CN110551026B - Modified curcumin and preparation method thereof - Google Patents
Modified curcumin and preparation method thereof Download PDFInfo
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- CN110551026B CN110551026B CN201810563233.0A CN201810563233A CN110551026B CN 110551026 B CN110551026 B CN 110551026B CN 201810563233 A CN201810563233 A CN 201810563233A CN 110551026 B CN110551026 B CN 110551026B
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
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- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
Abstract
The invention discloses modified curcumin and a preparation method thereof. The modified curcumin comprises at least one modified curcumin monomer. The modified curcumin monomer is prepared by chemical reaction of a curcumin monomer and an epoxy compound with a carbon-carbon double bond, and the structural end of the modified curcumin monomer has a carbon-carbon double bond structure.
Description
Technical Field
The invention relates to the technical field of chemical dyes, in particular to modified curcumin and a preparation method thereof.
Background
Curcumin is a chemical component extracted from the rhizome of some plants in the families of Zingiberaceae and Araceae, wherein the content of Curcuma rhizome is about 3-6%, which is a pigment with diketone, which is rare in the plant world. Curcumin is orange yellow crystal powder, slightly bitter in taste, insoluble in water and a natural yellow pigment, so that curcumin is mainly used for coloring products such as sausage products, cans, sauced products and the like in food production. In addition, curcumin itself has a remarkable coloring effect and is not liable to cause color change, and thus it has been widely used as a coloring agent and a dye for foods or other substances.
However, in the application of the traditional curcumin, the curcumin monomer is directly used for coloring and dyeing other substances, and after the curcumin is placed for a period of time or washed by other substances, the traditional curcumin is easily separated from other substances, so that the coloring and dyeing effects of other substances are reduced, and the application of the traditional curcumin for dyeing is greatly influenced.
Disclosure of Invention
The invention aims to provide modified curcumin and a preparation method thereof, wherein the structural terminal of a modified curcumin monomer in the modified curcumin has a carbon-carbon double bond structure, so that the modified curcumin and other substances are improved in binding stability.
Another object of the present invention is to provide modified curcumin and a preparation method thereof, which can improve the application effect of the modified curcumin to expand the application field of the modified curcumin.
The invention also aims to provide modified curcumin and a preparation method thereof, wherein the modified curcumin is prepared by the chemical reaction of curcumin and an epoxy compound with a carbon-carbon double bond, so that the structural end of a modified curcumin monomer in the modified curcumin has a carbon-carbon double bond structure.
Another object of the present invention is to provide a modified curcumin capable of stably binding to other substances having a carbon-carbon double bond, and a method for producing the same.
Another object of the present invention is to provide modified curcumin and a preparation method thereof, wherein the properties of the original curcumin monomer in the modified curcumin are not affected during the preparation of the modified curcumin, so as to ensure the dyeing effect of the modified curcumin monomer.
Another objective of the present invention is to provide modified curcumin and a preparation method thereof, wherein in the process of preparing the modified curcumin, the reactivity of a carbon-carbon double bond on an epoxy compound needs to be preserved in advance so as to prevent the carbon-carbon double bond structure on the epoxy compound from being damaged; meanwhile, the reaction efficiency and the reaction stability between curcumin and epoxy compound can be improved.
Another object of the present invention is to provide a modified curcumin and a preparation method thereof, wherein a catalyst is added during the preparation of the modified curcumin to increase the reaction rate between curcumin and an epoxy compound.
Another object of the present invention is to provide a modified curcumin and a preparation method thereof, wherein a reaction temperature range is maintained during the preparation of the modified curcumin, such that a curcumin monomer and an epoxy compound are reacted within the reaction temperature range, thereby increasing a reaction rate.
In order to achieve at least one of the above objects or other objects and advantages, the present invention provides a modified curcumin comprising at least one modified curcumin monomer, wherein the modified curcumin is prepared by chemically reacting curcumin 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.
In some embodiments of the invention, the modified curcumin monomer has the following general structural formula:
wherein: r1 is
Or
R2 is-OH or
R3 is hydrogen or methyl;
r4 is hydrogen or methoxy;
r5 is hydrogen radical or methoxy.
In some embodiments of the invention, the modified curcumin monomer has a structural formula selected from:
in some embodiments of the present invention, the epoxy compound having a carbon-carbon double bond is selected from one or more of glycidyl methacrylate, glycidyl monoacrylate, glycidyl crotonate, methyl glycidyl itaconate, glycidyl maleate, glycidyl fumarate, glycidyl itaconate, and other equivalent compounds having the same technical characteristics. .
In some embodiments of the invention, the modified curcumin is used for coloring or staining.
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-opened compound, wherein the curcumin solution comprises a curcumin monomer and the ring-opened compound;
(ii) preparing an epoxy compound solution, wherein the epoxy compound solution comprises an epoxy compound with a carbon-carbon double bond; and
(iii) adding the epoxy compound solution into the curcumin solution to enable the epoxy compound and the curcumin monomer to generate a chemical reaction so as to generate a modified curcumin monomer, thereby preparing the modified curcumin, wherein the modified curcumin monomer has the following structural general formula:
wherein: r1 is
Or
R2 is-OH or
R3 is hydrogen or methyl;
r4 is hydrogen or methoxy;
r5 is hydrogen radical or methoxy.
In some embodiments of the present invention, said step (iii) further comprises the steps of:
adding a catalyst to the curcumin solution, wherein the catalyst is selected from one or more of 4-dimethylaminopyridine, triethylene-tetramine, triphenylphosphine, 1,8-diazabicyclo [5.4.0] undec-7-ene and other compounds with similar amine group structures.
In some embodiments of the present invention, in step (i), a curcumin and the ring-opened compound are dissolved in a solvent to prepare the curcumin solution with the ring-opened 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 one or more of glycidyl methacrylate, glycidyl monoacrylate, glycidyl crotonate, methyl glycidyl itaconate, glycidyl maleate, glycidyl fumarate, glycidyl itaconate, and other equivalent compounds having the same technical characteristics.
In some embodiments of the invention, the ring-opening compound is a dimethyl sulfoxide.
In some embodiments of the present invention, said step (iii) further comprises the steps of:
and dropwise adding the epoxy compound solution into the curcumin solution to ensure that the epoxy compound and the curcumin monomer are fully reacted.
In some embodiments of the present invention, said step (iii) further comprises the steps of:
maintaining the reaction temperature between the epoxy compound and the curcumin monomer at 20-120 ℃.
In some embodiments of the present invention, said step (iii) further comprises the steps of:
maintaining the reaction temperature between the epoxy compound and the curcumin monomer at 50-80 ℃.
In some embodiments of the present invention, the method for preparing modified curcumin further comprises the steps of:
preparing an inhibiting solution, wherein the inhibiting solution comprises a free radical polymerization reaction inhibitor; and
the inhibiting solution is added to the epoxy compound solution to preserve the reactivity of the carbon-carbon double bond on the epoxy compound by the radical polymerization inhibitor.
In some embodiments of the invention, the free radical polymerization inhibitor is selected from one or more of hydroquinone monomethyl ether, 1, 4-benzoquinone, 1-diphenyl-2-picrylhydrazyl radical, nitrobenzene, or other equivalent compounds having the same technical characteristics.
Further objects and advantages of the invention will be fully apparent from the ensuing description and drawings.
These and other objects, features and advantages of the present invention will become more fully apparent from the following detailed description, the accompanying drawings and the claims.
Drawings
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 3 are schematic diagrams of analysis of 1H-NMR spectrum and mass spectrometer spectrum, respectively, of one of the modified curcumins obtained according to the above preferred embodiment of the present invention.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
It will be understood by those skilled in the art that in the present disclosure, the terms "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in an orientation or positional relationship indicated in the drawings for ease of description and simplicity of description, and do not indicate or imply that the referenced devices or components must be constructed and operated in a particular orientation and thus are not to be considered limiting.
In the present invention, the terms "a" and "an" in the claims and the description should be understood as meaning "one or more", that is, one element may be one in number in one embodiment, and the element may be more than one in number in another embodiment. The terms "a" and "an" should not be construed as limiting the number unless the number of such elements is explicitly recited as one in the present disclosure, but rather the terms "a" and "an" should not be construed as being limited to only one of the number. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, and/or components.
Curcumin is a natural yellow color, has obvious effect and is not easy to cause color change, and is widely used as a colorant and a dye for food or other substances at present. However, in the application of traditional curcumin, the curcumin monomer is directly used for coloring and dyeing other substances, but after a period of standing or washing of other substances, the curcumin monomer can be easily separated from other substances, so that the coloring and dyeing effects of other substances are reduced. It will be appreciated by those skilled in the art that there are typically three curcumin monomers in this conventional curcumin, which are one compound having the following structural formulae (1) to (3):
wherein, in the structural formula (1) and the structural formula (2), Me is methyl, that is, OMe is methoxy.
It is to be noted that the compounds of the above formulae (1) to (3) (i.e. curcumin monomers) are present in the conventional curcumin at the same time, differing only in the ratio of the ratio: the curcumin monomer of the structural formula (1) accounts for about 70-80 percent; the curcumin monomer of the structural formula (2) accounts for about 10 to 20 percent; the curcumin monomer of the structural formula (3) accounts for about 10 percent.
It is worth mentioning that the curcumin monomer has the following structural general formula (4):
wherein: in the general structural formula (4), R4 is hydrogen or methoxy; r5 is hydrogen radical or methoxy.
In the polymerization field, it is known to carry out polymerization using monomers having two or more different carbon-carbon double bonds, which have good performance in terms of bonding stability. Therefore, in order to improve the application effect of the curcumin, the invention provides the modified curcumin, so that the structural terminal of a modified curcumin monomer in the modified curcumin has a carbon-carbon double bond structure, the combination stability between the modified curcumin monomer and other substances is improved, and the curcumin can be applied to various related fields needing dyeing.
In the invention, the modified curcumin monomer is generated by chemical reaction between the curcumin monomer and an epoxy compound with a carbon-carbon double bond, so that the structural terminal of the modified curcumin monomer has a carbon-carbon double bond structure, the modified curcumin can be stably combined with other substances with carbon-carbon double bonds, the modified curcumin is prevented from being separated due to long-term use or washing, and the coloring and dyeing effects of the modified curcumin are enhanced.
Those skilled in the art will understand that: because the structure end of the modified curcumin monomer has a carbon-carbon double bond structure, and the carbon-carbon double bond belongs to unsaturated chemical bonds in the chemical field, the modified curcumin monomer can generate polymerization reaction with other carbon-carbon double bonds or other unsaturated chemical bonds to form more stable chemical bonds (namely covalent bonds), so that the acting force between the modified curcumin monomer and other substances with the carbon-carbon double bond structure is covalent bond force; however, the structural end of the curcumin monomer does not have a carbon-carbon double bond structure, so that the curcumin monomer cannot be subjected to polymerization reaction with other substances with the carbon-carbon double bond structure, and the curcumin monomer can be combined with other substances only through van der waals force, but the intermolecular covalent bond force is far greater than the intermolecular van der waals force, so that the modified curcumin can be combined with other substances containing the carbon-carbon double bond more stably to prevent the modified curcumin from falling off.
Specifically, the modified curcumin monomer has the following structural formula (5), namely the structural general formula of the modified curcumin monomer (namely the chemical formula of the modified curcumin monomer):
wherein: r1 is
(abbreviated as group I) or
(group II for short);
r2 is-OH or
(III group for short), wherein R1 is I group or II group, R3 is hydrogen group or methyl;
r3 is hydrogen or methyl;
r4 is hydrogen or methoxy;
r5 is hydrogen radical or methoxy.
More specifically, the modified curcumin monomer may be generated by reacting the curcumin monomer with the epoxy compound having a carbon-carbon double bond, which may be, but not limited to, implemented as Glycidyl Methacrylate (GMA), and may also be implemented as other compounds having a carbon-carbon double bond structure and an epoxy segment, such as glycidyl acrylate (glycidyl acrylate), glycidyl crotonate (glycidyl crotonate), methyl glycidyl itaconate (methyl glycidyl itaconate), glycidyl maleate (glycidyl maleate), glycidyl fumarate (glycidyl fumarate), glycidyl itaconate (glycidyl itaconate), or other equivalent compounds having the same technical characteristics.
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:
wherein: r1 is
Or
R2 is-OH or
R3 is hydrogen or methyl;
r4 is hydrogen or methoxy;
r5 is hydrogen radical or methoxy.
Notably, according to the above chemical reaction formula (6), compounds having the following structural formula (both of which are the modified curcumin monomers) can be produced:
compound J1:
in the general structural formula (5), R1 is a group I, R2 is — OH, R3 is methyl, R4 is methoxy, and R5 is methoxy, so that the compound J1 has the following structural formula 1-1:
compound J2:
in the general structural formula (5), R1 is a group I, R2 is — OH, R3 is methyl, R4 is hydrogen, and R5 is methoxy, so that the compound J2 has the following structural formula 1-2:
compound J3:
in the above general structural formula (5), R1 is a group I, R2 is — OH, R3 is methyl, R4 is methoxy, and R5 is hydrogen, then the compound J3 has the following structural formula 1-3:
compound J4:
in the general structural formula (5), R1 is a group I, R2 is — OH, R3 is methyl, R4 is hydrogen group, and R5 is hydrogen group, the compound J4 has the following structural formulas 1 to 4:
compound J5:
in the general structural formula (5), R1 is a group II, R2 is — OH, R3 is methyl, R4 is methoxy, and R5 is methoxy, so that the compound J5 has the following structural formulas 1 to 5:
compound J6:
in the general structural formula (5), R1 is a group II, R2 is — OH, R3 is methyl, R4 is hydrogen group, and R5 is methoxy group, the compound J6 has the following structural formulas 1 to 6:
compound J7:
in the above general structural formula (5), R1 is group II, R2 is — OH, R3 is methyl, R4 is methoxy, and R5 is hydrogen, then the compound J7 has the following structural formula 1-7:
compound J8:
in the general structural formula (5), R1 is a group II, R2 is — OH, R3 is methyl, R4 is hydrogen group, and R5 is hydrogen group, the compound J8 has the following structural formulas 1 to 8:
compound J9:
in the above general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group I, R3 is a methyl group), R3 is a methyl group, R4 is a methoxy group, and R5 is a methoxy group), the compound J9 has the following structural formulas 1 to 9:
compound J10:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group I, R3 is a methyl group), R3 is a methyl group, R4 is a hydrogen group, and R5 is a methoxy group), the compound J10 has the following structural formulas 1 to 10:
compound J11:
in the above general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group I, R3 is a methyl group), R3 is a methyl group, R4 is a hydrogen group, and R5 is a hydrogen group, the compound J11 has the following structural formulas 1 to 11:
compound J12:
in the above general structural formula (5), R1 is a group II, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a methyl group, R4 is a methoxy group, and R5 is a methoxy group), the compound J12 has the following structural formulas 1 to 12:
compound J13:
in the above general structural formula (5), R1 is a group II, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a methyl group, R4 is a methoxy group, and R5 is a hydrogen group, then the compound J13 has the following structural formulas 1 to 13:
compound J14:
in the general structural formula (5), R1 is a group II, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a methyl group, R4 is a hydrogen group, and R5 is a hydrogen group), the compound J14 has the following structural formulas 1 to 14:
compound J15:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a methyl group, R4 is a methoxy group, and R5 is a methoxy group), the compound J15 has the following structural formulas 1 to 15:
compound J16:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a methyl group, R4 is a hydrogen group, and R5 is a methoxy group), the compound J16 has the following structural formulas 1 to 16:
compound J17:
in the above general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a methyl group, R4 is a methoxy group, and R5 is a hydrogen group, then the compound J17 has the following structural formulas 1 to 17:
compound J18:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a methyl group, R4 is a hydrogen group, and R5 is a hydrogen group, the compound J18 has the following structural formulas 1 to 18:
compound J19:
in the above general structural formula (5), R1 is a group I, R2 is — OH, R3 is a hydrogen group, R4 is a methoxy group, and R5 is a methoxy group, the compound J19 has the following structural formulas 1 to 19:
compound J20:
in the general structural formula (5), R1 is a group I, R2 is — OH, R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a methoxy group, the compound J20 has the following structural formulas 1 to 20:
compound J21:
in the above general structural formula (5), R1 is a group I, R2 is — OH, R3 is a hydrogen group, R4 is a methoxy group, and R5 is a hydrogen group, then the compound J21 has the following structural formulas 1 to 21:
compound J22:
in the general structural formula (5), R1 is a group I, R2 is — OH, R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a hydrogen group, the compound J22 has the following structural formulas 1 to 22:
compound J23:
in the above general structural formula (5), R1 is a group II, R2 is — OH, R3 is a hydrogen group, R4 is a methoxy group, and R5 is a methoxy group, the compound J23 has the following structural formulas 1 to 23:
compound J24:
in the above general structural formula (5), R1 is a group II, R2 is — OH, R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a methoxy group, the compound J has the following structural formula 1 to 24:
compound J25:
in the general structural formula (5), R1 is a group II, R2 is — OH, R3 is a hydrogen group, R4 is a methoxy group, and R5 is a hydrogen group, the compound J25 has the following structural formulas 1 to 25:
compound J26:
in the general structural formula (5), R1 is a group II, R2 is — OH, R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a hydrogen group, the compound J26 has the following structural formulas 1 to 26:
compound J27:
in the above general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group I, R3 is a hydrogen group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a methoxy group), the compound J27 has the following structural formulas 1 to 27:
compound J28:
in the above general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group I, R3 is a methyl group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a methoxy group, the compound J28 has the following structural formulas 1 to 28:
compound J29:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group I, R3 is a hydrogen group), R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a methoxy group), the compound J29 has the following structural formulas 1 to 29:
compound J30:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group I, R3 is a methyl group), R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a methoxy group), the compound J30 has the following structural formula 1-30:
compound J31:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group I, R3 is a methyl group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a hydrogen group, the compound J31 has the following structural formula 1-J31:
compound J32:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group I, R3 is a hydrogen group), R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a hydrogen group), the compound J32 has the following structural formula 1-J32:
compound J33:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group I, R3 is a methyl group), R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a hydrogen group, the compound J33 has the following structural formula 1-J33:
compound J34:
in the general structural formula (5), R1 is a group II, R2 is a group III (wherein R1 in R2 is a group II, R3 is a hydrogen group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a methoxy group), the compound J34 has the following structural formulas 1 to 34:
compound J35:
in the general structural formula (5), R1 is a group II, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a methoxy group, the compound J35 has the following structural formulas 1 to 35:
compound J36:
in the general structural formula (5), R1 is a group II, R2 is a group III (wherein R1 in R2 is a group II, R3 is a hydrogen group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a hydrogen group), then the compound J36 has the following structural formula 1-36:
compound J37:
in the general structural formula (5), R1 is a group II, R2 is a group III (wherein R1 in R2 is a group II, R3 is a methyl group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a hydrogen group), the compound J37 has the following structural formula 1-37:
compound J38:
in the general structural formula (5), R1 is a group II, R2 is a group III (wherein R1 in R2 is a group II, R3 is a methyl group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a hydrogen group, then the structural formula 1-38 of the compound J38 is as follows:
compound J39:
in the above general structural formula (5), R1 is a group II, R2 is a group III (where R1 in R2 is a group II, R3 is a hydrogen group), R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a hydrogen group), the compound J39 has the following structural formulas 1 to 39:
compound J40:
in the general structural formula (5), R1 is a group II, R2 is a group III (wherein R1 in R2 is a group II, R3 is a methyl group), R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a hydrogen group, the compound J40 has the following structural formulas 1 to 40:
compound J41:
in the general structural formula (5), R1 is a group I, R2 is a group III (wherein R1 in R2 is a group II, R3 is a hydrogen group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a methoxy group), the compound J41 has the following structural formulas 1 to 41:
compound J41:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a methoxy group, the compound J41 has the following structural formulas 1 to 41:
compound J41:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a hydrogen group), R3 is a methyl group, R4 is a methoxy group, and R5 is a methoxy group), the compound J41 has the following structural formulas 1 to 41:
compound J42:
in the general structural formula (5), R1 is a group I, R2 is a group III (wherein R1 in R2 is a group II, R3 is a hydrogen group), R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a methoxy group), then the compound J42 has the following structural formulas 1 to 42:
compound J43:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a methoxy group, the compound J43 has the following structural formulas 1 to 43:
compound J44:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a hydrogen group), R3 is a methyl group, R4 is a hydrogen group, and R5 is a methoxy group), the compound J44 has the following structural formulas 1 to 44:
compound J45:
in the general structural formula (5), R1 is a group I, R2 is a group III (wherein R1 in R2 is a group II, R3 is a hydrogen group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a hydrogen group), then the compound J45 has the following structural formula 1-45:
compound J46:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a methyl group), R3 is a hydrogen group, R4 is a methoxy group, and R5 is a hydrogen group, the compound J46 has the following structural formulas 1 to 46:
compound J47:
in the general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a hydrogen group), R3 is a methyl group, R4 is a methoxy group, and R5 is a hydrogen group), the compound J47 has the following structural formulas 1 to 47:
compound J48:
in the above general structural formula (5), R1 is a group I, R2 is a group III (where R1 in R2 is a group II, R3 is a hydrogen group), R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a hydrogen group), the compound J48 has the following structural formulas 1 to 48:
compound J49:
in the general structural formula (5), R1 is a group I, R2 is a group III (wherein R1 in R2 is a group II, R3 is a methyl group), R3 is a hydrogen group, R4 is a hydrogen group, and R5 is a hydrogen group, the compound J49 has the following structural formulas 1 to 49:
compound J50:
in the general structural formula (5), R1 is a group I, R2 is a group III (wherein R1 in R2 is a group II, R3 is a hydrogen group), R3 is a methyl group, R4 is a hydrogen group, and R5 is a hydrogen group), the compound J50 has the following structural formula 1-50:
it is noted that, in order not to affect the characteristics (such as color characteristics, coloring characteristics, etc.) possessed by the curcumin monomer itself, the reaction planned by the present invention is designed to: the epoxy chain segment in the epoxy compound with the carbon-carbon double bond can generate addition reaction with-OH on a benzene ring of the curcumin monomer to generate the modified curcumin monomer, so that the structural terminal of the modified curcumin monomer has a carbon-carbon double bond structure, and the coloring and dyeing effects of the modified curcumin are improved.
According to another aspect of the invention, the invention further provides a preparation method of the modified curcumin. As shown in fig. 1, the method for preparing modified curcumin according to a preferred embodiment of the present invention comprises the following steps:
(A) preparing a curcumin solution, wherein the curcumin solution comprises a curcumin monomer.
More specifically, a conventional 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 one or more of the curcumin monomer groups consisting of the structural formulas (1) to (3), so that the curcumin monomer is dissolved in the solvent, and the curcumin monomer is easier to chemically react with other substances.
It is noted that the solvent may be, but is not limited to, embodied as an anhydrous organic solvent for dissolving the curcumin monomer and the epoxy compound having a carbon-carbon double bond. Preferably, the solvent is anhydrous Tetrahydrofuran (THF) to enhance the dissolution 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 other equivalent compounds having the same technical characteristics as the tetrahydrofuran to achieve the same effect.
(B) Preparing an epoxy compound solution, wherein the epoxy compound solution comprises an epoxy compound with a carbon-carbon double bond.
More specifically, the epoxy compound with a carbon-carbon double bond is dissolved in a solvent to prepare the epoxy compound solution, wherein the epoxy compound solution comprises the epoxy compound with a carbon-carbon double bond, so that the epoxy compound can react with other substances more easily. It should be understood that the solvent in step (B) is kept the same as the solvent in step (a) to avoid affecting subsequent purification and the like by adding new solvent.
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, and includes, but is not limited to, glycidyl methacrylate, glycidyl acrylate, glycidyl crotonate, methyl glycidyl itaconate, glycidyl maleate, glycidyl fumarate, glycidyl itaconate, or other equivalent compounds having the same technical characteristics.
(C) Adding a ring-opening compound to the curcumin solution.
More specifically, to enable the epoxy segment in the epoxy compound having a carbon-carbon double bond structure to react with other monomers, a ring opening reaction needs to be performed on the epoxy compound in advance, so that the epoxy segment of the epoxy compound generates a ring opening phenomenon, and the epoxy compound can react with the curcumin monomer. Therefore, in the preparation method of the modified curcumin provided by the invention, the ring-opening compound needs to be added into the curcumin solution, so that after the epoxy compound solution is mixed with the curcumin solution, the epoxy compound firstly carries out ring-opening reaction under the action of the ring-opening compound, and then the ring-opened epoxy compound reacts with the curcumin monomer. It is 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.
Notably, the ring-opening compound may be, but is not limited to being, embodied as dimethyl sulfoxide (DMSO). It should be understood that the ring-opening compound can also be implemented as other equivalent compounds having the same technical characteristics as the dimethyl sulfoxide to cause the ring-opening phenomenon of the epoxy segment of the epoxy compound.
Notably, the step (C) can be performed simultaneously with the step (a) to formulate the curcumin solution with the ring-opened compound such that the curcumin monomer and the ring-opened compound are present in the curcumin solution at the same time.
(D) 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 the modified curcumin monomer.
More specifically, the epoxy compound solution is slowly added dropwise to the curcumin solution to sufficiently mix the epoxy compound solution and the curcumin solution to form the mixed solution, so that a chemical reaction occurs between the epoxy compound in the mixed solution and the curcumin monomer to produce the modified curcumin.
It is to 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.
It will be understood by those skilled in the art that the steps (a) and (B) in the preparation method are not in sequential order, that is, the step (a) may be performed before the step (B) is completed; or said step (a) may be performed after said step (B) is completed; or said step (a) and said step (B) are performed synchronously.
In the preferred embodiment of the present invention, the step (C) of the preparation method further comprises the steps of: adding a catalyst to the curcumin solution.
Specifically, in order to increase the reactivity of the reactants, a catalyst is further added in 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 may also be embodied as Triethylenetetramine (TETA), Triphenylphosphine (TPP), 1,8-Diazabicyclo [5.4.0] undec-7-ene (1,8-Diazabicyclo [5.4.0] undec-7-ene, DBU) or other compounds having similar amine structures to achieve the same catalytic effect.
It is understood that the catalyst, like the ring-opening compound, can be added directly to formulate the curcumin solution in said step (a); can also be added separately to the curcumin solution after the completion of the step (a), without limitation in the present invention.
Further, the step (D) of the preparation method further comprises the steps 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 are reacted within the reaction temperature range.
More specifically, in the preferred embodiment of the present invention, the reaction temperature is in the range of 20 to 120 ℃ to maintain the efficiency and stability of the entire reaction, that is, by maintaining the temperature of the mixed solution in the reaction temperature range, a curcumin monomer and an epoxy compound are reacted in the reaction temperature range to increase the reaction rate and stability. It is understood that if the temperature of the mixed solution is too high, the epoxy compound having a carbon-carbon double bond structure is very easily triggered to undergo a radical polymerization reaction, thereby reducing the production efficiency of the modified curcumin.
Preferably, the reaction temperature range is 50-100 ℃.
More preferably, the reaction temperature ranges from 50 ℃ to 80 ℃.
It is noted that, in order to prevent the carbon-carbon double bond structure in the epoxy compound from being inactivated, that is, in order to retain the carbon-carbon double bond structure in the epoxy compound, a radical polymerization inhibitor is used in the present invention to inhibit the activity of the carbon-carbon double bond structure in the epoxy compound, so as to improve the reaction efficiency and reaction stability between the curcumin monomer and the epoxy compound. In other words, in the process of preparing the modified curcumin, the radical polymerization inhibitor needs to be used to preserve the reactivity of the carbon-carbon double bond on an epoxy compound in advance so as to prevent the carbon-carbon double bond structure on the epoxy compound from being damaged.
It is understood that the Free Radical polymerization inhibitor includes, but is not limited to, hydroquinone Monomethyl Ether (MEHQ), 1, 4-benzoquinone (1,4benzoquinone, BQ), 1-Diphenyl-2-picrylhydrazine Radical (1, 1-Diphenyl-2-piperidyl hydrochloride), nitrobenzene (nitrobenzene) or other equivalent compounds having the same technical characteristics.
More specifically, the preparation method further comprises the steps of:
preparing an inhibiting solution, wherein the inhibiting solution comprises a free radical polymerization reaction inhibitor; and
the inhibiting solution is added to the epoxy compound solution to preserve the reactivity of the carbon-carbon double bond of the epoxy compound by the radical polymerization inhibitor.
In the method for preparing modified curcumin according to the preferred embodiment of the present invention, grouping experiments are performed with the presence or absence of a catalyst, the presence or absence of a ring-opening compound, the selection of a reaction temperature range, and the presence or absence of a radical polymerization inhibitor as variables, for example:
experiment 1: dissolving 2.0g of curcumin in 20mL of anhydrous THF solvent (namely anhydrous tetrahydrofuran solvent) to prepare the curcumin solution, and placing the curcumin solution in a reactor for standby; dissolving 2.2g of Glycidyl Methacrylate (GMA) in 20mL of anhydrous THF solvent to prepare the epoxy compound solution, and placing the epoxy compound solution in a dropping tube for standby; slowly dripping the epoxy compound solution in the dripping pipe into the reactor within 1 hour, maintaining the reaction temperature between the epoxy compound and the curcumin monomer at 20-50 ℃, and reacting the epoxy compound and the curcumin monomer within 20-50 ℃ for 48 hours to ensure that the epoxy compound and the curcumin monomer are fully reacted.
Experiment 2: experiment 2 the preparation process and conditions were essentially the same as in experiment 1 above, except that 0.95g of the 4-dimethylaminopyridine was added to the reactor containing the curcumin solution, so that the 4-dimethylaminopyridine was dissolved in the curcumin solution, the other steps were the same as in experiment 1 above.
Experiment 3: experiment 3 was prepared in substantially the same manner and conditions as in experiment 1 above, except that 0.5mg of hydroquinone monomethyl ether was dissolved in 1.0mL of tetrahydrofuran solvent to prepare the inhibiting solution, and then 3.2g of the inhibiting solution was weighed and added to the epoxy compound solution, and the procedure was the same as in experiment 1 above.
Experiment 4: experiment 4 the preparation process and conditions were essentially the same as in experiment 1 above, except that 10mL of the dimethylsulfoxide was added to the reactor containing the curcumin solution, so that the dimethylsulfoxide was dissolved in the curcumin solution, and the other steps were the same as in experiment 1 above.
Experiment 5: experiment 5 the preparation process and conditions were essentially the same as in experiment 4 above, except that 0.95g of the 4-dimethylaminopyridine was added to the reactor containing the curcumin solution, so that the 4-dimethylaminopyridine was dissolved in the curcumin solution, the other steps were the same as in experiment 4 above.
Experiment 6: experiment 6 was basically the same as experiment 5, except that 0.5mg of hydroquinone monomethyl ether was dissolved in 1.0mL of tetrahydrofuran solvent to prepare the inhibiting solution, and then 3.2g of the inhibiting solution was weighed and added to the epoxy compound solution, the preparation process and conditions were the same as experiment 5.
Experiment 7: the preparation process and conditions of experiment 7 were substantially the same as those of experiment 1, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 50 to 80 ℃, and the other steps were the same as those of experiment 1.
Experiment 8: the preparation process and conditions of experiment 8 were substantially the same as those of experiment 2, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 50 to 80 ℃, and the other steps were the same as those of experiment 2.
Experiment 9: the preparation process and conditions of experiment 9 were substantially the same as those of experiment 3, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 50 to 80 ℃, and the other steps were the same as those of experiment 3.
Experiment 10: the preparation process and conditions of experiment 10 were substantially the same as those of experiment 4 above, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 50 to 80 ℃, and the other steps were the same as those of experiment 4 above.
Experiment 11: the preparation process and conditions of experiment 11 were substantially the same as those of experiment 5, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 50 to 80 ℃, and the other steps were the same as those of experiment 5.
Experiment 12: the preparation process and conditions of experiment 12 were substantially the same as those of experiment 6 above, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 50 to 80 ℃, and the other steps were the same as those of experiment 6 above.
Experiment 13: the preparation process and conditions of experiment 13 were substantially the same as those of experiment 1, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 80 to 120 ℃, and the other steps were the same as those of experiment 1.
Experiment 14: the preparation process and conditions of experiment 14 were substantially the same as those of experiment 2, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 80 to 120 ℃, and the other steps were the same as those of experiment 2.
Experiment 15: the preparation process and conditions of experiment 15 were substantially the same as those of experiment 3, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 80 to 120 ℃, and the other steps were the same as those of experiment 3.
Experiment 16: the preparation process and conditions of experiment 16 were substantially the same as those of experiment 4, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 80 to 120 ℃, and the other steps were the same as those of experiment 4.
Experiment 17: the preparation process and conditions of experiment 17 were substantially the same as those of experiment 5, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 80 to 120 ℃, and the other steps were the same as those of experiment 5.
Experiment 18: the preparation process and conditions of experiment 18 were substantially the same as those of experiment 6, except that the reaction temperature between the epoxy compound and the curcumin monomer was maintained at 80 to 120 ℃, and the other steps were the same as those of experiment 6.
The specific experimental results are shown in table 1 below:
table 1: summary of the results
It should be understood by those skilled in the art that the initial reaction concentration (i.e., initial amount) of the reactants is not important in the present invention, and the initial amount of the reactants used in the examples is only exemplary, and may be any other amount, which will not be described in detail herein.
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 spectroscopy) and mass spectrometer analysis (mass spectrometer spectroscopy) of the product obtained in the experiment are required. It will be appreciated that the 1H-NMR spectrum may be obtained by a nuclear magnetic resonance apparatus (such as NMR, Ascend TM 400MHz, available from Bruker); the MASs spectrometer profile may be acquired by a liquid chromatography tandem MASs spectrometer such as the UPLC/Q-TOF/MAS, DIONEX Ultimate 3000, available from Bruker.
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 according to the present invention is shown. From the 1H-NMR spectrum analysis shown in FIG. 2, it was found that: the Curcumin monomer (curcumine) can be converted into the modified Curcumin monomer (curcumine GMA derivitive) with a carbon-carbon double bond structure by the preparation method. According to a 1H-NMR spectrum, signals can be monitored at the positions a, b, c, d, e, f and k by the Curcumin monomer (Curcumin); the epoxy monomer (GMA) can monitor signals at the positions i, j, ga, gb and gc; and the modified Curcumin monomer (Curcumin GMA derivative) can monitor signals at the positions of a, b, c, d, e, f, k, i, j, m, n and o. From the above results, it is known that ga, gb, gc representing epoxy groups on the epoxy monomer are all converted into OH groups m, n, o on the benzene ring of curcumin monomer, indicating that the epoxy group site of the epoxy monomer reacts with OH groups on the benzene ring of curcumin. The compounds J1-J18 can all show that the epoxy group on the epoxy monomer actually reacts with the OH group on the benzene ring of curcumin monomer through the NMR structure. And other structures of the modified curcumin monomers cannot be accurately judged because the detected values are too small, and a mass spectrometer spectrum is required to be further used for analysis.
Further, as shown in fig. 3, the mass spectrometer spectrum analysis result of the modified curcumin monomer obtained by the production method according to the present invention is shown. From the mass spectrometer profile analysis shown in fig. 3, it can be seen that: the curcumin monomer (369.1, 339.1) was indeed converted into the modified curcumin monomer with a carbon-carbon double bond structure (single-substituted 511.2, 481.2; double-substituted 653.3, 623.3). In other words, from the above 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 is the compound having the structural formula 5.
However, in the invention, because the reactant (the curcumin monomer) belongs to a mixture, the result synthesized by the preparation method also belongs to the mixture, and other structures cannot be accurately judged because the detected value is too small, but the curcumin monomer with different chemical structures and the modified curcumin can be proved to exist simultaneously in the reaction process.
It will be appreciated by persons skilled in the art that the embodiments of the invention described above and shown in the drawings are given by way of example only and are not limiting of the invention. The objects of the invention have been fully and effectively accomplished. The functional and structural principles of the present invention have been shown and described in the examples, and any variations or modifications of the embodiments of the present invention may be made without departing from the principles.
Claims (9)
1. The preparation method of the modified curcumin is characterized by comprising the following steps:
(i) preparing a curcumin solution with a ring-opening compound, wherein the curcumin solution comprises a curcumin monomer and the ring-opening compound, and the ring-opening compound is dimethyl sulfoxide;
(ii) preparing an epoxy compound solution, wherein the epoxy compound solution comprises an epoxy compound with a carbon-carbon double bond; and
(iii) adding the epoxy compound solution and a catalyst into the curcumin solution to enable the epoxy compound and the curcumin monomer to generate a chemical reaction to generate a modified curcumin monomer, thereby preparing the modified curcumin, wherein the catalyst is selected from one or more of 4-dimethylamino pyridine, triethylene tetramine, triphenylphosphine and 1,8-diazabicyclo [5.4.0] undec-7-ene, and the modified curcumin monomer has the following structural general formula:
wherein: r1 is
R2 is-OH or
R3 is hydrogen or methyl;
r4 is hydrogen or methoxy;
r5 is hydrogen radical or methoxy.
2. The method for preparing modified curcumin as claimed in claim 1, wherein in said step (i), a curcumin and the ring-opened compound are dissolved in a solvent to prepare the curcumin solution with the ring-opened 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.
3. The method for producing modified curcumin of claim 2, wherein in said step (ii), the epoxy-based compound is dissolved in the solvent to prepare the epoxy-based compound solution.
4. The modified curcumin preparation method of claim 3, wherein the epoxy compound is selected from one or more of glycidyl methacrylate, glycidyl acrylate, glycidyl crotonate, methyl glycidyl itaconate, glycidyl maleate, glycidyl fumarate, and glycidyl itaconate.
5. The process for producing modified curcumin as claimed in any one of claims 1 to 4, wherein said step (iii) further comprises the steps of:
and dropwise adding the epoxy compound solution into the curcumin solution to ensure that the epoxy compound and the curcumin monomer are fully reacted.
6. The process for producing modified curcumin as claimed in any one of claims 1 to 4, wherein said step (iii) further comprises the steps of:
maintaining the reaction temperature between the epoxy compound and the curcumin monomer at 20-120 ℃.
7. The process for producing modified curcumin as claimed in any one of claims 1 to 4, wherein said step (iii) further comprises the steps of:
maintaining the reaction temperature between the epoxy compound and the curcumin monomer at 50-80 ℃.
8. The process for producing modified curcumin as claimed in any one of claims 1 to 4, further comprising the steps of:
preparing an inhibiting solution, wherein the inhibiting solution comprises a free radical polymerization reaction inhibitor; and
the inhibiting solution is added to the epoxy compound solution to preserve the reactivity of the carbon-carbon double bond on the epoxy compound by the radical polymerization inhibitor.
9. The method for preparing modified curcumin of claim 8, wherein the free radical polymerization inhibitor is selected from one or more of hydroquinone monomethyl ether, 1, 4-benzoquinone, 1-diphenyl-2-picrylhydrazyl radical, nitrobenzene.
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| JPH041186A (en) * | 1990-04-18 | 1992-01-06 | Mitsubishi Rayon Co Ltd | Epoxy (meth)acrylate, production thereof and coating composition thereof |
| CN1919826A (en) * | 2006-09-14 | 2007-02-28 | 南京林业大学 | Method for synthesizing acrylic acid and hydroxyalkyl methacrylate |
| CN106916085A (en) * | 2017-01-12 | 2017-07-04 | 永胜光学股份有限公司 | Modification curcumin |
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| JP4291296B2 (en) * | 2005-04-08 | 2009-07-08 | 株式会社メニコン | Novel polymerizable dye and ophthalmic lens containing the same |
| US7807230B2 (en) * | 2005-06-16 | 2010-10-05 | Rensselaer Polytechnic Institute | Curcumin and curcuminoid compounds, and use thereof as photosensitizers of onium salts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH041186A (en) * | 1990-04-18 | 1992-01-06 | Mitsubishi Rayon Co Ltd | Epoxy (meth)acrylate, production thereof and coating composition thereof |
| CN1919826A (en) * | 2006-09-14 | 2007-02-28 | 南京林业大学 | Method for synthesizing acrylic acid and hydroxyalkyl methacrylate |
| CN106916085A (en) * | 2017-01-12 | 2017-07-04 | 永胜光学股份有限公司 | Modification curcumin |
Non-Patent Citations (2)
| Title |
|---|
| 1-(3-Biaryloxy-2-oxopropyl)indole-5-carboxylic Acids and Related Compounds as Dual Inhibitors of Human Cytosolic Phospholipase A2a and Fatty Acid Amide Hydrolase;Stefan Zahov et al.;《CHEMMEDCHEM》;20111231;第6卷(第3期);第544-549页 * |
| Synthesis and Photopolymerizations of New Phosphonated Methacrylates from Alkyl a-Hydroxymethacrylates and Glycidyl Methacrylate;Gorkem Sahin et al.;《Journal of Applied Polymer Science》;20090528;第114卷;第97-106页 * |
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