Rosin-based beta-diketone derivatives, and preparation method and application thereof

Abstract

The application discloses a rosin-based beta-diketone derivative, a preparation method and application thereof, and belongs to the technical field of organic solvent extraction. The rosin-based beta-diketone derivative provided by the application improves the stability and hydrophobicity of the beta-diketone by constructing a beta-diketone functional group on a rosin-based skeleton, improves the lithium extraction effect, and reduces the solution loss of the rosin-based beta-diketone derivative during extraction. Moreover, the rosin is derived from a natural product rosin which is widely available and renewable, thereby reducing the production and use cost of the rosin-based beta-diketone derivative.

Description

Technical Field

[0001] This invention relates to the field of organic solvent extraction technology, and more specifically, to a rosin-based β-diketone derivative, its preparation method, and its application. Background Technology

[0002] Lithium is an important strategic metal, used in both traditional and emerging industries. Currently, various lithium-containing solutions, including lithium-containing wastewater generated during battery recycling from industrial-grade lithium carbonate production and lithium carbonate residues, still contain considerable amounts of lithium. Directly discharging these solutions not only wastes resources but also causes environmental pollution; therefore, effective treatment is necessary. Currently, lithium extraction from lithium-containing solutions can be achieved through various methods such as carbonate precipitation, electrodialysis, calcination, adsorption, and solvent extraction. Solvent extraction utilizes the specific selectivity of the extractant for lithium to effectively separate lithium from other metals, achieving lithium resource concentration and purification. This method is relatively mature and reliable, with advantages such as simple operation and ease of large-scale production, and has been widely used in lithium extraction and separation. The core of this method lies in the selection of the extractant. β-diketone extractants primarily react their hydroxyl or carbonyl groups with Li... + They combine to form a relatively stable chelate structure and can continue to form complexes with neutral extractants, reducing lithium hydration. However, common commercial β-diketone extractants have drawbacks such as flammability, low flash point, high water solubility, volatility, and high price, making them unsuitable for large-scale industrial use.

[0003] Chinese patent CN114317960A discloses an extraction system for extracting lithium ions and its application. The extraction system in this application includes a diketone compound, a modifier, and a diluent. The diketone compound contains R groups at both ends. 1 and R 2 Each is independently selected from the following group: halogen, substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted 5-7 membered heteroaryl, substituted or unsubstituted phenyl, naphthyl; intermediate group R 3 Selected from the following group: H, halogens, C1-6 alkyl groups, or benzyl groups. This extraction system achieves high lithium extraction rates, good separation selectivity for lithium sodium and lithium potassium, and reduces the water solubility of the extraction system. However, the long-chain alkyl groups attached to both ends of the diketone compound lead to high compound costs. Furthermore, these diketone compounds have relatively small molecular weights, inevitably resulting in volatility and significant solubility issues.

[0004] Rosin is a resin from the pine tree (Pinus spp.) and is used in various fields, including electronics, printing, food, and medical applications, as well as in coatings, inks, adhesives, and synthetic rubber. Rosin is environmentally friendly, biodegradable, and renewable, leading to its development and application in high-end sectors and establishing a dominant market position. my country is the world's largest producer and importer of rosin resin, with a production volume of approximately 1.45 million tons in 2020. However, rosin processing remains at a primary stage, resulting in low added value and overcapacity in low-end products, necessitating urgent development and upgrading.

[0005] The main component of rosin is abietic acid, accounting for about 90%. When rosin is heated to about 270℃, it will be converted into disproportionated rosin under the action of a catalyst, the main component of which is dehydroabietic acid (about 40%). Rosin is also converted into hydrogenated rosin under the action of hydrogenation catalysis. These rosin chemical products are all natural chiral tricyclic diterpenoids, containing three chiral carbon atoms, and are stable. These compounds all contain 20 carbon atoms, only one of which is a polar carboxyl group, and the others are nonpolar groups, thus exhibiting very high lipid solubility and strong hydrophobicity. However, these rosin chemical products have weak ability to separate and extract lithium and cannot be used for lithium extraction.

[0006] Therefore, there is an urgent need for a β-diketone extractant with good hydrophobicity and stability, low production and usage costs, and good lithium extraction performance. Summary of the Invention

[0007] 1. The technical problem that the invention aims to solve

[0008] The purpose of this invention is to overcome the shortcomings of the prior art. This invention provides a rosin-based β-diketone derivative, which reduces the volatility and water solubility of β-diketone by constructing β-diketone functional groups on the rosin-based skeleton, thereby improving its application in lithium extraction. Moreover, the rosin-based derivative is derived from rosin, a widely available and renewable natural product, which greatly reduces the cost of use.

[0009] 2. Technical Solution

[0010] To solve the above problems, the technical solution adopted by the present invention is as follows:

[0011] A rosin-based β-diketone derivative having the structure shown in formula (I), formula (II), or formula (III):

[0012]

[0013] In the formula, R is one of hydroxyl, alkoxy containing 1 to 8 carbon atoms, alkyl or fluoroalkyl containing 1 to 8 carbon atoms, or substituted aryl; the substituent in the substituted aryl is one of alkyl or fluoroalkyl containing 1 to 8 carbon atoms, and the aryl in the substituted aryl is one of benzene, pyridine, pyrazine, pyridazine, thiophene, or furan.

[0014] Furthermore, the rosin-based β-diketone derivative is one of the following compounds:

[0015]

[0016]

[0017] This invention also provides a method for preparing a rosin-based β-diketone derivative, comprising the following steps:

[0018] S1. React ketone compounds in solvent B in the presence of base A;

[0019] S2. Add ester compounds and continue the reaction. The target product is obtained through a condensation reaction between ketone compounds and ester compounds.

[0020] The target product is a rosinyl β-diketone derivative.

[0021] The molar ratio of the ketone compound, ester compound, base A and solvent B is 1:(0.1-20):(1-6):(20-300).

[0022] Furthermore, the alkali A includes one, two or more of sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide.

[0023] Solvent B includes one, two or more of the following: tetrahydrofuran, diethyl ether, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide, ethanol, methanol, benzene, toluene, xylene, hexane, and petroleum ether.

[0024] The hexane is n-hexane and / or cyclohexane.

[0025] Furthermore, in the ketone compound and ester compound, any one of the compounds contains a rosin group, and the other compound contains an R group. For example, one possible scenario is that the ketone compound is a ketone compound containing a rosin group, in which case the ester compound is an ester compound containing an R group; examples of ketone compounds in this scenario include: Examples of the ester compounds include, for example, any one or more of ethyl trifluoroacetate, ethyl pentafluoropropionate, and ethyl heptafluorobutyrate.

[0026] The second scenario can be: the ester compound is an ester compound containing a rosin group, in which case the ketone compound is a ketone compound containing an R group; examples of the ketone compound in this second scenario include: 2-acetylpyridine or 1,1,1-trifluoroacetone, and examples of the ester compound include: Any one or two or more of them.

[0027] Based on this, the rosin-based β-diketone derivative can be prepared by any of the following methods:

[0028] Method 1: S1. React ketone compounds containing rosin groups in solvent B in the presence of base A for 5–120 min.

[0029] S2. The ester compound containing the R group continues to react for 0.5 to 25 hours, and the target product is obtained through a condensation reaction between the ketone compound and the ester compound.

[0030] Method 2: S1. React ketone compounds containing the R group in solvent B in the presence of base A for 5–120 min.

[0031] S2. The ester compound containing rosin group continues to react for 0.5 to 25 hours, and the target product is obtained through the condensation reaction between the ketone compound and the ester compound.

[0032] Furthermore, steps S1 and S2 are both performed under the protection of an inert gas. Preferably, the inert gas is nitrogen, argon, or helium; for example, nitrogen is the inert gas.

[0033] Further, in step S1, the base A, solvent B, and ketone compound undergo an ice bath reaction for a period of 5–120 min.

[0034] Preferably, in step S1, the reaction time is 30 to 60 minutes.

[0035] Furthermore, the reaction temperature in step S2 is 0–150°C, the reaction time is 0.5–25 hours, and the reaction is quenched after completion.

[0036] It should be noted that if the reaction temperature is higher than 150℃, the reaction is prone to producing by-products, which will affect the yield of the target product, and the solvent will easily evaporate; if the temperature is too low, the reaction rate will be slow and the reaction efficiency will be low.

[0037] Furthermore, in step S2, the reaction is quenched with ethanol or water after completion.

[0038] Preferably, in step S2, the reaction temperature is 0–100°C and the reaction time is 6–12 h, for example, the reaction time is 12 h.

[0039] Further, step S2 includes:

[0040] The process includes the ice bath feeding stage, the heating stage, the isothermal reaction stage, and quenching after the reaction is completed.

[0041] The reaction time of the isothermal reaction stage is 0.5 to 24 hours, and the reaction temperature is 0 to 150°C.

[0042] Preferably, the reaction temperature in the isothermal reaction stage is 25–100°C.

[0043] Furthermore, after the reaction is complete, the separation of the target product includes: adjusting the pH of the solution to neutral with dilute hydrochloric acid, extracting the organic phase of the solution with dichloromethane, extracting the obtained organic phase by vacuum distillation, and purifying the target product by silica gel column chromatography with dichloromethane and petroleum ether.

[0044] The present invention also provides an application of the aforementioned rosin-based β-diketone derivative as a lithium extractant.

[0045] 3. Beneficial effects

[0046] Compared with the prior art, the technical solution provided by this invention has the following advantages:

[0047] (1) The rosin-based β-diketone derivative provided in this invention has a rosin group containing 20 carbon atoms and a stable and compact aliphatic ring, exhibiting strong lipophilicity and hydrophobicity. Therefore, the rosin-based β-diketone derivative has strong hydrophobicity and stability. When used as a lithium extractant, it can reduce dissolution loss in the aqueous phase during use, reduce water pollution, promote the transfer of lithium to the organic phase, and avoid the formation of a third phase during extraction. Moreover, this derivative has a high boiling point, exceeding 200°C, resulting in low volatilization loss, no odor, low toxicity, low environmental pollution, and a good operating environment.

[0048] (2) The rosin-based β-diketone derivative of the present invention has a rosin group derived from rosin, which is a renewable resource, widely available, and inexpensive natural product, which can greatly reduce the production and use costs of the derivative. Detailed Implementation

[0049] This disclosure can be more readily understood by referring to the following description in conjunction with examples, all of which form part of this disclosure. It should be understood that this disclosure is not limited to the specific products, methods, conditions, or parameters described and / or shown herein. Furthermore, the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting, unless otherwise stated.

[0050] It should also be understood that, for clarity, certain features of this disclosure may be described herein in the context of individual embodiments, but may also be provided in combination with each other in individual embodiments. That is, unless obviously incompatible or specifically excluded, each individual embodiment is considered to be combinable with any other embodiment, and such combination is considered to represent another different embodiment. Conversely, for brevity, various features of this disclosure described in the context of individual embodiments may also be provided individually or in any sub-combination. Finally, while a particular embodiment may be described as part of a series of steps or part of a more general structure, each step or substructure may also be considered an independent embodiment in itself.

[0051] Unless otherwise stated, it should be understood that each individual element in the list and each combination of individual elements in the list will be interpreted as a different embodiment. For example, a list of embodiments denoted as "A, B, or C" should be interpreted as including embodiments "A", "B", "C", "A or B", "A or C", "B or C", or "A, B, or C".

[0052] In this disclosure, the singular forms of the articles “a,” “one,” and “the” also include the corresponding plural references, and references to a particular value include at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to “substance” is a reference to at least one of such substance and its equivalents.

[0053] Ordinal terms such as “first” and “second” may be used to describe various components or fluids, but these components and fluids are not limited by these terms. Therefore, without departing from the teachings of this disclosure, these terms are used only to distinguish one component / fluid from another.

[0054] When an item is described using the combined terms “...and / or ...", the description should be understood to include any one of the listed items and all combinations thereof.

[0055] Generally, the use of the term "about" indicates an approximation that can vary depending on the desired characteristics obtained from the disclosed subject matter and will be interpreted in a context-dependent manner based on function. Therefore, those skilled in the art will be able to interpret a degree of difference on a case-by-case basis. In some cases, the number of significant figures used when expressing a particular value can be a representative technique for determining the difference allowed by the term "about." In other cases, a gradient within a range of values ​​can be used to determine the range of differences allowed by the term "about." Furthermore, all ranges in this disclosure are inclusive and composable, and references to values ​​within a range include every value within that range.

[0056] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains; the terms used herein and / or include any and all combinations of one or more of the associated listed items.

[0057] Unless otherwise specified in the following examples, the conditions were performed under standard conditions or as recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0058] The present invention will be further illustrated below with reference to specific embodiments, but these embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field. The essential features and significant effects of the present invention can be seen from the following embodiments. The described embodiments are some, but not all, embodiments of the present invention, and therefore do not limit the present invention in any way. Any non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are within the protection scope of the present invention.

[0059] The raw material Y1 was prepared by a nucleophilic substitution reaction according to the method reported in the literature (Cambie; Fullerton, Australian Journal of Chemistry, 1971, vol. 24, pp. 2611-2620);

[0060] Raw material Y2 was prepared by esterification reaction according to the method reported in the literature (Hou, Wei; Luo, Zhi; Zhang, Guanjun; Cao, Danhui; Li, Di; Ruan, Haoqiang; Ruan, Benfang Helen; Su, Lin; Xu, Hongtao, European Journal of Medicinal Chemistry, 2017, vol. 138, p. 1042-1052);

[0061] The raw material Y3 was prepared by esterification according to the method reported in any of the following literature: Rafferty, Ryan J.; Hicklin, Robert W.; Maloof, Katherine A.; Hergenrother, Paul J., Angewandte Chemie-International Edition, 2014, vol. 53, 1, pp. 220-224; Rafferty, Ryan J.; Hicklin, Robert W.; Maloof, Katherine A.; Hergenrother, Paul J., Angew. Chem., 2014, vol. 126, 1, pp. 224-228, 5; or Zhou, Bing; Li, Xiaomei; Feng, Huijin; Li, Yuanchao, Tetrahedron, 2010, vol. 66, 29, pp. 5396-5401.

[0062] The raw material Y4 was prepared by esterification according to the method reported in the literature (Huffman et al., Journal of Organic Chemistry, 1970, vol. 35, pp. 473-478).

[0063] Using Y1 to Y4 prepared by the above method as raw materials for the preparation of rosin-based β-diketone derivatives in this invention has the advantages of short route and low cost.

[0064] In the corresponding examples, the molar amount of the solvent 50 mL tetrahydrofuran was 618 mmol, the molar amount of 20 mL N,N-dimethylformamide was 260 mmol, and the molar amount of 50 mL 1,4-dioxane was 568 mmol.

[0065] Example 1

[0066] Sodium hydride (1.2 g, 50 mmol) was weighed and added to a 250 mL round-bottom reaction flask. The mixture was evacuated and purged with N2 gas three times. After 5 minutes in an ice bath, tetrahydrofuran (50 mL) and starting material Y1 (3 g, 10 mmol) were injected. After 30 minutes in an ice bath, ethyl trifluoroacetate (18 mL, 150 mmol) was injected. After stabilization, when bubbles were not obvious, the temperature was increased and the reaction was carried out at 80 °C for 12 hours. After the reaction was completed, the reaction was quenched with ethanol in an ice bath. The pH was adjusted to neutral with dilute hydrochloric acid, and the organic phase was extracted with dichloromethane. After the solvent was evaporated under reduced pressure, the product was purified by column chromatography with dichloromethane and petroleum ether to obtain 2.74 g of pale yellow oily product, with a yield of 69%.

[0067] NMR of the product:1 H NMR (400MHz, CDCl3) δ15.14(br,1H),7.19(d,J=8.2Hz,1H),7.03(dd,J=8.2,1.5 Hz,1H),6.90(s,1H),6.17(s,1H),2.89-2.80(m,3H),2.37(d,J=12.8Hz,1H),2.1 5(dd,J=12.6,2.1Hz,1H),1.89-1.76(m,3H),1.72(dd,J=12.9,4.2Hz,1H),1.59- 1.51(m,2H),1.42-1.36(m,1H),1.28(s,3H),1.26(s,3H),1.23(d,J=6.9Hz,6H). 19 F NMR (377MHz, CDCl3) δ-75.95 (s, CF3).

[0068] Product mass spectra: HRMS ((+)-ESI): m / z = 395.2220 (calcd. 395.2198 for [C 23 H 30 F3O2][M+H] + ).

[0069] The reaction formula is as follows:

[0070]

[0071] Example 2

[0072] Sodium methoxide (1.08 g, 20 mmol) was weighed and added to a 250 mL round-bottom reaction flask. The mixture was evacuated and purged with argon three times. N,N-dimethylformamide (20 mL) and raw material Y1 (3 g, 10 mmol) were injected under ice bath and stirring. After 10 minutes, ethyl trifluoroacetate (3 mL, 25 mmol) was injected. After stabilization, the formation of bubbles was minimal. The ice bath was removed and the temperature was raised to 140 °C for 2 h. After the reaction was completed, the mixture was quenched with water under ice bath conditions. The pH was adjusted to neutral with dilute sulfuric acid. The organic phase was extracted with ethyl acetate. After the solvent was evaporated under reduced pressure, the mixture was purified by column chromatography with dichloromethane and petroleum ether to obtain 1.6 g of pale yellow oily product, with a yield of 40%.

[0073] Example 3

[0074] Potassium tert-butoxide (1.68 g, 15 mmol) was weighed and added to a 250 mL round-bottom reaction flask. The mixture was evacuated and purged with helium three times. 1,4-Dioxane (50 mL) and starting material Y1 (3 g, 10 mmol) were injected under ice bath and stirring. After 2 h, ethyl trifluoroacetate (6 mL, 50 mmol) was injected. After stabilization, when bubbles were not obvious, the temperature was increased, the ice bath was removed, and the temperature was increased to 100 °C for 6 h. After the reaction was completed, the mixture was quenched with water under ice bath conditions. The pH was adjusted to neutral with dilute phosphoric acid, and the organic phase was extracted with petroleum ether. After the solvent was evaporated under reduced pressure, the mixture was purified by column chromatography with dichloromethane and petroleum ether to obtain 1.98 g of pale yellow oily product, with a yield of 50%.

[0075] Example 4

[0076] Sodium hydride (1.2 g, 50 mmol) was weighed and added to a 250 mL round-bottom reaction flask. The mixture was evacuated and purged with N2 gas three times. After 5 minutes in an ice bath, tetrahydrofuran (50 mL) and starting material Y1 (3 g, 10 mmol) were injected. After 30 minutes in an ice bath, ethyl pentafluoropropionate (18 mL, 150 mmol) was injected. After stabilization, when bubbles were not obvious, the temperature was increased and the reaction was carried out at 80 °C for 12 hours. After the reaction was completed, the reaction was quenched with ethanol in an ice bath. The pH was adjusted to neutral with dilute hydrochloric acid, and the organic phase was extracted with dichloromethane. After the solvent was evaporated under reduced pressure, the product was purified by column chromatography with dichloromethane and petroleum ether to obtain 2.98 g of pale yellow oily product, with a yield of 67%.

[0077] NMR of the product: 1 H NMR (400MHz, CDCl3) δ15.33(br,1H),7.19(d,J=8.0Hz,1H),7.04(d,J=7.9Hz,1H),6.91(s,1H),6.23(s,1H),2.88-2.82(m,3H),2.37(d,J=12 .6Hz,1H),2.15(d,J=12.0Hz,1H),1.89-1.69(m,4H),1.61-1.52(m,2H),1.44-1.38(m,1H),1.29(s,3H),1.26(s,3H),1.24(d,J=6.8Hz,6H). 19 F NMR (377MHz, CDCl3) δ-82.79 (s, CF3), -123.80 (s, CF2).

[0078] Product mass spectra: HRMS ((+)-ESI): m / z = 445.2171 (calcd. 445.2166 for [C 24 H 30 F5O2][M+H] + ).

[0079] The reaction formula is as follows:

[0080]

[0081] Example 5

[0082] Sodium hydride (1.2 g, 50 mmol) was weighed and added to a 250 mL round-bottom reaction flask. The flask was evacuated and purged with N2 gas three times. After 5 minutes in an ice bath, tetrahydrofuran (50 mL) and starting material Y1 (3 g, 10 mmol) were injected. After 30 minutes in an ice bath, ethyl heptafluorobutyrate (26 mL, 150 mmol) was injected. After stabilization, when bubbles were not obvious, the temperature was increased and the reaction was carried out at 80 °C for 12 hours. After the reaction was completed, the reaction was quenched with ethanol in an ice bath. The pH was adjusted to neutral with dilute hydrochloric acid, and the organic phase was extracted with dichloromethane. After the solvent was evaporated under reduced pressure, the product was purified by column chromatography with dichloromethane and petroleum ether to obtain 3.3 g of pale yellow oily product, with a yield of 67%.

[0083] NMR of the product: 1 H NMR (400MHz, CDCl3) δ15.35(br,1H),7.21(d,J=8.2Hz,1H),7.05(d,J=8.0Hz,1 H),6.92(s,1H),6.23(s,1H),2.94-2.81(m,3H),2.39(d,J=12.9Hz,1H),2.17(d d,J=12.5,1.7Hz,1H),1.91-1.77(m,3H),1.72(dd,J=13.0,4.1Hz,1H),1.62-1 .53(m,2H),1.45-1.40(m,1H),1.31(s,3H),1.28(s,3H),1.25(d,J=6.9Hz,6H). 19 F NMR (377MHz, CDCl3) δ -80.58 (t, J = 9.4Hz, CF3), -121.60 (q, J = 9.4Hz, CF2), -126.95 (s, CF2).

[0084] Product mass spectra: HRMS ((+)-ESI): m / z = 495.2140 (calcd. 495.2134 for [C 25 H 30 F7O2][M+H] + ).

[0085] The reaction formula is as follows:

[0086]

[0087] Example 6

[0088] Sodium hydride (1.2 g, 50 mmol) was weighed and added to a 250 mL round-bottom reaction flask. The flask was evacuated and purged with N2 gas three times. After 5 minutes in an ice bath, tetrahydrofuran (50 mL) and 2-acetylpyridine (1.2 g, 10 mmol) were injected. After 30 minutes in an ice bath, a tetrahydrofuran solution containing 3.1 g, 10 mmol of the starting material Y2 (50 mL of tetrahydrofuran) was injected. After the addition was complete, the ice bath was removed, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the mixture was quenched with ethanol in an ice bath. The pH was adjusted to neutral with dilute hydrochloric acid, and the organic phase was extracted with dichloromethane. After the solvent was evaporated under reduced pressure, the mixture was purified by column chromatography with dichloromethane and petroleum ether to obtain 2.0 g of a pale yellow oily product, with a yield of 50%.

[0089] NMR of the product: 1 H NMR (400MHz, CDCl3) δ8.66(d,J=4.7Hz,1H),8.03(d,J=7.9Hz,1H),7.81(t,J=7.3Hz,1H),7.44(t,J=6.7Hz,1H),7.14(d,J=8.2Hz,1H),6.97(d,J =8.2Hz,1H),6.86(s,1H),3.56(s,2H),2.95-2.76(m,3H),2.33-2.09(m, 2H),1.95-1.44(m,7H),1.23(s,3H),1.25(d,J=4.4Hz,6H),1.19(s,3H).

[0090] Product mass spectra: HRMS ((+)-ESI): m / z = 404.2598 (calcd. 404.2590 for [C 27 H 34 NO2][M+H] + ).

[0091] The reaction formula is as follows:

[0092]

[0093] Example 7

[0094] Sodium ethoxide (3.4 g, 50 mmol) was weighed and added to a 250 mL round-bottom reaction flask. The flask was evacuated and purged with N2 gas three times. Tetrahydrofuran (50 mL) and 1,1,1-trifluoroacetone (2.2 g, 20 mmol) were injected under ice bath and stirring. After 60 minutes, a tetrahydrofuran solution containing the starting material Y3 (3.2 g, 10 mmol) (containing 50 mL of tetrahydrofuran) was injected. After the addition was complete, the ice bath was removed, and the reaction was stirred at room temperature for 12 h. After the reaction was completed, the reaction was quenched with ethanol under ice bath conditions. The pH was adjusted to neutral with dilute hydrochloric acid, and the organic phase was extracted with dichloromethane. After the solvent was evaporated under reduced pressure, 1.8 g of a pale yellow oily product was obtained, with a yield of 45%.

[0095] NMR of the product: 1 H NMR (400MHz, CDCl3) δ16.77(s,1H),7.02(s,1H),5.70-5.80(m,1H),5.45-5.55(m,1H),1.90-2.50(m ,5H),1.70-1.80(m,1H),1.50-1.70(m,3H),1.30-1.50(m,5H),1.10-1.30(m,7H),0.80-0.90(m,6H).

[0096] Product mass spectra: HRMS ((+)-ESI): m / z = 397.2360 (calcd. 397.2354 for [C 23 H 32 F3O2][M+H] + ).

[0097]

[0098] Example 8

[0099] Sodium ethoxide (3.4 g, 50 mmol) was weighed and added to a 250 mL round-bottom reaction flask. The mixture was evacuated and purged with N2 gas three times. Tetrahydrofuran (50 mL) and 1,1,1-trifluoroacetone (2.2 g, 20 mmol) were injected under ice bath and stirring. After 60 minutes, a tetrahydrofuran solution containing the starting material Y4 (3.2 g, 10 mmol) (containing 50 mL of tetrahydrofuran) was injected. After the addition was complete, the ice bath was removed, and the reaction was stirred at room temperature for 12 h. After the reaction was completed, the mixture was quenched with ethanol under ice bath conditions. The pH was adjusted to neutral with dilute hydrochloric acid, and the organic phase was extracted with dichloromethane. After the solvent was evaporated under reduced pressure, 1.6 g of a pale yellow oily product was obtained, with a yield of 40%.

[0100] NMR of the product: 1H NMR (400MHz, CDCl3) δ16.78(s,1H),7.03(s,1H),1.50-1.80(m,7H),1.31-1.50(m,9H),1.00-1.30(m,8H),0.80-0.90(m,9H).

[0101] Product mass spectra: HRMS ((+)-ESI): m / z = 401.2671 (calcd. 401.2667 for [C 23 H 36 F3O2][M+H] + ).

[0102]

[0103] Example 9

[0104] Lithium extraction performance test

[0105] Take 20 mL of product S1 from Example 1 as the extractant, 20 mL of tributyl phosphate as the co-extractant, and 60 mL of ethyl acetate, mix them, and place them in a separatory funnel. Add 100 mL of an aqueous solution containing 0.74 g of lithium carbonate, shake and extract for 10 minutes, then separate the organic phase. No third phase is generated during the extraction process, and the organic phase and aqueous phase can be separated rapidly. The loaded organic phase is mixed with 20 mL of 1 mol / L hydrochloric acid solution to back-extract lithium ions.

[0106] Atomic absorption spectroscopy analysis showed that the lithium ion extraction rate was as high as 82%, and the back-extraction recovery rate was as high as 95%. This indicates that the extractant can be used for efficient lithium ion extraction.

Claims

1. A rosin-based β-diketone derivative, characterized in that, It has the structure shown in equation (I): ； In the formula, R is a fluoroalkyl or substituted aryl group containing 1 to 8 carbon atoms; the substituent in the substituted aryl group is one of an alkyl group containing 1 to 8 carbon atoms or a fluoroalkyl group containing 1 to 8 carbon atoms, and the aryl group in the substituted aryl group is one of benzene, pyridine, pyrazine, pyridazine, thiophene, and furan.

2. The rosin-based β-diketone derivative according to claim 1, characterized in that: The rosin-based β-diketone derivative is one of the following compounds: 、 、 。 3. The method for preparing the rosin-based β-diketone derivative according to claim 1 or 2, characterized in that, Includes the following steps: S1. React ketone compounds in solvent B for a period of time in the presence of base A; S2. Add ester compounds and continue the reaction for a period of time to obtain the target product through a condensation reaction between ketone compounds and ester compounds; Wherein, any one of the ketone compounds and ester compounds contains a rosin group, and the other compound contains an R group.

4. The method for preparing the rosin-based β-diketone derivative according to claim 3, characterized in that: The molar ratio of the ketone compound, ester compound, base A and solvent B is 1:(0.1~20):(1~6):(20~300).

5. The method for preparing the rosin-based β-diketone derivative according to claim 3, characterized in that: The alkali A mentioned includes one, two or more of the following: sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide. Solvent B includes one, two or more of the following: tetrahydrofuran, diethyl ether, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide, ethanol, methanol, benzene, toluene, xylene, hexane, and petroleum ether.

6. The method for preparing the rosin-based β-diketone derivative according to claim 3, characterized in that: The ketone compounds are: ， The ester compound is selected from any one of ethyl trifluoroacetate, ethyl pentafluoropropionate, and ethyl heptafluorobutyrate. Alternatively, the ketone compound may be 1,1,1-trifluoroacetone, and the ester compound may be: 。 7. The method for preparing the rosin-based β-diketone derivative according to claim 3, characterized in that: Both steps S1 and S2 are performed under inert gas protection.

8. The method for preparing the rosin-based β-diketone derivative according to claim 7, characterized in that: The reaction temperature in step S2 is 0~150℃, the reaction time is 0.5~25h, and the reaction is quenched after completion.

9. The method for preparing the rosin-based β-diketone derivative according to claim 8, characterized in that: Step S2 includes: The process includes the ice bath feeding stage, the heating stage, the isothermal reaction stage, and quenching after the reaction is completed. The reaction time for the isothermal reaction stage is 0.5 to 24 hours, and the reaction temperature is 25 to 150°C.

10. The method for preparing a rosin-based β-diketone derivative according to claim 8, characterized in that: In step S1, the base A, solvent B, and ketone compound undergo an ice bath reaction for 5 to 120 minutes.

11. The use of a rosin-based β-diketone derivative as described in claim 1 or 2, or a rosin-based β-diketone derivative obtained by any one of claims 3-10, as a lithium extractant.

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