KR20160115540A - Lithium selective crown ether and method for manufacturing the same - Google Patents

Abstract

The present invention relates to lithium-selective crown ethers and processes for their preparation, and more particularly to novel crown ethers having large bulk and hard groups and processes for their preparation.
The present invention provides a lithium-selective crown ether capable of efficiently recovering lithium ions through intramolecular cyclization of bulky epoxides and compounds comprising a hard aromatic group such as 1,2 dihydroxybenzene . According to the present invention, the rigidity of the crown ether skeleton can be improved by the hard aromatic group to prevent the preorganization effects and the blocking mechanism by the bulky subunits prevents the formation of complex ions of the large metal ions can do. As a result, lithium ions can be more efficiently recovered.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a lithium-selective crown ether and a method for producing the same,

The present invention relates to lithium-selective crown ethers and processes for their preparation, and more particularly to novel crown ethers having large bulk and hard groups and processes for their preparation.

12 to 14 membered crown ether rings are known to form stable complexes with lithium ions (Li ⁺ ) in both aqueous and aqueous solutions containing alkali metal ions. Specifically, dibenzo-14-crown-4 ether (DB14C4) and its derivatives can be used to form benzo groups that provide rigidity and complex formation with lithium ions Has been known as a lithium ion complex (Li + complexant) because of its 14-crown-4 ether backbone with ideal cavity dimensions. However, since DB14C4 is difficult to synthesize, it has only been applied as a carrier in electrodes with high sensitivity to lithium ions or as a carrier in liquid-liquid extraction systems. There have been attempts to develop new efficient methods for the synthesis of DB14C4, but there is a problem that it is difficult to prevent complex formation with metal ions larger than lithium ions.

In order to solve the above problems, the present inventors have found that the use of bulky bis-epoxide and a hard aromatic group such as 1,2-dihydroxybenzene The present invention provides a process for synthesizing lithium-selective crown ethers by intermolecular cyclization of compounds. The crown ether has both rigid and bulky subunits. Rigid aromatic groups can improve the rigidity of the crown ether backbone and bulky subunits can enhance the blocking mechanism to prevent the formation of complexes of larger metal ions, Can be provided.

Bartsch, R. A .; Czech, B.P .; Kang, S.I .; Stewart, L. E .; Wlkowiak, W .; Charewicz, W.A .; Heo, G.S .; Son, B. J. Am. Chem. Soc., 1985, 107, 4997-4998. Sachleben, R. A ,; Davis, M. C.; Bruce, J.J .; Ripple, E.S .; Driver, J. L .; Moyer, B.A. Tetrahedron Lett. 1993, 34, 34, 5373-5376. Sachleben, R. A .; Burns, J.H. J. Chem. Soc. Perkin Trans. 1992, 1971-1977.

The present invention provides novel crown ethers having large bulky and hard groups. Also provided is a process for preparing lithium-selective crown ethers by intermolecular cyclization of compounds containing bulky epoxides and hard aromatic groups.

The present invention relates to a process for preparing a di-alkene compound by reacting a diol with an allyl compound (step a); Reacting the di-alkene compound with benzoic acid to synthesize a bis-epoxide (step b); And a step (c) of reacting the bis-epoxide with hydroxybenzene to cyclize the lithium-selective crown ether.

Synthesis of di-alkene compounds

The step a may be carried out by mixing the diol and the allyl compound at a molar ratio of 1: 2 and refluxing for 12 to 48 hours, more preferably for 24 hours.

The diol may be selected from the group consisting of pinacol, 2,2-diethyl-1,3-propanediol, [1,1'-bicyclopentyl] -1 1,2'-cyclohexanediol, and cis-1,2-cyclohexanediol, and the cis-1,2-cyclohexanediol, And cyclopentanediol. The term " cis-1,2-cyclopentanediol "

The allyl compound may be allyl bromide.

The di-

,

,

,

And

≪ RTI ID = 0.0 > and / or < / RTI >

Bis-epoxide synthesis step

Step b above may be carried out by mixing the di-alkene compound with benzoic acid in a molar ratio of 1: 2.5 and stirring at room temperature for 12 to 36 hours, more preferably for 24 hours.

The benzoic acid may be m-chloroperbenzoic acid (m-CPBA).

The bis-

,

,

,

And

And at least one selected from the group consisting of

Cyclization step

Step c) may be carried out by adding bis-epoxide to a solution in which hydroxybenzene and metal hydroxide are dissolved and reacting.

Specifically, step c) may be carried out by adding a bis-epoxide to a solution in which benzene and a metal hydroxide are dissolved, and stirring for 3 to 9 hours, more preferably 6 hours. Further, after the step of stirring, the metal hydroxide may be further added.

More specifically, the step c is carried out by adding a bis-epoxide equivalent to the hydroxybenzene to a solution of hydroxybenzene and a metal hydroxide dissolved at a molar ratio of 1: 1, stirring the mixture, , And refluxing for 36 to 54 hours, more preferably for 42 hours. The refluxing may be carried out by stirring in a reflux condition.

The hydroxybenzene may be 1,2-dihydroxybenzene.

The metal hydroxide may include at least one selected from the group consisting of LiOH, NaOH and KOH. The metal hydroxide may serve as a catalyst (a template ion). Template ions play an important role in promoting cyclization. If the template ion does not have the proper size for the desired crown ether preparation, it may be difficult to obtain the expected yield.

The solution of step c may comprise at least one selected from the group consisting of t-BuOH, THF, and a mixture of THF and H ₂ O as a solvent.

The crown ether may be,

,

,

,

And

≪ RTI ID = 0.0 > and / or < / RTI >

The present invention also relates to a process for preparing a di-alkene compound by reacting a diol with allyl bromide to synthesize a di-alkene compound; Reacting the di-alkene compound with m-chloroperbenzoic acid to synthesize a bis-epoxide; And cyclizing the 1,2-dihydroxybenzene by reacting the bis-epoxide with 1,2-dihydroxybenzene, wherein the cyclization comprises reacting bis-epoxide with 1,2-dihydroxybenzene in a solution of 1,2-dihydroxybenzene and NaOH in t- -Epoxide is added to the reaction mixture to react with the lithium-containing crown ether. The details of each step and the like are the same as those described above, and thus will be omitted.

The present invention also relates to a process for preparing a di-alkene compound by reacting a diol with an allyl compound to synthesize a di-alkene compound; And reacting the di-alkene compound with benzoic acid to produce a bis-epoxide.

Reacting the diol with allyl bromide to synthesize a di-alkene compound; And reacting the di-alkene compound with m-chloroperbenzoic acid to synthesize a bis-epoxide.

Diol, allyl compound, di-alkene compound, benzoic acid, bis-epoxide and the like are the same as those described in the above-mentioned crown ether preparation method,

Further, according to the present invention,

,

,

,

And

Lt; RTI ID = 0.0 > crown < / RTI > ether comprising a compound selected from the group consisting of:

Further, according to the present invention,

,

,

,

And

Epoxide comprising a compound selected from the group consisting of: < RTI ID = 0.0 >

The present invention provides a lithium-selective crown ether capable of efficiently recovering lithium ions through intramolecular cyclization of bulky epoxides and compounds comprising a hard aromatic group such as 1,2 dihydroxybenzene . According to the present invention, it is possible to improve the rigidity of the crown ether skeleton by the hard aromatic group to block preorganization effects and to provide a shut-off mechanism by a bulky subunit, Complex formation can be prevented. As a result, the lithium ion selectivity can be remarkably improved, and as a result, lithium ions can be efficiently recovered.

1 shows the results of ¹ H NMR analysis of 14-crown-4 ether 1 according to an embodiment of the present invention.
2 shows the results of ¹ H ¹³ C NMR analysis of 14-crown-4 ether 1 according to an embodiment of the present invention.
3 shows the ¹ H NMR analysis results of 14-crown-4 ether 2 according to an embodiment of the present invention.
4 shows the results of ¹ H ¹³ C NMR analysis of 14-crown-4 ether 2 according to an embodiment of the present invention.
FIG. 5 shows the ¹ H NMR analysis results of 14-crown-4 ether 3 according to an embodiment of the present invention.
FIG. 6 shows ¹ H ¹³ C NMR analysis results of 14-crown-4 ether 3 according to an embodiment of the present invention.
Figure 7 is a graphical representation of the synthesis of dialkane 1 (2,3-bis (allyloxy) -2,3-dimethylbutane, 2,3-bis (allyloxy) -2,3-dimethylbutane) ≪ ¹ > H NMR analysis.
8 shows the ¹³ C NMR analysis results of dialkane 1 (2,3-bis (allyloxy) -2,3-dimethylbutane) synthesized according to an embodiment of the present invention.
Figure 9 is a schematic diagram of an embodiment of the bis-epoxide 1 (2,2 '- (2,3-dimethylbutane-2,3-diyl) bis (methylene) bis 2 '- (2,3-dimethylbutane- 2,3-diyl) bis shows a ¹ H NMR analysis of the (methylene) bis (oxirane)) .
10 is a service according to an embodiment of the present invention - ¹³ - ((2,3-dimethyl-butane-2,3-yl) bis (methylene) bis (oxirane) 2,2 ') epoxide 1 C NMR analysis results.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings and examples. The objects, features, and advantages of the present invention will be readily understood from the following detailed description. The present invention is not limited to the contents described here, but may be embodied in other forms. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. Therefore, the present invention should not be limited by the specific details for carrying out the following invention.

Example: Synthesis of lithium-selective crown ether (dihydroxy-14-crown-4 ether)

Reagents and laboratory equipment

Solvents, reagents, starting bulky diols and commercially available bis-epoxides were purchased from Sigma-Aldrich Korea or Fischer Scientific. NaH was washed with pentane (pentane) to remove the protective five days (protecting oil), to remove impurities m - chloroperbenzoic benzoic acid (m -chloroperbenzoic acid) was dissolved in ethyl ether (Ethyl ether) phosphate buffer and washed with phosphate buffer. All other compounds were used without purification. The structures of the synthesized novel compounds were confirmed by ¹ H and ¹³ C NMR (Varian, 400 MR Fourier Transform Nuclear Magnetic Resonance) in FTIR (Varian 2000) at 400 MHz and 100 MHz, respectively.

Synthesis of di-alkene intermediate

An equimolar diol solution was added to dry THF (Anhydrous THF, 200 mL), dissolved for 30 minutes, and mixed under argon at room temperature for 1 hour. To the mixture was added allyl bromide (1: 2 mole ratio diol : allyl bromide), and the mixture was stirred for 1 hour and the mixture was refluxed for 24 hours. The solution was slowly quenched into water and the solvent was removed in vacuo. It was then washed with water. The aqueous layer was extracted twice with dichloromethane and the organic layers were washed, dried over magnesium sulfate (MgSO ₄ ), concentrated and the residue was purified by silica gel column chromatography using ethyl acetate / .

Synthesis of bis-epoxide intermediate

Of chloroform at 0 ℃ m-chloroperbenzoic benzoic acid (m -chloroperbenzoic acid m-CPBA. ) To the stirred solution was added for 30 minutes during which the die was dissolved in dichloromethane-alkene intermediate (1: 2.5 mole ratio di -alkene : m -CPBA). The mixture was dried for 24 hours at room temperature while stirring, filtered and then washed with 10% NaHCO _3, MgSO _4. The solvent was removed in vacuo and purified using silica gel chromatography using dichloromethane as eluent.

Intramolecular cyclization of bis-epoxide with 1,2-dihydroxybenzene.

A solution prepared by adding equimolar amounts of 1,2-dihydroxybenzene and a suitable metal hydroxide to a suitable solvent (50 mL / mmol substrate) was refluxed under argon Then, a reaction mixture was prepared by adding 1: 1 mole ratio bis-epoxide (1,2-dihydroxybenzene) and stirred for 6 hours. Then, the same amount of metal hydroxide as above was further added, and the mixture was stirred and refluxed for 42 hours. The solvent was evaporated in vacuo and the residue was dissolved in chloroform. The chloroform solution was washed with water and the water layers were back-extracted with chloroform. The chloroform layers were dried over MgSO ₄ , filtered and evaporated in vacuo. The residue was dissolved in methanol and purified with alumina and silica using an ethyl acetate / methanol mixture as eluent.

Solvent and template effects analysis

To obtain optimum conditions for the synthesis of di-hydroxy functionalized crown ether via intramolecular cyclization of bis-epoxide and 1,2-dihydroxybenzene (see Scheme 1) Tests were conducted using various solvents and metal hydroxides (metal ion catalyst / template), and the results are shown in Table 1. Table 1 shows the results of cyclization with a commercially available bis-epoxide. When using t-BuOH as a solvent, NaOH as a catalyst and a template, a cyclized product was obtained in a yield of 70%. It is believed that t-BuOH exhibited improved yield due to good solvency to aromatic alkoxides such as 1,2-dihydroxybenzene. In order to serve as a template for facilitating the cyclization reaction, the metal hydroxide catalyst should fit the size of the target crown ether. When NaOH is used as a catalyst (template) to react 1,2-dihydroxybenzene with neopentyl glycol diglycidyl ether, small LiOH or much larger It was confirmed that the yield was better than using KOH.

[Reaction Scheme 1]

Intramolecular cyclization of bis-epoxide and 1,2-dihydroxybenzene

[Table 1]

Solvent and metal ion effect

^a reaction was carried out using a 1: 1 molar ratio of bis-epoxide and 1,2-dihydroxybenzene

^b Structure confirmed by ¹ H and ^{13 C} NMR

^c Tracing of the target compound identified using TLC (trace of target compound seen using TLC)

Synthesis of bulky and rigid 14-crown-4 ether (bulky and rigid bulky-14-crown-4 ether)

Units with bulky and rigid subunits by intramolecular cyclization of bulky bis-epoxides and bulky bis-epoxide with 1,2-dihydroxybenzene, Di-hydroxy functionalized 14-crown-4 ether was synthesized (see Scheme 2 and Table 2). Specifically, for the synthesis of di-alkene intermediates, bis (2-hydroxyethyl) amines containing bulky groups by reaction of allyl bromide with bulky starting diols -Epoxide was synthesized and epoxidation of terminal alkenes was carried out using m-CPBA (see Scheme 2).

[Reaction Scheme 2]

Intramolecular cyclization using bulky bis-epoxides

The results of the synthesis of bulky and rigid 14-crown-4-ether are shown in Table 2. 14-crown-4-ether was synthesized with a high yield according to the cyclization of bis-epoxide containing 1,2-dihydroxybenzene with bulky subunits and 1,2-dihydroxybenzene. The synthesized bis-epoxide (diglycidyl ether) was cyclized by reacting with 1,2-dihydroxybenzene. The 14-crown-4 ether synthesized according to the cyclization was 74 Yield of ~ 92%. The overall yield of di-hydroxy-14-Crown-4 ether with bulky and rigid groups with large volume and rigid groups (rigid group) neutral counterpart. This is because 1,2-dihydroxybenzene exhibits high activity as a nucleophile for the ring opening of the bis-epoxide which promotes cyclization.

[Table 2]

Intramolecular cyclization of bulky bis-epoxide and 1,2-dihydroxybenzene

According to one embodiment of the invention, the intramolecular cyclization reaction of bis-epoxide with 1,2-dihydroxybenzene leads to the formation of di-hydroxy functionalized 14 (all of which have both large and rigid groups - di-hydroxy functionalized 14-crown-4 ether can be synthesized with high yield. New crown ethers having both such large and hard groups are capable of efficiently recovering lithium ions from seawater or the like. The hydroxyl groups of the crown ether may also be modified to other functional groups for other applications. Specifically, for the fluoroionophore, the lithium battery electrolyte for sensing, the proton ionizable side arm for the liquid-liquid extraction of lithium, or the solid solution of lithium for the solid-liquid extraction of lithium, Can be modified to other functional groups for application to the support,

Structural analysis of synthesized new compounds

The structures of the novel compounds synthesized above (see Table 2) were confirmed by ¹ H and ¹³ C NMR (Varian, 400 MR Fourier Transform Nuclear Magnetic Resonance) (see FIGS. 1 to 10).

14-crown-4-ether 1:

7,7-dimethyl-3,4,6,7,8,10,11,12-octahydro-2H-benzo [1,4,8,12] tetraoxacyclopentadisine-3,11-di (7,7-dimethyl-3,4,6,7,8,10,11,12-octahydro-2H-benzo [1,4,8,12] tetraoxacyclopentadecine-3,11-diol)

Purification by column chromatography using eluent methanol / chloroform (5: 1) yielded 3.1 g (70%) of pale yellow viscous liquid.

^{1 H NMR (400 MHz, CDCl} 3) δ (ppm): 0.72-0.81 (m, 6H, -CH 3); _{3.03-3.21 (m, 4H, -CH 2} -), 3.36-3.67 (m, 4H, -CH 2 -), 3.79-4.06 (m, 6H, -CH 2 -, -CH-), 4.95 (d, 2H, -OH), 6.73-7.02 (m, 4H, ArH).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 22.62, 37.05, 67.70, 71.03, 72.87, 77.43, 77.54, 113.67, 115.89, 121.60, 122.59,

14-crown-4-ether 2:

2,3,4,6,7,8,9,11,12,13 Dicabohydrobenzo [1,4,8,13] tetraoxacyclohexadizine-3,12-diol (2,3,4, , 6,7,8,9,11,12,13decahydro benzo [1,4,8,13] tetraoxacyclohexadecine-3,12-diol)

Purification by column chromatography using eluent methanol / chloroform (8: 1) gave 2.2 g (65%) of pale yellow viscous liquid.

_{^{1 HNMR (400MHz, CDCl 3)}} δ (ppm): 1.49 (s, 4H, -CH 2 -); _{3.14-3.64 (m, 10H, -CH 2} -, -CH-), 3.85-4.36 (m, 4H, -CH 2 -), 4.94 (2, 2H, -OH), 6.85-6.96 (m, 4H, ArH).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 25.07, 68.39, 69.84, 70.66, 71.45, 71.58, 115.49, 121.86, 149.10.

14-crown-4-ether 3:

6,6,7,7-tetramethyl-2,3,4,6,7,8,10,11-octahydrobenzo [1,4,8,11] tetraoxacyclotetradisine-3,10- Diol (6,6,7,7-tetramethyl-2,3,4,6,7,8,10,11-octahydrobenzo [1,4,8,11] tetraoxacyclotetradecine-3,10-diol)

Purification by column chromatography using eluent zero dichloromethane gave 1.2 g (85%) of pale yellow viscous liquid.

¹ H NMR (400 MHz, CDCl ₃ )? (Ppm): 1.06 (s, 12 H, 4 -CH ₃ ); _{3.13-3.44 (m, 4H, -CH 2} -), 3.76-3.89 (m, 5H, -CH 2 -, -CH-), 4.82 (s, 2H, -OH), 6.87-6.38 (m, 4H, ArH).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 20.24, 20.76, 62.44, 64.31, 69.15, 72.17, 78.59, 117.77, 121.58, 149.65.

Intermediate 1a:

2,3-bis (allyloxy) -2,3-dimethylbutane, 2,3-bis (allyloxy)

The residue was purified by column chromatography using eluent hexane / ethyl acetate (2: 1) to obtain 10.7 g (85%) of a clear liquid.

¹ H NMR (400 MHz, CDCl ₃ )? (Ppm): 1.18 (s, 12H, 4-CH ₃ ); _{3.97 (d, 4H, -CH 2} ), 5.03-5.06 (dd, 2H, = CH 2), 5.20-5.26 (dd, 2H, = CH 2), 5.84-5.93 (m, 2H, CH = CH 2) .

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 20.41, 62.86, 79.67, 114.21, 136.722.

Intermediate 2a:

3,3-bis (allyloxy) methylpentane (3,3-bis (allyloxy)

The residue was purified by column chromatography eluting with hexane / ethyl acetate (2: 1) to give 13.21 g (98%) of a clear liquid.

_{^{1 H NMR (400MHz, CDCl 3}} ) δ (ppm): 0.78 (t, 6H, 2-CH 3); _{1.58 (q, 4H, -CH 2} -), 3.20 (s, 4H, -CH 2 -), 3.91-3.93 (m, 4H, -CH 2 -), 5.10-5.13 (dd, 2H, = CH 2) , 5.21-5.26 (m, 2H, = CH 2), 5.82-5.92 (m, 2H, CH = CH 2).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 7.22, 23.26, 40.99, 72.13, 72.21, 116, 135.39.

Intermediate 3a:

1,1'-bis (allyloxy) -1,1'bi (cylopentane) 1,1'-bis (allyloxy)

The residue was purified by column chromatography using an eluent hexane / ethyl acetate (3: 1) to obtain 7.35 g (95%) of a clear liquid.

_{^{1 H NMR (400MHz, CDCl 3}} ) δ (ppm): 0.78 (t, 6H, 2-CH 3; 1.51-1.82 (m, 16H, 8CH 2 -), 3.97-3.99 (dd, 4H, 2-CH 2 -), 5.0-5.08 (m, 2H , = CH 2), 5.18-5.25 (m, 2H, = CH 2), 5.82-5.91 (m, 2H, CH = CH 2).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 26.44, 32.63, 66.94, 92.58, 114.18, 136.66.

Intermediate 4a:

1,2-bis (allyloxy) cyclohexane, 1,2-bis (allyloxy) cyclohexane,

The residue was purified by column chromatography using eluent hexane / ethyl acetate (3: 1) to obtain 8.44 g (90%) of a clear liquid.

_{^{1 H NMR (400MHz, CDCl 3}} ) δ (ppm): 0.83-1.27 (m, 2H, -CH 2 -), 1.37-1.43 (m, 2H, -CH 2 -), 1.54-1.61 (m, 2H, _{-CH 2 -), 1.77-1.84 (m} , 2H, -CH 2 -), 3.46-3.48 (dd, 2H, -CH-), 4.0-4.07 (dd, 4H, 2-CH 2 -), 5.06- 5.10 (m, 2H, = CH 2), 5.19-5.25 (m, 2H, = CH 2), 5.83-5.93 (m, 2H, CH = CH 2).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 27.62, 69.56, 70.02, 116.11, 135.72.

Intermediate 5a:

Bis (allyloxy) cyclopentane, 1,2-bis (allyloxy) cyclopentane,

The residue was purified by column chromatography using an eluent of hexane / ethyl acetate (3: 1) to obtain 8.92 g (92%) of a clear liquid.

_{^{1 H NMR (400MHz, CDCl 3}} ) δ (ppm): 1.17-1.40 (m, 1H, -CH 2 -), 1.41-1.44 (m, 1H, -CH 2 -), 1.68-1.1.97 (m, _{4H, -CH 2 -), 3.71-3.77} (m, 2H, -CH -), 3.98-4.05 (dd, 4H, 2-CH 2 -), 5.06-5.10 (m, 2H, = CH 2), 5.18 -5.24 (m, 2H, = CH 2), 5.83-5.92 (m, 2H, CH = CH 2).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 18.91, 27.95, 70.41, 79.76, 116.39, 135.38.

Intermediate 1b:

2,2 '- (2,3-dimethylbutane-2,3-diyl) bis (methylene) bis (oxirane) (methylene) bis (oxirane))

The residue was purified by column chromatography using an eluent of hexane / ethyl acetate (3: 1) to obtain 4.2 g (90%) of a clear liquid.

¹ H NMR (400 MHz, CDCl ₃ )? (Ppm): 1.15 (s, 12 H, 4 -CH ₃ ); 2.58 (dd, J = 4.8, 1.2Hz, 4H, -CH 2), 2.74 (t, J = 4.8Hz, 2H, -CH 2 -), 3.04-3.07 (m, 2H, -CH-), 3.39- _{3.43 (m, 2H, -CH 2} -), 3.52-3.66 (m, 2H, -CH 2 -).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 20.45, 44.64, 51.63, 62.75, 79.91.

Intermediate 2b:

2,2'- (2,2-diethylpropane-1,3-diyl) bis (oxy) bis (methylene) bis -diyl) bis (oxy) bis (methylene) bis (oxirane))

Purification by column chromatography using eluent zero dichloromethane gave 3.7 g (80%) of a clear liquid.

¹ H NMR (400 MHz, CDCl ₃ )? (Ppm): 0.753 (t, 6 H, J = 7.6, 2 -CH ₃ ); 1.23 (p, J = 7.6, 4H, -CH 2), 2.55-2.57 (m, 2H, -CH-), 2.73-2.76 (m, 2H, -CH-), 3.07-3.11 (m, 2H, - CH-), 3.23-3.53 (m, 4H , -CH 2 -), 3.64-3.67 (m, 4H, -CH 2 -).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 7.12, 7.16, 23.0, 41.19, 44.18, 51.03, 71.75, 71.78, 73.19.

Intermediate 3b:

Bis (oxiran-2-ylmethoxy) -1,1'-bi (cyclopentane) (1,1'- )

Purification by column chromatography using eluent zero dichloromethane gave 2.08 g (92%) of a clear liquid.

¹ H NMR (400 MHz, CDCl ₃ )? (Ppm): 1.20-2.01 (m, 16 H, 4 -CH ₃ ); 2.58-2.60 (m, J = 7.2, 2.8, 2.4, 1.2Hz, 2H, -CH 2), 2.73 (t, 2H, -CH 2), 3.04-3.07 (m, J = 2.4, 1.2Hz, 2H, J = 2.8, 2.4 Hz, 2H, -CH-), 4.08 (p, J = 7.2 Hz, 2H, -CH-).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 25.20, 35.41, 44.61, 44.62, 51.72, 63.57, 63.66, 92.83.

Intermediate 4b:

1,2-bis (oxiran-2-ylmethoxy) cyclohexane, 1,2-bis (oxiran-2-ylmethoxy)

Purification by column chromatography using eluent zero dichloromethane gave 3.85 g (94%) of a clear liquid.

¹ H NMR (400 MHz, CDCl ₃ )? (Ppm): 0.79-0.85 (m, J = 6.8, 6.4 Hz, 1H, 4 -CH-); (M, J = 6.4 Hz, 4 H, -CH ₂ -), 1.21 (s, 4 H, 2-CH ₂ ), 1.44-1.47 ), 2.56-2.59 (m, J = 2.8, 2.4Hz, 2H, -CH 2 -), 2.74-3.12 (m, J = 4.4Hz, 4Hz, 2H, -CH 2 -), 3.13-3.15 (m, . J = 4,2 4Hz, 2H, -CH-), 3.41-3.50 (m, 2H, -CH 2 -), 3.73-3.84 (m, 2H, -CH 2 -).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 14.01, 28.27, 28.58, 44.30, 44.30, 44.34, 44.47, 44.49, 51.06, 70.18, 70.25, 70.39, 70.50, 81.13, 81.21.

Intermediate 5b:

 Bis (oxiran-2-ylmethoxy) cyclopentane, 1,2-bis (oxiran-2-ylmethoxy)

Purification by column chromatography using eluent zero dichloromethane gave 4.4 g (85%) of a clear liquid.

¹ H NMR (400 MHz, CDCl ₃ )? (Ppm): 1.18-1.23 (m, J = 7.2, 3.6 Hz, 2 H, -CH ₂ -); 1.39-1.46 _{CH 2), 1.54-1.62 (m,} J = 9.2 Hz, 6 Hz, 2 H, -CH 2 -), 1.75-1.84 (m, J = 9.2, 6Hz, 2H, -CH 2 -), 2.56-2.59 (m, J = 2.8, 2.4Hz , 2H, -CH 2 -), 2.71-2.74 (m, J = 4.4Hz, 4Hz, 2H, -CH 2 -), 3.08-3.12 (m, 2H, -CH- ), 3.40-3.53 (m, 2H, -CH 2 -), 3.71-3.79 (m, 2H, -CH 2 -).

¹³ C NMR (100 MHz, CDCl ₃ ):? (Ppm) 14.10, 20.93, 21.87, 44.15, 44.26, 44.41, 44.43, 53.40, 63.63.

Claims (16)

Reacting a diol with an allyl compound to synthesize a di-alkene compound (step a);
Reacting the di-alkene compound with benzoic acid to synthesize a bis-epoxide (step b); and
(C) reacting said bis-epoxide with hydroxybenzene and cyclizing said bis-epoxide and said hydroxybenzene to form a lithium-selective crown ether.
The method according to claim 1,
The diol may be selected from the group consisting of pinacol, 2,2-diethyl-1,3-propanediol, [1,1 '-bicyclopentyl] -1,1'-diol, cis-1,2- And cis-1, 2-cyclopentane diol. 2. A process for preparing a lithium-selective crown ether, comprising:
The method according to claim 1,
Wherein the allyl compound is allyl bromide.
The method according to claim 1,
The di-

,

,

,

And

Wherein the lithium-containing crown ether comprises at least one member selected from the group consisting of lithium,
The method according to claim 1,
Wherein said benzoic acid is m-chloroperbenzoic acid.
The method according to claim 1,
The bis-

,

,

,

And

Wherein the lithium-containing crown ether comprises at least one member selected from the group consisting of lithium,
The method according to claim 1,
Lt; RTI ID = 0.0 > 1, < / RTI > wherein said hydroxybenzene is 1,2-dihydroxybenzene.
The method according to claim 1,
Wherein step c) is carried out by adding a bis-epoxide to a solution in which hydroxybenzene and a metal hydroxide are dissolved, and reacting the lithium-selective crown ether.
The method of claim 8,
Wherein the metal hydroxide comprises at least one selected from the group consisting of LiOH, NaOH, and KOH.
The method of claim 8,
Wherein the solvent of the solution comprises at least one selected from the group consisting of t-BuOH, THF, and a mixture of THF and H ₂ O.
The method according to claim 1,
The crown ether may be,

,

,

,

And

Wherein the lithium-containing crown ether comprises at least one member selected from the group consisting of lithium,
Reacting the diol with allyl bromide to synthesize a di-alkene compound (step a);
Reacting the di-alkene compound with m-chloroperbenzoic acid to synthesize a bis-epoxide (step b); and
(C) cyclizing by reacting the bis-epoxide with 1,2 dihydroxybenzene,
Wherein said step c) is carried out by adding bis-epoxide to a solution of 1,2-dihydroxybenzene and NaOH dissolved in t-BuOH.
Reacting a diol with an allyl compound to synthesize a di-alkene compound; And
And reacting the di-alkene compound with benzoic acid.
Reacting a diol with allyl bromide to synthesize a di-alkene compound; And reacting the di-alkene compound with m-chloroperbenzoic acid to synthesize a bis-epoxide.

,

,

,

And

≪ / RTI > wherein the lithium crown ether is selected from the group consisting of lithium cations.

,

,

,

And

≪ RTI ID = 0.0 > bis-epoxide. ≪ / RTI >

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