Chiral triazine cage compounds, methods of making and using the same

Abstract

The application discloses a kind of chiral triazine cage compounds and its preparation method and application.The structure of the compound is as shown in formula I.The triazine cage compound I provided in the application is obtained by nucleophilic substitution reaction of the compound as shown in formula II with nucleophilic reagent and base.The compound as shown in formula II is obtained by nucleophilic substitution reaction of commercial readily available raw material cyanuric chloride,metaphenol and the like with base in organic solvent.The synthetic method has the characteristics of cheap and readily available raw material, simple operation, efficient reaction, mild reaction condition, stable and easy to separate and split product, and multi-kilogram preparation, and the inherent chiral cage compound has unique chiral cavity environment, can recognize chiral phosphate as anion detection reagent, and shows good practicability and application prospect in the field of chiral chemistry.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic chemistry, and relates to a kind of inherent chiral cage compounds with bicyclic trisbromooxocalix[2]arene[2]triazine skeleton and synthesis and chiral anion detection performance research thereof. BACKGROUND

[0002] Chirality is a widespread phenomenon in nature, which refers to the property of an object that cannot coincide with its mirror image. Its concept has always permeated various fields of chemical research. Chiral species are diverse, in addition to traditional central chirality, planar chirality, axial chirality and helical chirality, inherent chirality is a new member, which is characterized by the overall chirality of the structure constructed from the macrocyclic skeleton of the molecule. V.J. Inclusion Phenom. Mol. Recognit. Chem. 1994, 19, 17-39; Dalla Cort, A. “Inherent Chirality” and Curvature. New J. Chem. 2004, 28, 1198-1199; Szumna, A. Chem. Soc. Rev. 2010, 39, 4274-4285.) Inherent chiral molecules expand the diversity of chiral molecules and provide new models for understanding basic chiral problems in chemistry and life sciences. Anions play an important role in life processes (Smith, A. E. Cell. 1993, 73, 1251-1254;), and it is of great significance to study the chiral recognition of anions by means of inherent chiral molecules.

[0003] Supramolecular chemistry is widely used in molecular recognition and transport as well as crystal engineering, which mainly relies on the complementary action of non-covalent forces. Among them, anion-π interaction has gradually become a research hotspot of weak interactions in recent years, and is currently widely used in anion recognition (Wang, M.-X. Angew. Chem., Int. Ed. 2014, 53, 13548; Saha, S. Acc. Chem. Res. 2018, 51, 2225; Wang, D.-X. Angew. Chem., Int. Ed. 2018, 57, 15827.) and catalysis (Matile, S. Acc. Chem. Res. 2018, 51, 2255.).

[0004] Although anion recognition based on anion-π interactions has been reported, there is no precedent for chiral recognition, especially for inherently chiral molecular systems, which have a natural chiral cavity and are a good platform for realizing chiral molecular recognition functions. We have previously successfully constructed a unique class of bisoxa calix[2]arene[2]triazine molecular cages (Wang, Q.-Q. J. Am. Chem. Soc. 2017, 139, 635; Wang, D.-X. Inorg. Chem. 2019, 58, 5980), which have advantages including easy and efficient preparation, containing an electron-deficient triazine ring, having a discrete cavity and multiple derivatization sites, etc. SUMMARY

[0005] The present application provides a class of inherently chiral molecular cage compounds containing polysubstituted bisoxa calix[2]arene[2]triazine and a synthesis method thereof and its application in anion chiral recognition.

[0006] The bisoxa calix[2]arene[2]triazine molecular cage provided by the present application has a structural general formula as shown in formula I:

[0007]

[0008] In the structural general formula of formula I,

[0009] R 1 , R 2 and R 3 are independently selected from Cl, (n and m are independently integers from 1 to 10), (R is at least one of halogen, C1-6alkyl, C1-6alkoxy, nitro, cyano);

[0010] (n is an integer from 1 to 10), (n is an integer from 1 to 10), and R 1 , R 2 and R 3 cannot be Cl at the same time.

[0011] Specifically,

[0012] R 1 is selected from any one of the following groups:

[0013]

[0014] R 2 is selected from any one of the following groups:

[0015] -Cl,

[0016] R 3 is selected from any one of the following groups: -Cl,

[0017] the compound of formula I, R 2 and R 3 are both Cl, the structural formula is shown as formula I-1,

[0018] only R 3 is Cl, the structural formula is shown as formula I-2,

[0019] R 2 and R 3 are both not Cl, the structural formula is shown as formula I-3,

[0020]

[0021] In formula I-1, R 1 has the same definition as R 1 in the aforementioned formula I;

[0022] In formula I-2, R 1 , R 2 have the same definition as R 1 , R 2 in the aforementioned formula I;

[0023] In formula I-3, R 1 , R 2 , R 3 have the same definition as R 1 , R 2 , R 3 in the aforementioned formula I;

[0024] The compound of formula I can be divided into the compound of formula I-p and formula I-m according to the arrangement direction of the groups (R 1 ≠ R 2 ≠ R 3 ), wherein:

[0025]

[0026] In the structure of formula I-p and formula I-m, R 1 , R 2 , R 3 have the same definition as R 1 , R 2 , R 3 in the aforementioned formula I, and formula I-p and formula I-m are a pair of enantiomers. For convenience of description, formula I-p is used to represent formula I in the following description.

[0027] The application also provides a simple and efficient preparation method of the inherently chiral molecular cage compound shown in the formula I.

[0028] The preparation method of the inherently chiral molecular cage compound shown in the formula I provided by the application comprises the following steps:

[0029] The compound shown in the formula II is subjected to a nucleophilic substitution reaction with a nucleophilic reagent 1 and a base in an organic solvent to obtain a compound shown in the formula I-1 containing R 1 , R 2 and R 3 , wherein R

[0030] The compound shown in the formula I-1 is subjected to a nucleophilic substitution reaction with a nucleophilic reagent 2 and a base in an organic solvent to obtain a compound shown in the formula I-2 containing R 1 , R 2 and R 3 , wherein R

[0031] The compound shown in the formula I-2 is subjected to a nucleophilic substitution reaction with a nucleophilic reagent 3 and a base in an organic solvent to obtain a compound shown in the formula I-3 containing R 1 , R 2 , R 3 and R 1 , R 2 and R 3 , wherein R

[0032]

[0033] In the formula I-1 to I-3, the definitions of R 1 , R 2 and R 3 are the same as those in the aforementioned formula I.

[0034] In the step of constructing the structure shown in the formula I-1, the base is at least one of potassium carbonate, sodium hydroxide, triethylamine and DIPEA (diisopropylethylamine), and preferably DIPEA;

[0035] The organic solvent is at least one of tetrahydrofuran, acetonitrile and acetone, and preferably tetrahydrofuran;

[0036] The nucleophilic reagent 1 is selected from any one of the following: (n and m are independently integers from 1 to 10), (R is at least one of halogen, C1-6alkyl, C1-6alkoxy, nitro and cyano),

[0037] N(C n H 2n+1)2 (n is an integer from 1 to 10), (n is an integer from 1 to 10),

[0038] The compound of formula II and the nucleophile 1, the base, the solvent are used in the ratio of 0.2-1.0 mmol: 0.2-1.0 mmol: 0.4-2.0 mmol: 1-200 mL, preferably 1 mmol: 1 mmol: 2 mmol: 200 mL;

[0039] In the reaction step, the temperature is -20℃-0℃, preferably 0℃, and the time is 1-4 hours, preferably 4 hours.

[0040] In the step of constructing the structure of formula I-2, the base is at least one of potassium carbonate, sodium hydroxide, triethylamine, DIPEA (diisopropylethylamine), preferably DIPEA;

[0041] The organic solvent is selected from at least one of tetrahydrofuran, acetonitrile, acetone, preferably tetrahydrofuran;

[0042] The nucleophile 2 is selected from any one of the following: (n, m are independently integers from 1 to 10), (R is at least one of halogen, C1-6alkyl, C1-6alkoxy, nitro, cyano),

[0043] N(C n H 2n+1 )2 (n is an integer from 1 to 10), (n is an integer from 1 to 10),

[0044] The compound of formula I-1 and the nucleophile 2, the base, the organic solvent are used in the ratio of 0.2-1.0 mmol: 0.2-1.0 mmol: 0.2-1.0 mmol: 1-10 mL, preferably 0.2 mmol: 0.2 mmol: 0.4 mmol: 10 mL;

[0045] In the reaction step, the temperature is 0℃-25℃, preferably 0℃, and the time is 1-4 hours, preferably 4 hours.

[0046] In the step of constructing the structure of formula I-3, the base is at least one of potassium carbonate, sodium hydroxide, triethylamine, DIPEA (diisopropylethylamine), preferably DIPEA;

[0047] The organic solvent is selected from at least one of tetrahydrofuran, acetonitrile, acetone, preferably tetrahydrofuran;

[0048] The nucleophile 3 is selected from any one of the following: (n, m are independently integers from 1 to 10), (R is at least one of halogen, C1-6alkyl, C1-6alkoxy, nitro, cyano);

[0049] N(C n H 2n+1 )2(n is an integer from 1 to 10), (n is an integer from 1 to 10);

[0050] The compound of formula I-2 and the nucleophile 3, the base, the organic solvent are used in the ratio of 0.1-1.0 mmol: 0.1-1.0 mmol: 0.1-1.0 mmol: 1-10 mL, preferably 0.2 mmol: 0.2 mmol: 0.4 mmol: 1 mL;

[0051] In the reaction step, the temperature is 0-25°C, preferably 25°C, and the time is 1-4 hours, preferably 4 hours.

[0052] The compound of formula II also falls within the scope of the present application:

[0053]

[0054] The compound of formula II is prepared by a method comprising the following steps:

[0055] 1) reacting 2,4,6-tribromoresorcinol and cyanuric chloride, a base in an organic solvent to obtain the compound of formula III;

[0056] 2) reacting the compound of formula III with resorcinol, a base in an organic solvent to obtain the compound of formula II;

[0057]

[0058] In step 1), the organic solvent can be tetrahydrofuran, acetonitrile, dichloromethane, trichloromethane, acetone, etc., preferably tetrahydrofuran;

[0059] The base can be at least one of potassium carbonate, sodium hydroxide, triethylamine, DIPEA (diisopropylethylamine), preferably DIPEA;

[0060] The 2,4,6-tribromoresorcinol and cyanuric chloride, a base, an organic solvent are used in the ratio of 0.1-10 mmol: 0.3-30 mmol: 0.1-36 mmol: 1-200 mL;

[0061] The temperature of the reaction can be 0-25℃, preferably the temperature is 0℃; the reaction time can be 3 hours-96 hours.

[0062] In step 2), the organic solvent can be tetrahydrofuran, dichloromethane, chloroform, acetone, etc., preferably the solvent is dichloromethane;

[0063] The base can be at least one of potassium carbonate, sodium hydroxide, triethylamine, DIPEA (diisopropylethylamine), preferably DIPEA;

[0064] The molar ratio of the compound shown in formula III, phloroglucinol and base can be 0.1-10 mmol: 0.1-10 mmol: 0.3-30 mmol;

[0065] The temperature of the reaction can be 0-25℃, preferably the temperature is 25℃; the reaction time can be 3 hours-96 hours.

[0066] The compound shown in formula I above (wherein R 1 ≠R 2 ≠R 3 The application of the compound shown in formula I in chiral anion-π recognition also belongs to the protection scope of the present application.

[0067] The application includes but is not limited to the compound shown in formula I as a host to recognize chiral phosphate anions, chiral sulfonic acid anions, chiral carboxylic acid anions, etc.

[0068] The present application selects cheap and readily available raw materials, and starts from cyanuric chloride, phloroglucinol and several cheap and readily available reagents, and a racemic inherently chiral bicyclic tribromooxacalix[2]arene[2]triazine molecular cage can be quickly prepared through a simple nucleophilic substitution reaction. The chiral resolution of the key intermediate can be realized through chiral high performance liquid chromatography. The chiral molecular cage after resolution can be subjected to subsequent derivatization to obtain optically pure products, and can be applied to chiral anion recognition, and has good practicability and application prospect. DETAILED DESCRIPTION

[0069] The present application will be further described in detail below in combination with specific embodiments. The examples given below are only for illustrating the present application, and are not intended to limit the scope of the present application. The examples provided below can serve as a guide for further improvement by those skilled in the art, and do not constitute any limitation on the present application in any way.

[0070] In the following examples, the experimental methods are all conventional methods, and are carried out according to the techniques or conditions described in the literature in the art or according to the product instructions, unless otherwise specified. The materials, reagents, etc. used in the following examples can be obtained from commercial channels, unless otherwise specified.

[0071] Example 1: Preparation of I-1a (R1 -N(Benzyl)2, R 2 , R 3 as shown in the compound of formula I-1a

[0072] The reaction is as follows:

[0073]

[0074] The specific preparation method is:

[0075] To the clean two mouth bottles add magnetic son, the compound shown in formula II (823 mg, 1.0 mmol), DIPEA (258 mg, 2.0 mmol) and 100 mL tetrahydrofuran. Dissolve dibenzylamine (197 mg, 1.0 mmol) in 100 mL tetrahydrofuran, slowly drop the above solution into the two mouth bottles under-20 ℃ ice bath, 1 h drop is completed, after 3 h of low temperature reaction, spin dry the solvent, column chromatography (silica gel 100-200 mesh, eluent: dichloromethane), get the white solid compound shown in formula I-1a 415 mg, the yield is 42%.

[0076] 1 H NMR (CDCl3, 500 MHz) δ 7.39-7.29 (m, 10H), 6.68 (m, 2H), 6.60 (t, J = 1.9 Hz, 1H), 4.91 (s, 2H), 4.86 (s, 2H);

[0077] 13 C{ 1 H} NMR (CDCl3, 125 MHz) δ 175.4, 172.8, 172.4, 170.5, 170.0, 169.0, 154.1, 152.6, 148.4, 147.0, 136.03, 136.00, 128.81, 128.78, 128.17, 128.07, 127.87, 115.7, 113.9, 112.6, 110.6, 49.2, 48.9;

[0078] HRMS (APCI + ) calc. for [M+H] + (C 35 H 18 Br3Cl2N 10 O6 + ): 980.8332, found 980.8320.

[0079] From the above, the compound structure is correct, which is the compound shown in formula I-1a.

[0080] The preparation method of the compound shown in formula II is as follows:

[0081]

[0082] A solution of 2,4,6-tribromophloroglucinol (14.5 g, 40.0 mmol) in tetrahydrofuran (100 mL) and a solution of DIPEA (19.4 g, 149.7 mmol) in tetrahydrofuran (100 mL) were added dropwise to a solution of cyanuric chloride (33.2 g, 178.0 mmol) in tetrahydrofuran (300 mL) at 0 °C, dropwise for about 1 h. The mixture was stirred at 0 °C for another 3 h after the addition was completed. After the reaction was completed, the mixture was filtered and the solvent was removed by rotary evaporation. The residue was separated by column chromatography (petroleum ether / acetone = 6:1) to give compound 23 as a white solid (23.45 g, 73% yield).

[0083] A solution of the above white solid (10.1 g, 12.5 mmol) in dichloromethane (250 mL) was added dropwise to a suspension of phloroglucinol (1.6 g, 12.5 mmol) and DIPEA (5.8 g, 45.0 mmol) in dichloromethane (2 L) at room temperature for 30 h. After the reaction was completed, the solvent was removed by rotary evaporation. The residue was separated by column chromatography (100-200 mesh silica gel, eluent: petroleum ether / acetone = 3:1) to give compound 4 as a white solid (4.04 g, 40% yield).

[0084] 1 H NMR (CDCI3 / 500 MHz) δ 6.68 (s, 6H);

[0085] 13 C NMR (CDCI3 / 125 MHz) δ 175.7, 172.7, 170.3, 153.0, 147.4, 115.1, 112.0;

[0086] HRMS (APCI + ) calc. for [M+H] + (C 21 H4Br3Cl3N9O6 + ): 819.6895, found 819.6893.

[0087] Example 2: Preparation of molecular cage of structural formula I I-1b (R 1 is R 2 , R 3 is -Cl)

[0088] The reaction scheme is as follows:

[0089]

[0090] The specific preparation method is:

[0091] To the clean two-port bottle, add magnetic son, compound II (823 mg, 1.00 mmol), DIPEA (258 mg, 1.97 mmol) and 100 mL of tetrahydrofuran. Dissolve tetrahydropyrrole (71 mg, 1.00 mmol) in 100 mL of tetrahydrofuran, slowly drop the above solution into the two-port bottle under-20℃ ice bath, 1h drop completion, low temperature reaction for 3h, spin dry the solvent, column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 4:1), to obtain white solid compound of formula I-1a 354 mg, yield 41%.

[0092] 1 H NMR (CDCl3, 500MHz) δ 6.62 (m, 2H), 6.58 (t, J = 1.9 Hz, 1H), 3.74-3.69 (m, 4H), 2.06-2.03 (m, 4H);

[0093] 13 C{ 1 H}NMR (CDCl3, 125MHz) δ 175.4, 172.8, 171.6, 170.5, 169.3, 165.6, 154.0, 152.6, 148.4, 146.9, 115.7, 113.8, 112.6, 110.5, 47.22, 47.20, 25.16, 25.14;

[0094] MS (MALDI-TOF) m / z for [M+H] + (C 25 H 12 Br3Cl2N 10 O6 + ): 854.7.

[0095] As can be seen from the above, the compound structure is correct, which is a compound of formula I-1b.

[0096] The preparation method of the compound of formula II is described in detail in Example 1.

[0097] Example 3: Preparation of the molecular cage of general structure I, formula I-1c (R 1 is R 2 , R 3 is -Cl)

[0098] The reaction formula is as follows:

[0099]

[0100] The specific preparation method is:

[0101] To a clean two-mouth flask, add magnetic sub, compound of formula II (823 mg, 1.00 mmol), potassium carbonate (276 mg, 1.97 mmol) and 100 mL of acetonitrile. Dissolve 4-hydroxypyridine (95 mg, 1.00 mmol) in 100 mL of acetonitrile, slowly drop the above solution into the two-mouth flask under 0 ℃ ice bath, drop for 1 h, after 4 h of low temperature reaction, spin dry the solvent, column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / acetone = 1:1), to obtain 266 mg of white solid compound of formula I-1c, with a yield of 30%.

[0102] 1 H NMR (CDCl3, 500 MHz) δ 8.85 (d, J = 8.2 Hz, 2H), 6.68 (s, 3H), 6.55 (d, J = 8.2 Hz, 2H);

[0103] 13 C{ 1 H} NMR (CDCl3, 125 MHz) δ 180.9, 175.7, 173.3, 172.7, 171.0, 170.3, 166.2, 153.14, 153.00, 147.47, 147.36, 133.9, 119.5, 115.1, 115.0, 112.0, 111.9;

[0104] MS (MALDI-TOF) m / z for [M+H] + (C 26 H8Br3Cl2N 10 O7 + ): 878.6.

[0105] As can be seen from the above, the compound is correct in structure, which is a compound of formula I-1c.

[0106] The preparation method of the compound of formula II is described in detail in Example 1.

[0107] Example 4: Preparation of a molecular cage of general structure I, formula I-1d (R 1 is R 2 , R 3 is -Cl)

[0108] The reaction is as follows:

[0109]

[0110] The specific preparation method is:

[0111] To a clean two-mouth flask, add magnet, compound of formula II (823 mg, 1.00 mmol), potassium carbonate (276 mg, 1.97 mmol) and 100 mL of acetonitrile. Dissolve phenol (94 mg, 1.00 mmol) in 100 mL of acetonitrile, slowly drop the above solution into the two-mouth flask under 0 °C ice bath, drop for 1 h, after 4 h of low temperature reaction, spin dry the solvent, column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 5:1), to obtain compound of formula I-1c white solid 224 mg, yield 26%.

[0112] 1 H NMR (CDCI3, 500 MHz) δ 7.49 (t, J = 7.8 Hz, 2H), 7.35 (t, J = 7.4 Hz, 1H), 7.28 (d, J = 8.2 Hz, 2H), 6.65-6.64 (m, 3H);

[0113] 13 C{ 1 H} NMR (CDCI3, 125 MHz) δ 175.5, 174.9, 173.8, 172.7, 171.5, 170.4, 153.4, 152.8, 151.3, 147.8, 147.2, 129.9, 126.8, 121.3, 115.3, 114.6, 112.2, 111.4;

[0114] MS (MALDI-TOF) m / z for [M+H] + (C 27 H9Br3Cl2N9O7 + ): 877.6.

[0115] From the above, the compound structure is correct, which is compound of formula I-1d.

[0116] The preparation method of compound of formula II is described in detail in Example 1.

[0117] Example 5: Preparation of molecular cage of general structure formula I, formula I-2a (R 1 is -N(Benzyl)2, R 2 is R 3 is -Cl)

[0118] The reaction formula is as follows:

[0119]

[0120] The specific preparation method is:

[0121] To a clean two-mouth flask, add magnet, compound shown in formula I-1a (197 mg, 0.20 mmol), DIPEA (52 mg, 0.40 mmol) and 10 mL of tetrahydrofuran. Dissolve tetrahydropyrrole (14 mg, 0.20 mmol) in 10 mL of tetrahydrofuran, slowly drop the above solution into the two-mouth flask under 0 ℃ ice bath, drop for 1 h, after 3 h of low temperature reaction, spin dry the solvent, column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 4:1), obtain compound shown in formula I-2a 111 mg of white solid, yield 55%.

[0122] 1 H NMR (CDCI3, 500 MHz) δ 7.39-7.30 (m, 10H), 6.64 (t, J = 1.8 Hz, 1H), 6.59 (t, J = 1.8 Hz, 1H), 6.55 (t, J = 1.8 Hz, 1H), 4.91 (s, 2H), 4.87 (s, 2H), 3.75-3.69 (m, 4H), 2.05-2.02 (m, 4H);

[0123] 13 C{ 1 H} NMR (CDCI3, 125 MHz) δ 175.1, 173.0, 172.5, 171.8, 170.6, 170.1, 169.5, 169.1, 165.7, 153.6, 152.2, 148.00, 147.95, 146.6, 136.20, 136.16, 128.78, 128.73, 128.20, 128.09, 127.8, 116.4, 114.52, 114.46, 113.3, 111.4, 111.2, 49.1, 49.8, 47.17, 47.13, 25.18, 25.15;

[0124] MS (MALDI-TOF) m / z for [M+H] + (C 39 H 26 Br3ClN 11 O6 + ): 1015.9281.

[0125] From the above, the compound structure is correct, which is compound shown in formula I-2a.

[0126] The preparation method of compound shown in formula I-1a is described in detail in Example 1.

[0127] Example 6: Preparation of molecular cage shown in general formula I I-2b (R 1 is -N(Benzyl)2, R2 For R 3 -Cl)

[0128] The reaction is as follows:

[0129]

[0130] The specific preparation method is:

[0131] To the clean two-port bottle, add magnetic son, compound shown in formula I-1a (197 mg, 0.20 mmol), DIPEA (52 mg, 0.40 mmol) and 10 mL of tetrahydrofuran. Dissolve morpholine (18 mg, 0.20 mmol) in 10 mL of tetrahydrofuran, slowly drop the above solution into the two-port bottle under 0°C ice bath, drop for 1 h, after 3 h of low temperature reaction, spin dry the solvent, column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 3:1), to obtain white solid compound shown in formula I-2b 108 mg, yield 52%.

[0132] 1 H NMR (CDCI3, 500 MHz) δ 7.40-7.30 (m, 10H), 6.64 (t, J = 1.9 Hz, 1H), 6.61 (t, J = 1.9 Hz, 1H), 6.55 (t, J = 1.9 Hz, 1H), 4.91 (s, 2H), 4.87 (s, 2H), 4.00-3.95 (m, 4H), 3.82-3.79 (m, 4H);

[0133] 13 C{ 1 H} NMR (CDCI3, 125 MHz) δ 175.2, 172.9, 172.5, 172.4, 170.6, 170.11, 170.09, 169.1, 167.6, 153.6, 153.4, 152.2, 148.0, 147.9, 146.6, 136.2, 136.1, 128.80, 128.75, 128.21, 128.08, 127.8, 116.3, 114.6, 114.5, 113.2, 111.4, 111.3, 66.57, 66.50, 49.1, 48.9, 44.51, 44.46;

[0134] HRMS (APCI + ) calc. for [M+H] + (C 39 H 26 Br3ClN 11 O7 +) : 1031.9250, found 1031.9230.

[0135] From the above, the structure of the compound is correct, which is a compound shown in formula I-2b.

[0136] The preparation method of the compound shown in formula I-1a is shown in Example 1.

[0137] Example 7: Preparation of a molecular cage shown in general formula I I-2c (R 1 is -N(Benzyl)2, R 2 is R 3 is -Cl)

[0138] The reaction is as follows:

[0139]

[0140] The specific preparation method is:

[0141] A clean two-port bottle is added with a magnet, a compound shown in formula I-1a (197 mg, 0.20 mmol), potassium carbonate (55 mg, 0.40 mmol) and 10 mL of acetonitrile. 4-Hydroxypyridine (19 mg, 0.20 mmol) is dissolved in 10 mL of acetonitrile, and the above solution is slowly added dropwise to the two-port bottle under ice bath at 0°C. The dropwise addition is completed in 1 h, and the low-temperature reaction is carried out for 3 h. After the solvent is spun dry, column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / acetone = 1:1) is performed to obtain a white solid compound shown in formula I-2c 71 mg, with a yield of 34%.

[0142] 1 H NMR (CDCl3, 500MHz) δ 8.87 (d, J = 6.2 Hz, 2H), 7.39-7.31 (m, 10H), 6.69 (s, 2H), 6.61 (s, 1H), 6.54 (d, J = 6.2 Hz, 2H), 4.92 (s, 2H), 4.87 (s, 2H);

[0143] 13 C{ 1H}NMR (CDC13, 125 MHz) δ 180.9, 175.4, 173.4, 172.9, 172.4, 171.2, 170.5, 169.97, 169.02, 166.2, 154.1, 152.7, 152.6, 148.4, 147.1, 147.0, 136.0, 135.9, 134.0, 128.82, 128.79, 128.2, 128.1, 127.9, 119.5, 115.8, 115.7, 114.0, 112.7, 112.6, 110.7, 49.2, 49.0;

[0144] MS (MALDI-TOF) m / z for [M+H] + (C 40 H 22 Br3ClN 11 O7 + ) : 1040.0.

[0145] From the above, the compound structure is correct, which is a compound shown in formula I-2c.

[0146] The preparation method of the compound shown in formula I-1a is described in detail in Example 1.

[0147] Example 8: Preparation of the molecular cage shown in general formula I formula I-2d (R 1 -N(Benzyl)2, R 2 is R 3 -Cl)

[0148] The reaction is as follows:

[0149]

[0150] The specific preparation method is:

[0151] Into a clean two-port bottle, add magnetic son, compound shown in formula I-1a (197 mg, 0.20 mmol), potassium carbonate (55 mg, 0.40 mmol) and 10 mL of acetonitrile. Phenol (19 mg, 0.20 mmol) is dissolved in 10 mL of acetonitrile, and the above solution is slowly added dropwise into the two-port bottle, and the dropwise addition is completed in 1 h, and then the reaction is carried out for 10 h. The solvent is rotary evaporated, and column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 10:1) is carried out to obtain 74 mg of white solid compound shown in formula I-2c, with a yield of 35%.

[0152] 1H NMR (CDC13, 500 MHz) δ 7.49 (t, J = 5.8 Hz, 2H) 7.39 - 7.28 (m, 13H), 6.66 (t, J = 1.9 Hz, 1H), 6.64 (t, J = 1.9 Hz, 1H), 6.57 (d, J = 1.9 Hz, 1H), 4.91 (s, 2H), 4.87 (s, 2H);

[0153] 13 C{ 1 H} NMR (CDC13, 125 MHz) δ 175.3, 174.8, 173.9, 172.9, 172.4, 171.6, 170.5, 170.0, 169.0, 153.9, 153.0, 152.4, 151.4, 148.3, 147.4, 146.8, 136.10, 136.07, 129.9, 128.81, 128.77, 128.2, 128.1, 127.8, 126.7, 121.4, 115.9, 115.2, 114.1, 112.9, 112.1, 110.9, 49.1, 48.9;

[0154] MS (MALDI-TOF) m / z for [M+H] + (C 41 H 23 Br3ClN 10 O7 + ) : 1039.0

[0155] From the above, the compound structure is correct, which is a compound represented by formula I-2d.

[0156] The preparation method of the compound represented by formula I-1a is described in detail in Example 1.

[0157] Example 9: Preparation of the molecular cage represented by general formula I, formula I-2e (R 1 is- R 2 is R 3 is-Cl)

[0158] The reaction is as follows:

[0159]

[0160] The specific preparation method is:

[0161] To a clean two-necked flask, add magnet, compound shown in formula I-1b (172 mg, 0.20 mmol), potassium carbonate (83 mg, 0.60 mmol) and 10 mL acetonitrile. Dissolve phenol (19 mg, 0.20 mmol) in 10 mL acetonitrile, slowly drop the above solution into the two-necked flask, drop for 1 h, then react for 9 h. After the reaction, spin dry the solvent, column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 3:1), to obtain compound shown in formula I-2e 74 mg, yield 41% white solid.

[0162] 1 H NMR (CDCI3, 500 MHz) δ 7.48 (t, J = 7.5 Hz, 2H), 7.33 (t, J = 7.5 Hz, 1H), 7.28 (d, J = 7.5 Hz, 2H), 6.60-6.56 (m, 3H), 3.74-3.68 (m, 4H), 2.05-2.02 (m, 4H);

[0163] 13 C{ 1 H} NMR (CDCI3, 125 MHz) δ 175.3, 174.8, 173.9, 172.9, 171.7, 171.6, 170.5, 169.4, 165.6, 153.8, 153.0, 152.4, 151.4, 148.2, 147.4, 146.8, 129.9, 126.7, 121.4, 115.9, 115.2, 114.0, 112.9, 112.1, 110.8, 47.20, 47.17, 25.17, 25.14;

[0164] MS (MALDI-TOF) m / z for [M+H] + (C 31 H 17 Br3ClN 10 O7 + ): 913.0.

[0165] From the above, the compound structure is correct, which is compound shown in formula I-2e.

[0166] The preparation method of compound shown in formula I-1b is described in detail in Example 2.

[0167] Example 10: Preparation of molecular cage shown in general formula I formula I-2f (R 1 is R 2 is R 3 is -Cl)

[0168] The reaction is as follows:

[0169]

[0170] The specific preparation method is:

[0171] To the clean two-port bottle, add magnetic son, compound shown in formula I-1d (172 mg, 0.20 mmol), DIPEA (52 mg, 0.40 mmol) and 10 mL of tetrahydrofuran. Dissolve morpholine (18 mg, 0.20 mmol) in 10 mL of tetrahydrofuran, slowly drop the above solution into the two-port bottle under 0°C ice bath, drop for 1 h, after 3 h of low temperature reaction, spin dry the solvent, column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 3:1), to obtain white solid compound shown in formula I-2f 73 mg, the yield is 40%.

[0172] 1 H NMR (CDCI3, 500 MHz) δ 7.48 (t, J = 7.6 Hz, 2H), 7.34 (t, J = 7.5 Hz, 1H), 7.28 (d, J = 7.4 Hz, 2H), 6.60-6.57 (m, 3H), 3.99-3.94 (m, 4H), 3.81-3.79 (m, 4H);

[0173] 13 C{ 1 H} NMR (CDCI3, 125 MHz) δ 175.3, 174.8, 173.9, 172.9, 172.3, 171.6, 170.5, 170.0, 167.5, 153.7, 153.0, 152.8, 152.4, 151.4, 148.1, 147.4, 146.8, 129.9, 126.7, 121.3, 115.9, 115.4, 115.1, 114.2, 112.8, 112.3, 112.0, 111.0, 66.53, 66.47, 44.53, 44.47;

[0174] MS (MALDI-TOF) m / z for [M+H] + (C 31 H 17 Br3ClN 10 O8 + ): 928.7.

[0175] As can be seen from the above, the compound structure is correct, which is the compound shown in formula I-2f.

[0176] The preparation method of the compound shown in formula I-1d is described in detail in Example 4.

[0177] Example 11: Preparation of molecular cage of structure general formula I I-3a (R 1 is -N(Benzyl)2, R 2 is R 3 is )

[0178] The reaction is as follows:

[0179]

[0180] The specific preparation method is:

[0181] To a clean single-mouth flask was added a magnetic stirrer, compound of formula I-2a (102 mg, 0.10 mmol), DIPEA (26 mg, 0.20 mmol) and 10 mL of tetrahydrofuran, dimethylamine tetrahydrofuran (2M in THF, 100 uL, 0.20 mmol) solution was added, and the reaction was stirred for 1 h. After the solvent was dried, column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 2:1) was performed to obtain 99 mg of white solid compound of formula I-3a, with a yield of 96%.

[0182] 1 H NMR (CDCI3, 500 MHz) δ 7.39-7.30 (m, 10H), 6.57-6.56 (m, 2H), 6.52 (t, J = 1.9 Hz, 1H), 4.91 (s, 2H), 4.87 (s, 2H), 3.75-3.69 (m, 4H), 3.31 (s, 3H), 3.29 (s, 3H), 2.05-2.02 (m, 4H);

[0183] 13 C{ 1 H} NMR (CDCI3, 125 MHz) δ 172.7, 172.2, 172.0, 170.3, 169.9, 169.7, 169.2, 168.2, 165.8, 153.08, 153.06, 147.55, 147.53, 147.52, 136.36, 136.31, 128.75, 128.70, 128.2, 128.1, 127.7, 115.23, 115.21, 115.17, 112.12, 112.01, 111.98, 49.0, 48.7, 47.12, 47.08, 37.1, 37.0, 25.20, 25.17;

[0184] HRMS (APCI + ) calc. for [M+H] + (C 41 H32 Br3N 12 O6 + ) : 1025.0112, found 1025.0107.

[0185] From the above, the structure of the compound is correct, which is a compound represented by formula I-3a.

[0186] The preparation method of the compound represented by formula I-2a is described in detail in Example 5.

[0187] Example 12: Preparation of a molecular cage represented by general structural formula I, formula I-3b (R 1 -N(Benzyl)2, R 2 is R 3 is )

[0188] The reaction is as follows:

[0189]

[0190] The specific preparation method is:

[0191] Into a clean single-mouth bottle, add magnetic beads, a compound represented by formula I-2a (102 mg, 0.10 mmol), DIPEA (26 mg, 0.20 mmol) and 10 mL of tetrahydrofuran, and then add a diethanolamine (21 mg, 0.20 mmol) solution. After stirring for 1 h, spin dry the solvent, and column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 2:1) to obtain a white solid compound represented by formula I-3a 99 mg, with a yield of 96%.

[0192] 1 H NMR (CDCl3, 500MHz) δ 7.39-7.29 (m, 10H), 6.57-6.51 (m, 3H), 4.95-4.82 (m, 4H), 4.05-4.37 (m, 4H), 3.96-3.94 (m, 4H), 3.75-3.69 (m, 4H), 2.57 (br, 2H), 2.05-2.02 (m, 4H);

[0193] 13 C{ 1H}NMR (CDC13, 125 MHz) δ 172.6, 172.1, 171.9, 170.3, 169.8, 169.6, 169.2, 169.0, 165.8, 153.14, 153.12, 152.9, 147.60, 147.57, 147.3, 136.33, 136.28, 128.8, 128.7, 128.22, 128.10, 127.7, 115.4, 115.1, 115.1, 112.2, 112.0, 111.9, 61.5, 52.7, 52.3, 49.00, 48.76, 47.13, 47.10, 25.19, 25.17;

[0194] HRMS (APCI + ) calc. for [M+H] + (C 43 H 36 Br3N 12 O8 + ) 1085.0324, found 1085.0315.

[0195] From the above, the compound structure is correct, which is a compound represented by formula I-3b.

[0196] The preparation method of the compound represented by formula I-2a is described in detail in Example 5.

[0197] Example 13: Preparation of a molecular cage represented by general structural formula I, formula I-3c (R 1 is -N(Benzyl)2, R 2 is R 3 is )

[0198] The reaction is as follows:

[0199]

[0200] The specific preparation method is:

[0201] Into a clean single-mouth bottle, add magnetic beads, a compound represented by formula I-2a (102 mg, 0.10 mmol), DIPEA (26 mg, 0.20 mmol) and 10 mL of tetrahydrofuran, and stir. Add morpholine (18 mg, 0.20 mmol), and after 1 h of reaction, spin dry the solvent, and column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 2:1) to obtain a white solid compound represented by formula I-3a 101 mg, with a yield of 97%.

[0202] 1H NMR(CDCl3,500MHz)δ7.39-7.30(m,10H),6.57-6.52(m,3H),4.91(s,2H),4.87(s ,2H),3.99-3.94(m,4H),3.81-3.79(m,4H),3.75-3.68(m,4H),2.05-2.02(m,4H);

[0203] 13 C{ 1 H}NMR(CDCl3,125MHz)δ172.7,172.5,171.9,170.3,170.2,169.6,169.2,1 67.6,165.8,153.12,153.11,152.9,147.58,147.55,147.4,136.33,136.2 8,128.75,128.70,128.23,128.09,127.7,115.3,115.2,115.1,112.2,112.0,111.9,66.6,66.5,49.0,48.8,47.12,47.10,44.5,44.4,25.19,25.17;

[0204] HRMS (APCI) + calc.for[M+H] + (C 43 H 34 Br3N 12 O7 + ): 1067.0218, found 1067.0204.

[0205] As can be seen from the above, the structure of the above compound is correct, and it is the compound shown in formula I-3c.

[0206] The preparation method of the compound shown in Formula I-2a is detailed in Example 5.

[0207] Example 14: Preparation of molecular cage I-3d(R) with general structural formula I 1 For -N(Benzyl)2, R 2 for R 3 for )

[0208] The reaction equation is as follows:

[0209]

[0210] The specific preparation method is as follows:

[0211] To a clean single-mouth flask, add magnet, compound shown in formula I-2a (102 mg, 0.10 mmol), DIPEA (26 mg, 0.20 mmol) and 10 mL of tetrahydrofuran, and stir. Add 1-methylpiperazine (20 mg, 0.20 mmol), and react for 1 h. Spin dry the solvent, and column chromatograph (silica gel 100-200 mesh, eluent: petroleum ether / acetone = 1:1) to obtain 105 mg of white solid compound shown in formula I-3d, with a yield of 97%.

[0212] 1 H NMR (CDCI3, 500 MHz) δ 7.39-7.31 (m, 10H), 6.56-6.52 (m, 3H), 4.91 (s, 2H), 4.87 (s, 2H), 4.20-3.80 (m, 4H), 3.75-3.69 (m, 4H), 2.75-2.49 (m, 4H), 2.42 (s, 3H), 2.05-2.02 (m, 4H);

[0213] 13 C{ 1 H} NMR (CDCI3, 125 MHz) δ 172.7, 172.5, 171.9, 170.3, 169.6, 169.2, 167.5, 165.8, 153.1, 153.0, 147.6, 147.5, 147.4, 136.33, 136.29, 128.8, 128.7, 128.2, 128.1, 127.7, 115.3, 115.2, 115.1, 112.12, 112.06, 111.9, 54.5, 49.0, 48.7, 47.11, 47.07, 25.19, 25.16;

[0214] HRMS (APCI + ) calc. for [M+H] + (C 44 H 37 Br3N 13 O6 + ) 1080.0534, found 1080.0523.

[0215] As can be seen from the above, the compound is correct in structure, and is a compound shown in formula I-3d.

[0216] The preparation method of the compound shown in formula I-2a is described in detail in Example 5.

[0217] Example 15: Preparation of a molecular cage shown in general formula I, formula I-3e (R 1 is -N(Benzyl)2, R 2 is R 3 For )

[0218] The reaction is as follows:

[0219]

[0220] The specific preparation method is:

[0221] To a clean single-mouth flask was added a magnetic stirrer, a compound represented by Formula I-2a (102 mg, 0.10 mmol), potassium carbonate (26 mg, 0.20 mmol), and 10 mL of acetonitrile, which was stirred, phenol (19 mg, 0.20 mmol) was added, the reaction was carried out for 1 h, the solvent was spun dry, column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / ethyl acetate = 3:1) was performed, and a compound represented by Formula I-3e was obtained as a white solid, 101 mg, in a yield of 94%.

[0222] 1 H NMR (CDCI3, 500 MHz) δ 7.48 (t, J = 7.7 Hz, 2H), 7.39-7.28 (m, 13H), 6.61 (t, J = 1.9 Hz, 1H), 6.57 (t, J = 1.9 Hz, 1H), 6.54 (t, J = 1.9 Hz, 1H), 4.91 (s, 2H), 4.87 (s, 2H), 3.75-3.69 (m, 4H), 2.05-2.02 (m, 4H);

[0223] 13 C{ 1 H} NMR (CDCI3, 125 MHz) δ 174.8, 174.0, 172.6, 171.9, 171.8, 170.2, 169.5, 169.1, 165.7, 153.4, 152.5, 151.5, 147.82, 147.79, 147.0, 136.26, 136.21, 129.8, 128.77, 128.71, 128.2, 128.1, 127.8, 126.5, 121.4, 115.9, 114.8, 114.7, 112.8, 111.7, 111.5, 49.0, 48.8, 47.14, 47.10, 25.18, 25.16;

[0224] HRMS (APCI + ) calc. for [M+H] + (C 45 H 31 Br3N 11 O7 + ) 1073.9953, found 1073.9950.

[0225] From the above, the structure of the compound is correct, which is a compound shown in formula I-3e.

[0226] The preparation method of the compound shown in formula I-2a is shown in Example 5.

[0227] Example 16: Preparation of the molecular cage shown in general formula I I-3f (R 1 -N(Benzyl), R 2 -N(Benzyl), R -N(Benzyl), R 3 -N(Benzyl), R )

[0228] The reaction is as follows:

[0229]

[0230] The specific preparation method is as follows:

[0231] Into a clean single-mouth bottle, add magnetic beads, the compound shown in formula I-2b (103 mg, 0.10 mmol), potassium carbonate (26 mg, 0.20 mmol) and 10 mL of acetonitrile, and stir. Add 4-hydroxypyridine (10 mg, 0.10 mmol), and after 1 h of reaction, spin dry the solvent, and column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / acetone = 1:1) to obtain 90 mg of the compound shown in formula I-3f as a white solid, with a yield of 83%.

[0232] 1 H NMR (CDCl3, 500 MHz) δ 8.89 (d, J = 7.4 Hz, 2H), 7.39-7.30 (m, 10H), 6.65-6.54 (m, 5H), 4.92 (s, 2H), 4.87 (s, 2H), 4.00-3.94 (m, 4H), 3.82-3.79 (m, 4H);

[0233] 13 C{ 1 H} NMR (CDCl3, 125 MHz) δ 180.9, 173.5, 172.5, 172.4, 171.3, 170.11, 170.09, 169.1, 167.6, 166.1, 153.6, 153.4, 152.3, 148.0, 147.9, 146.7, 136.2, 136.1, 134.1, 128.80, 128.75, 128.2, 128.1, 127.8, 119.3, 116.2, 114.7, 114.5, 113.2, 111.5, 111.3, 66.56, 66.49, 49.1, 48.9, 44.52, 44.46;

[0234] HRMS (APCI + ) calc. for [M+H] + (C 44 H 30 Br3N 12 O8 + ): 1090.9854, found 1090.9857.

[0235] From the above, the structure of the above compound is correct, which is a compound represented by formula I-3f.

[0236] The preparation method of the compound represented by formula I-2b is described in detail in Example 6.

[0237] Example 17: Preparation of a molecular cage represented by general structural formula I, formula I-3g (R 1 is -N(Benzyl)2, R 2 is R 3 is )

[0238] The reaction is as follows:

[0239]

[0240] The specific preparation method is:

[0241] Into a clean single-mouth bottle, add magnetic beads, a compound represented by formula I-2d (104 mg, 0.10 mmol), potassium carbonate (26 mg, 0.20 mmol) and 10 mL of acetonitrile, and stir. Add 4-hydroxypyridine (10 mg, 0.10 mmol), and after 1 h of reaction, spin dry the solvent, and column chromatography (silica gel 100-200 mesh, eluent: petroleum ether / acetone = 1:1) to obtain 89 mg of a compound represented by formula I-3g as a white solid, with a yield of 81%.

[0242] 1 H NMR (CDCl3, 500 MHz) δ 8.93 (d, J = 6.7 Hz, 2H), 7.49 (t, J = 7.8 Hz, 2H), 7.39-7.27 (m, 13H), 6.68-6.59 (m, 5H), 4.92 (s, 2H), 4.87 (s, 2H);

[0243] 13 C{ 1H}NMR (CDC13, 125 MHz) δ 180.9, 174.8, 173.9, 173.5, 172.4, 171.6, 171.2, 170.0, 169.1, 166.1, 153.8, 152.97, 152.51, 151.4, 148.3, 147.4, 146.9, 136.09, 136.05, 134.1, 129.9, 128.81, 128.77, 128.2, 128.1, 127.9, 127.0, 126.7, 121.3, 119.3, 116.0, 115.3, 114.1, 112.9, 112.2, 111.0, 49.1, 48.9;

[0244] HRMS (APCI + ) calc. for [M+H] + (C 46 H 27 Br3N 11 O8 + ) 1097.9589, found 1097.9575.

[0245] From the above, the above-mentioned compound structure is correct, which is a compound represented by formula I-3g.

[0246] The preparation method of the compound represented by formula I-2d is described in detail in Example 8.

[0247] Example 18: Selective recognition performance of chiral phosphonate anion

[0248] The series of double-ring tribromooxacalix[2]arene[2]triazine cage molecules prepared by the application are a new type of anion detection reagent, and have good recognition effect on chiral phosphonate anions.

[0249] In a series of molecular cages, the compounds shown in formulas I-2 to I-3 all exist as a pair of enantiomers. Compound I-2a can be separated by high-performance liquid chromatography (HPLC) at the gram scale. The separated compounds, I-2a-p and I-2a-m, were identified as having an optical purity of over 99% ee. We conducted NMR titration experiments on optically pure I-2a-p and I-2a-m with optically pure (S)-CPA and (R)-CPA tetrabutylammonium salts based on the binaphthalene skeleton, respectively, using deuterated acetonitrile as the solvent. In the recognition experiment, with increasing anion concentration, the electron-deficient V-shaped cavity of the molecular cage compound represented by general formula I-2a binds to the anion through anion-π interaction. The hydrogen atoms along the pyrogallol in the molecular cage shift to a lower field due to the shielding effect of oxygen atoms on the phosphate groups. Fitting results showed that I-2a-p had a larger binding constant with the (S)-CPA anion and a smaller binding constant with the (S)-CPA anion; conversely, I-2a-p had a smaller binding constant with the (S)-CPA anion and a larger binding constant with the (R)-CPA anion. A series of NMR titration experiments demonstrated that the inherent chiral molecular cage has a recognition function for chiral anions. This is also the first application to date of anion chiral recognition based on anion-π interaction. The specific binding constants are as follows:

[0250]

[0251] Table 1 shows the anion chiral recognition performance of the compounds represented by Formula I.

[0252]

[0253] The present invention has been described in detail above. Those skilled in the art will recognize that the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope, and without requiring unnecessary experiments. While specific embodiments have been provided, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including changes made using conventional techniques known in the art that depart from the scope disclosed herein.

Claims

1. A compound represented by formula I-2: ###0001### I-2 wherein, R1 is selected from the group consisting of H, F, Cl, Br, I, CF3, CH3, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3, CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3, CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2 ​ R 1 selected from the group consisting of: n, m are independently integers from 1 to 10; R 2 selected from the group consisting of: . ​ The compound of formula II undergoes a nucleophilic substitution reaction with a nucleophile 1, a base in an organic solvent to obtain a compound of formula I-1 containing R 1 substituents. The compound of formula I-1 undergoes a nucleophilic substitution reaction with a nucleophile 2 and a base in an organic solvent to give a compound of formula I-2 containing R 1 and R 2 substituents; R 1 is selected from: , n, m are independently integers from 1 to 10; R 2 selected from: ; 。 3. The method of claim 2, wherein: ​ ​ The nucleophile 1 is selected from: n, m are independently integers from 1 to 10; ​ ​ 4. The method of claim 2, wherein: ​ ​ The nucleophile 2 is: ; ​ ​ ​

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