TWI698499B - Modified curcumin and related preparation method - Google Patents

Abstract

The present invention discloses a modified curcumin and related preparation method. The modified curcumin includes at least a modified curcumin monomer which is formed from a curcumin monomer and an epoxy compound through a chemical reaction, and one end of the structure of the modified curcumin monomer has a C=C double-bond structure.

Description

Modified curcumin and its preparation method

The present invention relates to a technical field of chemical dyes, and more specifically to a modified curcumin and a preparation method thereof.

Curcumin is a chemical component extracted from the rhizomes of some plants in the Zingiberaceae and Araceae family. Turmeric contains about 3% to 6%. It is a rare pigment with diketones in the plant kingdom and is a diketone chemical. . Because curcumin is an orange-yellow crystalline powder with a bit bitter taste and is insoluble in water, it is a natural yellow pigment. Therefore, it is mainly used for coloring products such as sausage products, canned food, and soy sauce products in food production. In addition, because curcumin itself has obvious coloring effect and is not easy to cause color change, it has been widely used as a coloring agent and dye for food or other substances.

However, in the application of traditional curcumin, the monomer of curcumin is directly used to color and dye other substances. After a period of time of storage or washing with other substances, the traditional curcumin will be easily separated from other substances, causing other substances. The coloring and dyeing effect of the substance is reduced, which has a greater impact on the dyeing application of the traditional curcumin.

An object of the present invention is to provide a modified curcumin and a preparation method thereof, wherein the modified curcumin monomer in the modified curcumin has a carbon-carbon double bond structure at the end of the structure for improving the Improve the binding stability between curcumin and other substances.

Another object of the present invention is to provide a modified curcumin and a preparation method thereof, which can improve the application effect of the modified curcumin, so as to expand the application field of the modified curcumin.

Another object of the present invention is to provide a modified curcumin and a preparation method thereof, wherein the modified curcumin is prepared by a chemical reaction between a curcumin and an epoxy compound with a carbon-carbon double bond, so that The modified curcumin monomer in the modified curcumin has a one-carbon-carbon double bond structure at the structural end.

Another object of the present invention is to provide a modified curcumin and a preparation method thereof, wherein the modified curcumin can be stably combined with other substances containing carbon-carbon double bonds.

Another object of the present invention is to provide a modified curcumin and a preparation method thereof, wherein in the process of preparing the modified curcumin, the properties of the original curcumin monomer in the modified curcumin are not affected, To ensure the dyeing effect of the modified curcumin monomer.

Another object of the present invention is to provide a modified curcumin and a preparation method thereof, wherein in the process of preparing the modified curcumin, the reactivity of the carbon-carbon double bond on an epoxy compound needs to be preserved in advance to prevent The carbon-carbon double bond structure on the epoxy compound is destroyed; at the same time, the reaction efficiency and stability of the reaction between a curcumin and an epoxy compound can also be improved.

Another object of the present invention is to provide a modified curcumin and a preparation method thereof, wherein in the process of preparing the modified curcumin, a catalyst is added to increase the reaction between a curcumin and an epoxy compound rate.

Another object of the present invention is to provide a modified curcumin and a preparation method thereof, wherein in the process of preparing the modified curcumin, a reaction temperature range is maintained so that a curcumin monomer and an epoxy compound are The reaction is carried out within the reaction temperature range to increase the reaction rate.

In order to achieve at least one object of the invention or other objects and advantages, the present invention provides a modified curcumin comprising at least one modified curcumin monomer, wherein the modified curcumin is composed of a curcumin and a carbon-carbon double The epoxy compound of the bond is made through a chemical reaction, and the modified curcumin mono The structure end of the body has a carbon-carbon double bond structure.

其中：R1為

或

； R2為-OH或

； R3為氫基或甲基；R4為氫基或甲氧基；R5為氫基或甲氧基。 In some embodiments of the present invention, the modified curcumin monomer has the following general structural formula:

Among them: R1 is

or

; R2 is -OH or

; R3 is hydrogen or methyl; R4 is hydrogen or methoxy; R5 is hydrogen or methoxy.

In some embodiments of the present invention, the structural formula of the modified curcumin monomer is selected from:

In some embodiments of the present invention, the epoxy compound having a carbon-carbon double bond is selected from Glycidyl monomethacrylate, glycidyl monoacrylate, glycidyl monocrotonate, methyl glycidyl itaconate, glycidyl monomaleate, glycidyl fumarate, itaconate One or more of glycidyl acid esters and other equivalent compounds with the same technical characteristics.

In some embodiments of the present invention, the modified curcumin is used for coloring or dyeing.

其中：R1為

或

； R2為-OH或

； R3為氫基或甲基； R4為氫基或甲氧基； R5為氫基或甲氧基。 According to another aspect of the present invention, the present invention further provides a method for preparing modified curcumin, which is characterized by comprising the following steps: (i) preparing a curcumin solution with a ring-opening compound, wherein the curcumin solution Comprising a curcumin monomer and the ring-opening compound; (ii) preparing an epoxy compound solution, wherein the epoxy compound solution includes an epoxy compound having a carbon-carbon double bond; and (iii) adding the The epoxy compound solution is in the curcumin solution, so that a chemical reaction occurs between the epoxy compound and the curcumin monomer to generate a modified curcumin monomer, thereby making the modified curcumin, wherein The modified curcumin monomer has the following general structural formula:

Among them: R1 is

or

; R2 is -OH or

; R3 is a hydrogen group or a methyl group; R4 is a hydrogen group or a methoxy group; R5 is a hydrogen group or a methoxy group.

In some embodiments of the present invention, the step (iii) further includes the step: A catalyst is added to the curcumin solution, wherein the catalyst is selected from 4-dimethylaminopyridine, triethylenetetramine, triphenylphosphine, 1,8-diazabicyclo[5.4.0]undec- One or more of 7-ene and other compounds with similar amine structure.

In some embodiments of the present invention, in the step (i), a curcumin and the ring-opening compound are dissolved in a solvent to prepare the curcumin solution with the ring-opening compound, wherein the solvent is selected From one or more of anhydrous tetrahydrofuran, anhydrous dimethylformamide, anhydrous tert-butyl methyl ether, anhydrous acetone, anhydrous ethanol or other anhydrous organic solvents.

In some embodiments of the present invention, in the step (ii), the epoxy compound is dissolved in the solvent to prepare the epoxy compound solution.

In some embodiments of the present invention, the epoxy compound is selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, glycidyl crotonic acid, methyl glycidyl itaconate, and glycidyl methacrylate. One or more of glycidyl acid, glycidyl fumarate, glycidyl itaconic acid and other equivalent compounds with the same technical characteristics.

In some embodiments of the present invention, the ring-opening compound is monodimethylsulfene.

In some embodiments of the present invention, the step (iii) further includes the step of dropping the epoxy compound solution into the curcumin solution so that the epoxy compound and the curcumin monomer fully react.

In some embodiments of the present invention, the step (iii) further includes the step of maintaining the reaction temperature between the epoxy compound and the curcumin monomer at 20 to 120°C.

In some embodiments of the present invention, the step (iii) further includes the step of maintaining the reaction temperature between the epoxy compound and the curcumin monomer at 50-80°C.

In some embodiments of the present invention, the preparation method of the modified curcumin further includes the steps of: preparing an inhibitory solution, wherein the inhibitory solution includes a free radical polymerization inhibitor; and The inhibitor solution is added to the epoxy compound solution to pre-store the reactivity of the carbon-carbon double bond on the epoxy compound through the radical polymerization inhibitor.

In some embodiments of the present invention, the radical polymerization inhibitor is selected from hydroquinone monomethyl ether, 1,4-benzoquinone, 1,1-diphenyl-2-picrylhydrazine radical, One or more of nitrobenzene or other equivalent compounds with the same technical characteristics.

Through the understanding of the following description and the drawings, the further objectives and advantages of the present invention will be fully embodied.

These and other objectives, features, and advantages of the present invention are fully embodied by the following detailed description, drawings and claims.

A~D: Step

a, b, c, d, e, f, ga, gb, gc, i, j, k, m, n, o: position

Fig. 1 is a schematic flow diagram of a method for preparing modified curcumin according to a preferred embodiment of the present invention.

Fig. 2 and Fig. 3 are respectively an analysis schematic diagram of a 1H-NMR spectrum and a mass spectrometer spectrum of one of the modified curcumin obtained according to the above preferred embodiment of the present invention.

The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments in the following description are only examples, and those skilled in the art can think of other obvious variations. The basic principles of the present invention defined in the following description can be applied to other embodiments, modifications, improvements, equivalents, and other technical solutions that do not depart from the spirit and scope of the present invention.

Those skilled in the art should understand that in the disclosure of the present invention, the terms " longitudinal " , " horizontal " , " upper " , " lower " , " front " , " rear " , " left " , " right " and " vertical, "" standard, "" top "," bottom "," inner ", orientation or positional relationship of" outside "position or the like is indicated by figures based on the positional relationship shown, it is only for convenience of description of the present invention and The description is simplified, rather than indicating or implying that the pointed device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore the above terms should not be construed as limiting the present invention.

In the present invention, the scope of the patent application and the term "one" in the specification should be understood as "one "Or multiple", that is, in one embodiment, the number of an element may be one, and in another embodiment, the number of the element may be multiple. Unless the disclosure of the present invention clearly indicates that the number of the element is only One, otherwise the term "a" cannot be understood as unique or singular, and the term "a" cannot be understood as a limitation on quantity. It can be further understood that the terms "including" and/or "including" used in this specification indicate what is meant The presence of features, wholes, steps, operations, elements, and/or components does not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, and/or other components.

Curcumin is a natural yellow color. Because of its obvious coloring effect and not easy to cause color change, it has been widely used as a coloring agent and dye for food or other substances. However, in the application of traditional curcumin, the curcumin monomer can be directly used to color and dye other substances, but after a period of time of storage or washing with other substances, the curcumin monomer will easily be removed from other substances. The detachment from the top will cause the coloring and dyeing effect of other substances to decrease. Those skilled in the art should understand that there are usually three curcumin monomers in the traditional curcumin, and the curcumin monomer is a compound having the following structural formulas (1) to (3):

Among them, in structural formula (1) and structural formula (2), Me is a methyl group, that is, OMe is a methoxy group.

It is worth noting that the compounds of the above structural formulas (1)~(3) (ie curcumin monomers) will exist in the traditional curcumin at the same time, and the difference lies in the proportion of their existence: structural formula ( 1) Curcumin monomer accounts for about 70%~80%; structural formula (2) curcumin monomer accounts for about 10%-20%; structural formula (3) curcumin monomer accounts for about 10% .

It is worth mentioning that the curcumin monomer has the following general structural formula (4):

Wherein: in the general formula (4), R4 is a hydrogen group or a methoxy group; R5 is a hydrogen group or a methoxy group.

In the field of polymerization, it is known to use monomers with two or more different carbon-carbon double bonds for polymerization reactions, which have good performance in bonding stability. Therefore, in order to improve the application effect of curcumin, the present invention provides a modified curcumin, so that the modified curcumin monomer in the modified curcumin has a carbon-carbon double bond structure at the end of the structure to improve the modified curcumin. The binding stability between curcumin monomer and other substances, which enables curcumin to be used in various related fields that require dyeing.

In the present invention, the modified curcumin monomer is generated by a chemical reaction between the curcumin monomer and an epoxy compound having a carbon-carbon double bond, so that the modified curcumin monomer The end of the structure has a carbon-carbon double bond structure, so that the modified curcumin can be stably combined with other substances containing carbon-carbon double bonds to prevent the modified curcumin from being detached due to long-term use or washing, Furthermore, the coloring and dyeing effects of the modified curcumin are enhanced.

Those skilled in the art should understand that: since the structural end of the modified curcumin monomer has a carbon-carbon double bond structure, the carbon-carbon double bond is an unsaturated chemical bond in the chemical field and can be combined with other carbon-carbon double bonds or A polymerization reaction occurs between other unsaturated chemical bonds to form a more stable chemical bond (ie covalent bond), so that the force between the modified curcumin monomer and other substances with a carbon-carbon double bond structure is covalent Valence bond strength; however, since the structural end of the curcumin monomer itself does not have a carbon-carbon double bond structure, the curcumin monomer cannot polymerize with other substances with a carbon-carbon double bond structure, so the curcumin monomer The body can only bind to other substances through van der Waals forces, but the covalent bond force between molecules is much greater than the van der Waals force between molecules, so the modified curcumin can be more stably bound to other substances containing carbon-carbon double bonds. Prevent the modified curcumin from falling off.

其中：R1為

(簡稱I基)或

(簡稱II基)； R2為-OH或

(簡稱III基)，其中R1為I基或II基，R3為氫基或甲基； R3為氫基或甲基；R4為氫基或甲氧基；R5為氫基或甲氧基。 Specifically, the modified curcumin monomer has the following structural formula (5), that is, the general structural formula of the modified curcumin monomer (that is, the chemical formula of the modified curcumin monomer):

Among them: R1 is

(Abbreviated as I base) or

(Abbreviated as group II); R2 is -OH or

(Group III for short), wherein R1 is a group I or group II, R3 is a hydrogen group or a methyl group; R3 is a hydrogen group or a methyl group; R4 is a hydrogen group or a methoxy group; R5 is a hydrogen group or a methoxy group.

More specifically, the modified curcumin monomer can be combined with the curcumin monomer and the carbon The epoxy compound with carbon double bond is reacted to be generated. The epoxy compound with carbon-carbon double bond can be, but not limited to, be implemented as glycidyl methacrylate (GMA), or can be It is implemented as other compounds having a carbon-carbon double bond structure and epoxy segments, such as glycidyl acrylate, glycidyl crotonate, methyl glycidyl itaconate ), glycidyl maleate, glycidyl fumarate, glycidyl itaconate or other equivalent compounds with the same technical characteristics.

其中：R1為

或

； R2為-OH或

； R3為氫基或甲基；R4為氫基或甲氧基；R5為氫基或甲氧基。 For example, taking the glycidyl methacrylate as the epoxy compound as an example, the chemical reaction formula for generating the modified curcumin monomer is as follows:

Among them: R1 is

or

; R2 is -OH or

; R3 is hydrogen or methyl; R4 is hydrogen or methoxy; R5 is hydrogen or methoxy.

It is worth noting that according to the above chemical reaction formula (6), a compound with the following structural formula (all of the modified curcumin monomers) can be generated: Compound J1: In the above structural formula (5), R1 It is the I group, R2 is -OH, R3 is methyl, R4 is methoxy, R5 is methoxy, then the structural formula 1-1 of the compound J1 is as follows:

Compound J2: In the above general formula (5), R1 is the I group, R2 is -OH, R3 is the methyl group, R4 is the hydrogen group, R5 is the methoxy group, then the structure of the compound J2 is 1-2 as follows:

Compound J3: In the above general formula (5), R1 is the I group, R2 is -OH, R3 is the methyl group, R4 is the methoxy group, and R5 is the hydrogen group, then the structure of the compound J3 is 1-3 as follows:

Compound J4: In the above general formula (5), R1 is the I group, R2 is -OH, R3 is the methyl group, R4 is the hydrogen group, R5 is the hydrogen group, then the structure 1-4 of the compound J4 is as follows :

Compound J5: In the above general formula (5), R1 is group II, R2 is -OH, R3 is methyl, R4 is methoxy, R5 is methoxy, then the structure of compound J5 is 1- 5 as follows:

Compound J6: In the above general formula (5), R1 is group II, R2 is -OH, R3 is methyl, R4 is hydrogen, R5 is methoxy, then the structure of compound J6 is 1-6 as follows:

Compound J7: In the above general formula (5), R1 is group II, R2 is -OH, R3 is methyl, R4 is methoxy, R5 is hydrogen, then the structure of compound J7 is 1-7 as follows:

Compound J8: In the above general formula (5), R1 is the II group, R2 is -OH, R3 is the methyl group, R4 is the hydrogen group, R5 is the hydrogen group, then the structural formula 1-8 of the compound J8 is as follows :

Compound J9: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group I, R3 is methyl), R3 is methyl, R4 is methoxy, R5 If it is a methoxy group, the structural formulas 1-9 of the compound J9 are as follows:

Compound J10: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group I, R3 is methyl), R3 is methyl, R4 is hydrogen, and R5 is Methoxy, the structural formulas 1-10 of the compound J10 are as follows:

Compound J11: In the above general formula (5), R1 is group I, R2 is group III (wherein R1 in R2 is group I, R3 is methyl), R3 is methyl, R4 is hydrogen, and R5 is Hydrogen group, the structural formulas 1-11 of the compound J11 are as follows:

Compound J12: In the above general formula (5), R1 is group II, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is methyl, R4 is methoxy, R5 Is a methoxy group, then the structural formulas 1-12 of the compound J12 are as follows:

Compound J13: In the above general formula (5), R1 is group II, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is methyl, R4 is methoxy, R5 Is a hydrogen group, the structure of the compound J13 is as follows:

Compound J14: In the above general formula (5), R1 is group II, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is methyl, R4 is hydrogen, and R5 is Hydrogen group, the structural formulas 1-14 of the compound J14 are as follows:

Compound J15: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is methyl, R4 is methoxy, R5 If it is a methoxy group, the structural formulas 1-15 of the compound J15 are as follows:

Compound J16: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is methyl, R4 is hydrogen, and R5 is Methoxy, the structural formulas 1-16 of the compound J16 are as follows:

Compound J17: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is methyl, R4 is methoxy, R5 If it is a hydrogen group, the structural formula 1-17 of the compound J17 is as follows:

Compound J18: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is methyl, R4 is hydrogen, and R5 is Hydrogen group, the structural formulas 1-18 of the compound J18 are as follows:

Compound J19: In the above general formula (5), R1 is an I group, R2 is -OH, R3 is a hydrogen group, R4 is a methoxy group, and R5 is a methoxy group, then the structure of the compound J19 is 1- 19 is as follows:

Compound J20: In the above general formula (5), R1 is an I group, R2 is -OH, R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a methoxy group, then the structure of the compound J20 is 1-20 as follows:

Compound J21: In the above general formula (5), R1 is the I group, R2 is -OH, R3 is the hydrogen group, R4 is the methoxy group, and R5 is the hydrogen group, then the structure of the compound J21 is 1-21 as follows:

Compound J22: In the above general formula (5), R1 is the I group, R2 is -OH, R3 is the hydrogen group, R4 is the hydrogen group, R5 is the hydrogen group, then the structure 1-22 of the compound J22 is as follows :

Compound J23: In the above general formula (5), R1 is group II, R2 is -OH, R3 is hydrogen group, R4 is methoxy group, R5 is methoxy group, then the structure of compound J23 is 1- 23 is as follows:

Compound J24: In the above general formula (5), R1 is group II, R2 is -OH, R3 is hydrogen group, R4 is hydrogen group, R5 is methoxy group, then the structure of compound J is 1-24 as follows:

Compound J25: In the above general formula (5), R1 is group II, R2 is -OH, R3 is hydrogen group, R4 is methoxy group, R5 is hydrogen group, then the structure of compound J25 is 1-25 as follows:

Compound J26: In the above general formula (5), R1 is group II, R2 is -OH, R3 is hydrogen group, R4 is hydrogen group, R5 is hydrogen group, then the structure of compound J26 is as follows: 1-26 :

Compound J27: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group I, R3 is hydrogen group), R3 is hydrogen group, R4 is methoxy group, R5 If it is a methoxy group, the structural formula 1-27 of the compound J27 is as follows:

Compound J28: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group I, R3 is methyl), R3 is hydrogen group, R4 is methoxy group, R5 If it is a methoxy group, the structural formula 1-28 of the compound J28 is as follows:

Compound J29: In the above general formula (5), R1 is the I group, R2 is the III group (wherein R2 in R1 is the I group, R3 is the hydrogen group), R3 is the hydrogen group, R4 is the hydrogen group, and R5 is the Methoxy, the structural formula 1-29 of the compound J29 is as follows:

Compound J30: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group I and R3 is methyl), R3 is hydrogen group, R4 is hydrogen group, and R5 is Methoxy, the structure of the compound J30 is as follows:

Compound J31: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group I, R3 is methyl), R3 is hydrogen group, R4 is methoxy group, R5 Is a hydrogen group, the structural formula 1-J31 of the compound J31 is as follows:

Compound J32: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group I, R3 is hydrogen group), R3 is hydrogen group, R4 is hydrogen group, and R5 is Hydrogen group, the structural formula 1-J32 of the compound J32 is as follows:

Compound J33: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group I, R3 is methyl), R3 is hydrogen group, R4 is hydrogen group, R5 is Hydrogen group, the structural formula 1-J33 of the compound J33 is as follows:

Compound J34: In the above general formula (5), R1 is group II, R2 is group III (wherein R2 in R1 is group II, R3 is hydrogen group), R3 is hydrogen group, R4 is methoxy group, and R5 Is a methoxy group, the structural formula 1-34 of the compound J34 is as follows:

Compound J35: In the above general formula (5), R1 is group II, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is hydrogen group, R4 is methoxy group, R5 If it is a methoxy group, the structural formula 1-35 of the compound J35 is as follows:

Compound J36: In the above general formula (5), R1 is group II, R2 is group III (wherein R1 in R2 is group II and R3 is hydrogen group), R3 is hydrogen group, R4 is methoxy group, R5 If it is a hydrogen group, the structural formula 1-36 of the compound J36 is as follows:

Compound J37: In the above general formula (5), R1 is group II, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is hydrogen group, R4 is methoxy group, R5 Is a hydrogen group, then the structural formula 1-37 of the compound J37 is as follows:

Compound J38: In the above general formula (5), R1 is group II, R2 is group III (wherein R1 in R2 is group II and R3 is methyl), R3 is hydrogen group, R4 is methoxy group, R5 Is a hydrogen group, then the structural formula 1-38 of the compound J38 is as follows:

Compound J39: In the above general formula (5), R1 is group II, R2 is group III (wherein R2 in R1 is group II, R3 is hydrogen group), R3 is hydrogen group, R4 is hydrogen group, and R5 is Hydrogen group, the structural formula 1-39 of the compound J39 is as follows:

Compound J40: In the above general formula (5), R1 is group II, R2 is group III (wherein R2 in R1 is group II and R3 is methyl), R3 is hydrogen group, R4 is hydrogen group, and R5 is Hydrogen group, the structure of the compound J40 is as follows:

Compound J41: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II and R3 is hydrogen group), R3 is hydrogen group, R4 is methoxy group, R5 Is a methoxy group, then the structural formula 1-41 of the compound J41 is as follows:

Compound J41: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is hydrogen group, R4 is methoxy group, R5 Is a methoxy group, then the structural formula 1-41 of the compound J41 is as follows:

Compound J41: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 is group II and R3 is hydrogen group), R3 is methyl, R4 is methoxy, R5 Is a methoxy group, then the structural formula 1-41 of the compound J41 is as follows:

Compound J42: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II, R3 is hydrogen group), R3 is hydrogen group, R4 is hydrogen group, and R5 is Methoxy, the structural formula 1-42 of the compound J42 is as follows:

Compound J43: In the above general formula (5), R1 is the I group, R2 is the III group (wherein R2 in R1 is the II group, R3 is the methyl group), R3 is the hydrogen group, R4 is the hydrogen group, and R5 is the Methoxy, the structural formula 1-43 of the compound J43 is as follows:

Compound J44: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 is group II, R3 is hydrogen group), R3 is methyl, R4 is hydrogen group, and R5 is Methoxy, the structural formula 1-44 of the compound J44 is as follows:

Compound J45: In the above general formula (5), R1 is group I, R2 is group III (wherein R1 in R2 is group II, R3 is hydrogen group), R3 is hydrogen group, R4 is methoxy group, R5 Is a hydrogen group, the structural formula 1-45 of the compound J45 is as follows:

Compound J46: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II and R3 is methyl), R3 is hydrogen group, R4 is methoxy group, R5 Is a hydrogen group, the structural formula 1-46 of the compound J46 is as follows:

Compound J47: In the above general formula (5), R1 is group I, R2 is group III (wherein R1 in R2 is group II and R3 is hydrogen group), R3 is methyl, R4 is methoxy, R5 If it is a hydrogen group, the structural formula 1-47 of the compound J47 is as follows:

Compound J48: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II, R3 is hydrogen group), R3 is hydrogen group, R4 is hydrogen group, and R5 is Hydrogen group, the structural formula 1-48 of the compound J48 is as follows:

Compound J49: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II, R3 is methyl), R3 is hydrogen group, R4 is hydrogen group, and R5 is Hydrogen group, the structural formula 1-49 of the compound J49 is as follows:

Compound J50: In the above general formula (5), R1 is group I, R2 is group III (wherein R2 in R1 is group II, R3 is hydrogen group), R3 is methyl, R4 is hydrogen group, and R5 is Hydrogen group, the structural formula 1-50 of the compound J50 is as follows:

It is worth noting that, in order not to affect the characteristics of the curcumin monomer itself (such as color characteristics, coloring characteristics, etc.), the reaction planned in the present invention is designed to: make the epoxy compound with carbon-carbon double bond The epoxy segment in the monomer can produce an addition reaction with the -OH on the benzene ring of the curcumin monomer to generate the modified curcumin monomer, so that the structural end of the modified curcumin monomer has Carbon-carbon double bond structure to improve the coloring and dyeing effect of the modified curcumin.

According to another aspect of the present invention, the present invention further provides a preparation method of the modified curcumin. As shown in Fig. 1, the method for preparing the modified curcumin according to a preferred embodiment of the present invention includes the following steps:

(A) Prepare a curcumin solution, wherein the curcumin solution contains a curcumin monomer.

More specifically, a traditional curcumin is dissolved in a solvent to prepare the curcumin solution, so that the curcumin solution contains the curcumin monomer, wherein the curcumin monomer is selected from the group having the structural formula ( 1)~(3) One or more of the curcumin monomer group consisting of, so that the curcumin monomer is dissolved in the solvent, so that the curcumin monomer can more easily chemically react with other substances.

It is worth noting that the solvent can be, but is not limited to, implemented as an anhydrous organic solvent for dissolving curcumin monomers and epoxy compounds with carbon-carbon double bonds. Preferably, the solvent is anhydrous tetrahydrofuran (tetrahydrofuran, THF) to enhance the dissolving effect of the curcumin monomer. It should be understood that the solvent can also be implemented as anhydrous dimethylformamide (DMF), anhydrous tert-butyl methyl ether (tert-butyl methyl ether), anhydrous acetone (acetone), anhydrous ethanol (ethanol) or others. Equivalent compounds with the same technical characteristics as the tetrahydrofuran to achieve the same effect.

(B) Prepare an epoxy compound solution, wherein the epoxy compound solution includes an epoxy compound having a carbon-carbon double bond.

More specifically, the epoxy compound having a carbon-carbon double bond is dissolved in a solvent to prepare the epoxy compound solution, wherein the epoxy compound solution includes the ring having a carbon-carbon double bond The oxy compound makes the epoxy compound easier to react with other substances. It should be understood that the solvent in the step (B) is consistent with the solvent in the step (A), so as to avoid the addition of a new solvent to affect subsequent purification and other processing.

It should be understood that the epoxy compound having a carbon-carbon double bond is a compound having a carbon-carbon double bond structure and an epoxy segment, which includes (but is not limited to) glycidyl methacrylate, glycidyl acrylate, croton Glycidyl acid, methyl glycidyl itaconate, glycidyl maleate, glycidyl fumarate, glycidyl itaconate or other equivalent compounds with the same technical characteristics.

(C) Add a ring-opening compound to the curcumin solution.

More specifically, if the epoxy segment in the epoxy compound having a carbon-carbon double bond structure can react with other monomers, it is necessary to perform a ring-opening reaction on the epoxy compound first, so that the ring The epoxy segment of the oxy compound generates a ring opening phenomenon, so that the epoxy compound can react with the curcumin monomer. Therefore, in the preparation method of the modified curcumin provided by the present invention, the ring-opening compound needs to be added to the curcumin solution, so that when the epoxy compound solution is mixed with the curcumin solution Then, the epoxy compound first undergoes a ring-opening reaction under the action of the ring-opening compound, and then the epoxy compound after the ring-opening reacts with the curcumin monomer. It should be understood that, in some other embodiments of the present invention, the ring-opening compound may also be added to the epoxy compound solution to achieve the same ring-opening effect.

It is worth noting that the ring-opening compound can be, but is not limited to, implemented as dimethyl sulfoxide (DMSO). It should be understood that the ring-opening compound can also be implemented as other equivalent compounds with the same technical characteristics as the dimethyl sulfoxide, so that the epoxy segment of the epoxy compound produces a ring-opening phenomenon.

It is worth noting that the step (C) can be performed simultaneously with the step (A) to The curcumin solution with the ring-opening compound is prepared so that the curcumin monomer and the ring-opening compound are simultaneously present in the curcumin solution.

(D) adding the epoxy compound solution to the curcumin solution to cause a chemical reaction between the epoxy compound and the curcumin monomer to generate the modified curcumin monomer.

More specifically, the epoxy compound solution is slowly added dropwise to the curcumin solution to thoroughly mix the epoxy compound solution and the curcumin solution to form the mixed solution, so that the A chemical reaction occurs between the epoxy compound in the mixed solution and the curcumin monomer to generate the modified curcumin.

It should be understood that the reaction time between the epoxy compound and the curcumin monomer is adjusted and determined according to experimental conditions, and is not limited in the present invention.

Those skilled in the art should understand that the step (A) and the step (B) in the preparation method are in no particular order, that is, the step (A) can be completed in the step (B) It is executed before; or the step (A) can also be executed after the step (B) is completed; or the step (A) and the step (B) are executed simultaneously.

In the preferred embodiment of the present invention, the step (C) of the preparation method further includes the step of adding a catalyst to the curcumin solution.

Specifically, in order to increase the reaction activity of the reactants, a catalyst is further added to the preparation method of the present invention to increase the reaction rate between the curcumin monomer and the epoxy compound.

Preferably, the catalyst is 4-dimethylaminopyridine (DMAP). It should be understood that the catalyst can also be implemented as triethylenetetramine (TETA), triphenylphosphine (TPP), 1,8-diazabicyclo[5.4.0]undec-7 -En (1,8-Diazabicyclo[5.4.0]undec-7-ene, DBU) or other compounds with similar amine structure to achieve the same catalytic effect.

It should be understood that the catalyst and the ring-opening compound can be used in the step (A), It is directly added to prepare the curcumin solution; it can also be added to the curcumin solution separately after the step (A) is completed, which is not limited in the present invention.

Further, the step (D) of the preparation method further includes the step of maintaining the reaction temperature between the epoxy compound and the curcumin monomer within a reaction temperature range, so that the epoxy compound and the curcumin monomer The curcumin monomer reacts within the reaction temperature range.

More specifically, in the preferred embodiment of the present invention, the reaction temperature ranges from 20 to 120°C to maintain the efficiency and stability of the entire reaction, that is, by maintaining the temperature of the mixed solution at Within the reaction temperature range, a curcumin monomer and an epoxy compound are allowed to react within the reaction temperature range to increase the reaction rate and stability. It should be understood that if the temperature of the mixed solution is too high, the epoxy compound with a carbon-carbon double bond structure is easily triggered to undergo a radical polymerization reaction, thereby reducing the production efficiency of the modified curcumin.

Preferably, the reaction temperature ranges from 50 to 100 degrees Celsius.

More preferably, the reaction temperature ranges from 50 to 80 degrees Celsius.

It is worth noting that, in order to prevent the carbon-carbon double bond structure in the epoxy compound from losing activity, that is to say, in order to retain the carbon-carbon double bond structure in the epoxy compound, a radical polymerization reaction is used in the present invention. The inhibitor inhibits the activity of the carbon-carbon double bond structure in the epoxy compound to improve the reaction efficiency and stability of the reaction between the curcumin monomer and the epoxy compound. In other words, in the process of preparing the modified curcumin, it is necessary to use the radical polymerization inhibitor to pre-store the reactivity of the carbon-carbon double bond on an epoxy compound to prevent damage to the epoxy group. The carbon-carbon double bond structure on the compound.

It should be understood that the radical polymerization inhibitors include (but are not limited to) mono-methyl ether hydroquinone (MEHQ), 1,4-benzoquinone (1,4 benzoquinone, BQ), 1, 1-Diphenyl-2-picrylhydrazyl free radical (1,1-Diphenyl-2-picrylhydrazyl Free Radical, DPPH Free Radical), nitrobenzene or other equivalent compounds with the same technical characteristics.

More specifically, the preparation method further includes the steps of: preparing an inhibitory solution, wherein the inhibitory solution includes a radical polymerization inhibitor; and adding the inhibitory solution to the epoxy compound solution to pass the free radical A polymerization inhibitor is used to preserve the reactivity of the carbon-carbon double bond on the epoxy compound in advance.

For the preparation method of the modified curcumin of the preferred embodiment of the present invention, the variables are grouped according to the presence or absence of catalysts, the presence or absence of ring-opening compounds, the selection of the reaction temperature range, and the presence or absence of radical polymerization inhibitors. Experiment, for example:

Experiment 1: Dissolve 2.0 g of curcumin in 20 mL of anhydrous THF solvent (ie, anhydrous tetrahydrofuran solvent) to prepare the curcumin solution, and place the curcumin solution in a reactor for standby; 2.2 g Glycidyl methacrylate (GMA) was dissolved in 20 mL of anhydrous THF solvent to prepare the epoxy compound solution, and the epoxy compound solution was placed in a dropper for later use; The epoxy compound solution in the pipe is slowly dropped into the reactor within 1 hour, and the reaction temperature between the epoxy compound and the curcumin monomer is maintained at 20-50°C, so that the The epoxy compound and the curcumin monomer are reacted at 20-50°C for 48 hours to fully react.

Experiment 2: The preparation process and conditions of experiment 2 were basically the same as those of experiment 1, except that 0.95 g of 4-dimethylaminopyridine was added to the reactor containing the curcumin solution, so that the 4-dimethylaminopyridine Except that the pyridine was dissolved in the curcumin solution, the other steps were the same as the above experiment 1.

Experiment 3: The preparation process and conditions of Experiment 3 were basically the same as Experiment 1 above, except that 0.5 mg of hydroquinone monomethyl ether was dissolved in 1.0 mL of tetrahydrofuran solvent to prepare the inhibitory solution, and then weighed 3.2 Except that g of the inhibitory solution was added to the epoxy compound solution, the other steps were the same as in Experiment 1 above.

Experiment 4: The preparation process and conditions of experiment 4 were basically the same as the above experiment 1, except that 10 mL of the dimethyl sulfide was added to the reactor containing the curcumin solution to make the dimethyl sulfide Except for dissolving in the curcumin solution, the other steps are the same as the above experiment 1.

Experiment 5: The preparation process and conditions of experiment 5 were basically the same as experiment 4 above, except that 0.95 g of the 4-dimethylaminopyridine was added to the reactor containing the curcumin solution to make the 4-dimethylaminopyridine Except that the pyridine is dissolved in the curcumin solution, the other steps are the same as the above experiment 4.

Experiment 6: The preparation process and conditions of experiment 6 were basically the same as experiment 5 above, except that 0.5 mg of hydroquinone monomethyl ether was dissolved in 1.0 mL of tetrahydrofuran solvent to prepare the inhibitory solution, and then weighed 3.2 Except that g of the inhibitory solution was added to the epoxy compound solution, the other steps were the same as in Experiment 5 above.

Experiment 7: The preparation process and conditions of Experiment 7 are basically the same as Experiment 1 above, except that the reaction temperature between the epoxy compound and the curcumin monomer is maintained at 50~80℃, the other steps are the same as Experiment 1 above. the same.

Experiment 8: The preparation process and conditions of Experiment 8 are basically the same as Experiment 2 above, except that the reaction temperature between the epoxy compound and the curcumin monomer is maintained at 50~80℃, the other steps are the same as Experiment 2 above. the same.

Experiment 9: The preparation process and conditions of Experiment 9 are basically the same as Experiment 3 above, except that the reaction temperature between the epoxy compound and the curcumin monomer is maintained at 50~80℃, the other steps are the same as the above experiment 3 is the same.

Experiment 10: The preparation process and conditions of Experiment 10 are basically the same as those of Experiment 4 above, except that the reaction temperature between the epoxy compound and the curcumin monomer is maintained at 50~80℃, the other steps are the same as the above experiment 4 is the same.

Experiment 11: The preparation process and conditions of experiment 11 are basically the same as experiment 5 above, except that the reaction temperature between the epoxy compound and the curcumin monomer is maintained at 50~80℃, the other steps are the same as the above experiment 5 is the same.

Experiment 12: The preparation process and conditions of experiment 12 are basically the same as experiment 6 above, except that the Except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 50-80° C., the other steps were the same as the above experiment 6.

Experiment 13: The preparation process and conditions of Experiment 13 are basically the same as the above experiment 1, except that the reaction temperature between the epoxy compound and the curcumin monomer is maintained at 80~120℃, the other steps are the same as the above experiment 1 is the same.

Experiment 14: The preparation process and conditions of Experiment 14 are basically the same as Experiment 2 above, except that the reaction temperature between the epoxy compound and the curcumin monomer is maintained at 80~120℃, the other steps are the same as the above experiment 2 is the same.

Experiment 15: The preparation process and conditions of Experiment 15 were basically the same as Experiment 3 above, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 80~120℃, the other steps were the same as the above experiment 3 is the same.

Experiment 16: The preparation process and conditions of Experiment 16 are basically the same as Experiment 4 above, except that the reaction temperature between the epoxy compound and the curcumin monomer is maintained at 80~120℃, the other steps are the same as the above experiment 4 is the same.

Experiment 17: The preparation process and conditions of Experiment 17 are basically the same as Experiment 5 above, except that the reaction temperature between the epoxy compound and the curcumin monomer is maintained at 80~120℃, the other steps are the same as the above experiment 5 is the same.

Experiment 18: The preparation process and conditions of Experiment 18 were basically the same as Experiment 6 above, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 80~120℃, the other steps were the same as the above experiment. 6 is the same.

The specific experimental results are shown in Table 1 below:

Those skilled in the art should understand that in the present invention, the initial reaction concentration (ie, the initial amount) of the reactants is not the focus of the present invention, and the initial amount of the reactants used in the examples is only exemplary. , It can also be any other amount, which will not be repeated in this invention.

It is worth mentioning that, in order to determine whether the modified curcumin monomer is obtained in the experiment, nuclear magnetic resonance analysis (1H-NMR spectrum analysis) and mass spectrometer analysis (mass spectrometer spectrum analysis) of the products obtained in the experiment are required. ). It should be understood that the 1H-NMR spectrum can be obtained by a nuclear magnetic resonance instrument (such as NMR, Ascend TM 400MHz, sold by Bruker); the mass spectrometer spectrum can be obtained by a liquid chromatography tandem mass spectrometer (such as UPLC/ Q-TOF/MAS, DIONEX UltiMate 3000, Bruker for sale) to obtain.

In the preferred embodiment of the present invention, as shown in FIG. 2, the 1H-NMR spectrum analysis result of a modified curcumin monomer obtained by the preparation method of the present invention is shown. From the analysis of the 1H-NMR spectrum shown in Figure 2, it can be seen that the curcumin monomer (Curcumin) can indeed be converted into the modified curcumin monomer (Curcumin GMA) with a carbon-carbon double bond structure through the preparation method. deribative). It can be seen from the 1H-NMR spectrum that the curcumin monomer (Curcumin) can detect signals at positions a, b, c, d, e, f, and k; while the epoxy monomer (GMA) can be detected at positions i, Signals are detected at the positions of j, ga, gb, and gc; and the modified curcumin monomer (Curcumin GMA deribative) can be used in a, b, c, d, e, f, k, i, j, m, n The signal is detected at the position of o. From the above results, it can be known that the epoxy monomer represents epoxy ga, gb, gc will all be converted into OH groups m, n, o on the benzene ring of curcumin monomer, indicating that the epoxy group of the epoxy monomer reacts with the OH group on the benzene ring of curcumin . Compounds J1~J18 can show through this NMR structure that the epoxy group on the epoxy monomer does react with the OH group on the benzene ring of the curcumin monomer. However, other structures of the modified curcumin monomer cannot be accurately interpreted because the detected value is too small, and it needs to be further analyzed using a mass spectrometer spectrum.

Further, as shown in FIG. 3, the mass spectrometer profile analysis result of the modified curcumin monomer obtained according to the preparation method of the present invention is shown. From the analysis of the mass spectrometer profile shown in Figure 3, it can be seen that the curcumin monomer (369.1, 339.1) can indeed be converted into the modified curcumin monomer with a carbon-carbon double bond structure (single-side substitution 511.2, 481.2). ; Bilateral replacement 653.3, 623.3). In other words, from the analysis result of the 1H-NMR spectrum and the analysis result of the mass spectrometer spectrum, it can be confirmed that the modified curcumin monomer obtained by the preparation method of the present invention has the structural formula 5. Of the compound.

However, in the present invention, because the reactant (curcumin monomer) belongs to a mixture, the result synthesized by the preparation method is also a mixture. As a result, other structures cannot be accurately interpreted because the detected value is too small, but it can be proved that the reaction is here. During the process, curcumin monomers with different chemical structures and the modified curcumin will exist simultaneously.

Those skilled in the art should understand that the embodiments of the present invention shown in the above description and the drawings are merely examples and do not limit the present invention. The purpose of the present invention has been completely and effectively achieved. The functions and structural principles of the present invention have been shown and explained in the embodiments. Without departing from the principles, the implementation of the present invention may have any deformation or modification.

A~D: Step

Claims (16)

A modified curcumin comprising at least one modified curcumin monomer, wherein the modified curcumin monomer is prepared by a chemical reaction between a curcumin monomer and an epoxy compound having a carbon-carbon double bond And the structural end of the modified curcumin monomer has a carbon-carbon double bond structure. The modified curcumin according to claim 1, wherein the modified curcumin monomer has the following general structural formula:

Among them: R1 is

or

; R2 is -OH or

; R3 is a hydrogen group or a methyl group; R4 is a hydrogen group or a methoxy group; and R5 is a hydrogen group or a methoxy group. The modified curcumin according to claim 2, wherein the structural formula of the modified curcumin monomer is selected from:

The modified curcumin according to claim 1, wherein the epoxy compound having a carbon-carbon double bond is selected from the group consisting of glycidyl monomethacrylate, glycidyl monoacrylate, glycidyl monocrotonate, and Methyl glycidyl aconic acid, glycidyl monomaleate, glycidyl fumarate, and glycidyl itaconic acid. The modified curcumin according to any one of claims 1 to 4, wherein the modified curcumin is used for coloring or dyeing. A preparation method of modified curcumin, characterized by comprising the following steps: (i) preparing a curcumin solution with a ring-opening compound, wherein the curcumin solution contains a curcumin monomer and the ring-opening compound; (ii) preparing an epoxy compound solution, wherein the epoxy compound solution includes an epoxy compound having a carbon-carbon double bond; and (iii) adding the epoxy compound solution to the curcumin solution so that A chemical reaction occurs between the epoxy compound and the curcumin monomer to generate a modified curcumin monomer to produce the modified curcumin, wherein the modified curcumin monomer has the following general structural formula:

Among them: R1 is

or

; R2 is -OH or

; R3 is a hydrogen group or a methyl group; R4 is a hydrogen group or a methoxy group; and R5 is a hydrogen group or a methoxy group. The method for preparing modified curcumin according to claim 6, wherein said step (iii) further comprises the step of adding a catalyst to the curcumin solution, wherein the catalyst is selected from 4-dimethylaminopyridine, tri Ethylenetetramine, triphenylphosphine, and 1,8-diazabicyclo[5.4.0]undec-7-ene. The method for preparing modified curcumin according to claim 6, wherein in the step (i), a curcumin and the ring-opening compound are dissolved in a solvent to prepare the ring-opening compound Curcumin solution, wherein the solvent is selected from anhydrous tetrahydrofuran, anhydrous dimethylformamide, anhydrous tert-butyl methyl ether, anhydrous acetone, and anhydrous ethanol. The method for preparing modified curcumin according to claim 7, wherein in the step (ii), the epoxy compound is dissolved in the solvent to prepare the epoxy compound solution. The method for preparing modified curcumin according to claim 9, wherein the epoxy compound is selected from the group consisting of glycidyl methacrylate, glycidyl monoacrylate, glycidyl monocrotonate, and methyl itaconic acid. Glycidyl ester, glycidyl monomaleate, glycidyl fumarate, and glycidyl itaconic acid. The method for preparing modified curcumin according to claim 6, wherein the ring-opening compound is monodimethylsulfene. The method for preparing modified curcumin according to any one of claims 6 to 11, wherein said step (iii) further comprises the step of: dripping the epoxy compound solution in the curcumin solution so that the ring The oxy compound fully reacts with the curcumin monomer. The method for preparing modified curcumin according to any one of claims 6 to 11, wherein the step (iii) further includes the step of maintaining the reaction temperature between the epoxy compound and the curcumin monomer at 20~120℃. The method for preparing modified curcumin according to any one of claims 6 to 11, wherein the step (iii) further includes the step of maintaining the reaction temperature between the epoxy compound and the curcumin monomer at 50~80℃. The method for preparing modified curcumin according to any one of claims 6 to 11, further comprising the steps of: preparing an inhibitory solution, wherein the inhibitory solution includes a radical polymerization inhibitor; and adding the inhibitory solution to the ring The oxy compound solution is used to pre-store the reactivity of the carbon-carbon double bond on the epoxy compound by the radical polymerization inhibitor. The method for upgrading curcumin monomers according to claim 15, wherein the radical polymerization inhibitor is selected from the group consisting of hydroquinone monomethyl ether, 1,4-benzoquinone, 1,1-diphenyl -2-picrylhydrazine radical, nitrobenzene.

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