[0187] Table 3 Average results of the test data of each component of Curcuma zedoaria

[0188]

[0189] The results showed that compared with open-air cultivation of Guangxi Curcuma zedoaria and conventional organic films, the light conversion agent prepared in the embodiment of the present invention was made into organic film I and organic film II and applied to the cultivation of Guangxi Curcuma zedoaria, which achieved better yield and accumulation of medicinal ingredients. Using organic membrane I in the cultivation of Guangxi zedoary turmeric, the diameter of the turmeric turmeric in Guangxi increased from 28.42 mm to 52.73 mm (an increase of 85.5%), the weight of the turmeric turmeric increased from 18.40 g to 50.40 g (an increase of 173.9%), and the extract content increased from 9% to 20.20%. The content of zedoary turmeric oil and key components in zedoary turmeric oil also increased significantly: zedoary turmeric oil increased from 3.20 ml / g to 8.1 ml / g (an increase of 153.1%); germacronone (9.80% → 17.92%, an increase of 82.9%), curcumol (11.05% → 29.32%, an increase of 165.3%), and curdione (19.32% → 32.58%, an increase of 68.6%). Conclusion: The organic film prepared by using the light conversion agent of the present invention can significantly improve the accumulation of medicinal ingredients by regulating the secondary metabolic pathways of Curcuma zedoaria (such as terpenoid synthase activity).

[0190] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A light conversion agent containing a carbazole D-π-A conjugated system for use in traditional Chinese medicine planting, or a pharmaceutically acceptable salt, tautomer, racemate, hydrate, or solvate thereof, wherein the structure is shown in formula (I): in, Each A is independently selected from N or CR 4 ; R 1 、R 2 and R 4 each independently selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxy, -COOH, alkyl-COOH, -SO3H, alkyl-SO3H, alkyl-C(=O)-, amido, alkyl-COOalkyl, haloalkyl, aryl-C(=O)-, amino, nitro, alkoxy, alkylthio, cycloalkyl, heterocyclyl, aryl, heteroaryl or alkyl; n is selected from 0, 1, 2, 3, 4 or 5; m is selected from 0, 1, 2, 3, 4 or 5; R is H, alkyl, alkyl-COOH, alkyl-COOalkyl, alkyl-SO3H, cycloalkyl, heterocyclyl, aryl or heteroaryl; R 1 、R 2 、R 4 The alkoxy, alkylthio, alkyl, alkyl-COOH, alkyl-SO3H, cycloalkyl, cycloalkyl, heterocyclyl, aryl and heteroaryl groups in R are further optionally substituted independently by the same or different substituents R 3 Single or multiple substitutions; the substituent R 3 It is hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxy, -COOH, alkyl-COOH, -SO3H, alkyl-SO3H, alkyl-C(=O)-, amide, alkyl-COOalkyl, haloalkyl, aryl-C(=O)-, amino, nitro, alkoxy, alkylthio, cycloalkyl, heterocyclyl, aryl, heteroaryl or alkyl.

2. The light conversion agent according to claim 1, characterized in that The R 1 、R 2 、R 3 and R 4 Each independently selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxyl, -COOH, C 1-6 Alkyl-COOH, -SO3H, C 1-6 Alkyl-SO3H, C 1-6 Alkyl-C(=O)-, -CON(R 5 )2. -C 1-6 Alkyl-COOC 1-6 Alkyl, C 1-6 Halogenated alkyl, C 6-12 Aryl-C(=O)-, amino, nitro, C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkyl, C 2-6 Heterocyclic group, C 6-12 Aryl, C 1-6 Heteroaryl or C 1-6 Alkyl; each R 5 are independently selected from hydrogen, or C 1-6 alkyl; R is H, C 1-12 Alkyl, C 1-12 Alkyl-COOH, -C 1-12 Alkyl-COOC 1-12 Alkyl, C 1-12 Alkyl-SO3H, C 3-6 Cycloalkyl, C 2-6 Heterocyclic group, C 6-12 Aryl or C 1-6 Heteroaryl.

3. The light conversion agent according to any one of claims 1 to 2, characterized in that The R 1 、R 2 、R 3 and R 4 Each independently selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxyl, -COOH, C 1-4 Alkyl-COOH, -SO3H, -CON(R 5 )2, amino, nitro, -C 1-4 Alkyl-COOC 1-4 Alkyl, C 1-4 Haloalkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclobutyl, cyclopropyl, cyclohexyl, cyclopentyl, phenyl; Each R 5 independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl; R is H, C 1-12 Alkyl, C 1-6 Alkyl-COOH, -C 1-6 Alkyl-COOC 1-6 Alkyl, C 1-12 Alkyl-SO3H, C 3-6 Cycloalkyl, C 2-6 Heterocyclic group, C 6-12 Aryl or C 1-6 heteroaryl; More preferably, R is H, C 1-12 Alkyl, C 1-4 Alkyl-COOH, -C 1-4 Alkyl-COOC 1-4 Alkyl, C 1-4 Alkyl-SO3H, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, dioxolanyl, dioxanyl, dithianyl, piperazinyl, pyrrolidine, dihydropyranyl, oxathiolanyl, dithiolane, oxathiolane, thiothienyl, thiomorpholino, oxiranyl, aziridinyl, oxetanyl, oxepanyl, azetidinyl, tetrahydrofuranyl, tetrahydrothiopyranyl, phenyl, naphthyl, pyrrolyl, pyridinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl or thiazolyl.

4. The light conversion agent according to any one of claims 1 to 3, characterized in that It is one of the following structures: wherein q is each independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; Each X is independently selected from O, S, NR 5 or CHR 4 .

5. The light conversion agent according to any one of claims 1 to 4, characterized in that: It is selected from one of the following structures:

6. The method for preparing the light conversion agent according to any one of claims 1 to 5, characterized in that: The specific steps are as follows: S1: The compound of formula (A) and the compound of formula (B) are reacted in the presence of a first alkaline reagent and a first catalyst to produce a compound of formula (C); S2: reacting a compound of formula (C) with HBF4 in the presence or absence of a compound of formula (D) to obtain a compound of formula (E); or, S2: The compound of formula (C) reacts with the compound of formula (H) to produce the compound of formula (J), which is further reacted with HBF4 in the presence of the compound of formula (D) to produce the compound of formula (E); wherein Y and Q are each independently a leaving group, preferably, the leaving group is -Cl, -Br, -I, -B(OH)2, hydroxyl, -COOH, -NH2, ester or -SO3H; R 6 is selected from hydrogen, -F, -Cl, -Br, -I, -CN, -CHO, -B(OH)2, hydroxy, -COOH, alkyl-COOH, -SO3H, alkyl-SO3H, alkyl-C(=O)-, aryl-C(=O)-, amino, nitro, alkoxy, alkylthio, cycloalkyl, heterocyclyl, aryl, heteroaryl or alkyl; x is selected from 0, 1, 2, 3, 4 or 5.

7. The preparation method according to claim 6, characterized in that: The compound of formula (A) is prepared by the following method: S1A: The compound of formula (F) and the compound of formula (G) are reacted with a second alkaline reagent and a second catalyst to prepare the compound of formula (A).

8. The preparation method according to any one of claims 6 to 7, characterized in that: The first alkaline agent and the second alkaline agent are each independently selected from one or more of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal phosphates, alkali metal carbonates, alkaline earth metal carbonates and organic amines; and / or, the first alkaline agent and the second alkaline agent are each independently selected from one or more of cesium carbonate, potassium carbonate, sodium hydride, sodium amide, butyl lithium, potassium tert-butoxide, lithium tert-butoxide, lithium diisopropylamide, sodium acetate, potassium acetate, sodium bicarbonate, potassium bicarbonate, diethylamine, ethylenediamine, potassium phosphate, sodium carbonate, sodium phosphate, potassium hydroxide, sodium hydroxide, lithium hydroxide, triethylamine and N,N-diisopropylethylamine; And / or, the first catalyst and the second catalyst are each independently selected from at least one of a palladium catalyst, a ruthenium catalyst, a platinum catalyst, an Fe catalyst, and a Cu catalyst, And / or, the palladium catalyst is selected from at least one of palladium carbon, Pd(PPh3)4, PdCl2(dppf), Pd(OAc)2, a combination of triphenylphosphine and Pd(OAc)2, Pd(dba)2 and Pd2(dba)3.

9. A light conversion material or light conversion base film or organic light conversion material comprising the light conversion agent containing a carbazole D-π-A conjugated system for use in planting traditional Chinese medicine according to any one of claims 1 to 5.

10. Use of the light conversion agent containing a carbazole D-π-A conjugated system for Chinese medicinal plant cultivation according to any one of claims 1 to 5, or the light conversion material, light conversion base film, or organic light conversion material according to claim 9 in the preparation of an organic light conversion film; Optionally, the organic light-converting film is used for traditional Chinese medicine cultivation.

Images