Double-fluorine-chain phosphorylcholine compound and intermediate thereof

Abstract

The invention discloses a double-fluorine-chain phosphorylcholine compound and an intermediate thereof. The invention provides a compound as shown in a formula I or a salt thereof. The compound as shown in the formula I or the salt thereof provided by the invention has excellent surface activity, good solubility, good environmental and biological friendliness, easiness in storage at high concentration, convenience in transportation and good application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to a double fluorine chain choline phosphate compound and intermediates thereof. BACKGROUND

[0002] Fluorinated surfactants have high surface activity, high thermal stability, high chemical stability, and hydrophobic and oleophobic properties (Fluorinated Surfactants and Repellents, Marcel Dekker Inc., New York, 2001, pp. 1-21.), which are indispensable in the fields of materials, fire fighting, electroplating, and textiles. With its extensive use, people have begun to pay attention to its environmental risks. Studies have found that long fluorinated alkyl chain compounds PFOS / PFOA, due to their environmental persistence, bioaccumulation, toxicity, and long-distance migration ability, belong to persistent organic pollutants (POPs), and were banned by the Stockholm Convention in 2009 and 2019, respectively. In 2024, the European Union REACH Committee passed a proposal to restrict perfluorohexanoic acid (PFHxA) and its salts and related substances, strengthening the control of fluorinated compounds.

[0003] The existing substitutes have better environmental effects than PFOS / PFOA products, but there is still a certain gap in performance. In actual application, PFOS / PFOA has good surface activity and exhibits extremely low surface tension, but has poor environmental effect; while short-chain fluorinated surfactants of the same type have better environmental effect, but the solution surface tension rises and the surface activity becomes poor, so the substitutes often show performance degradation or increased dosage. The common substitutes on the market are perfluorohexyl ethyl structures, such as Capstone 1157 (wherein the effective ingredient is fluorinated surfactant 6:2 FTAB). In actual use, long-chain fluorinated (ether) surfactants are needed to provide high surface activity, and after use, they need to be environmentally friendly like short fluorinated (ether) chain structures, which requires that the new generation of fluorinated surfactant products need to balance the contradiction between environmental friendliness and excellent performance. SUMMARY

[0004] The technical problem to be solved by the present application is to overcome the defects of existing surfactants, such as strong biological toxicity, high environmental persistence, and poor surface activity performance. The present application provides a double fluorine chain choline phosphate compound and intermediates thereof. The surfactant compound provided by the present application has high surface activity and environmental biological friendliness, better solubility, easy storage at high concentration, convenient transportation, and good application prospect.

[0005] The present application solves the above technical problems through the following technical solutions.

[0006] The present application provides a compound as shown in formula I or a salt thereof,

[0007]

[0008] Where n is 0, 1, or 2; p is 2, 3, 4, 5, or 6;

[0009] R F1 and R F2 Each independently Where each Y is independently *-CF2-**, *-OCF2-**, *-OCF(CF3)-**, or *-CH(CF3)-**, and R F1 and / or R F2 In the given information, at least one Y is *-OCF2-** or *-OCF(CF3)-**; m is independently 1, 2, 3, 4, or 5; the direction from the "*" end to the "**" end is from the CF3 direction to... The direction;

[0010] R1 and R2 are each independently C1-C6 alkyl groups.

[0011] In some embodiments of the present invention, R F1 and R F2 In this context, the ratio of the total number of fluorinated carbon atoms to the total number of oxygen atoms is less than 3. A fluorinated carbon atom refers to a carbon atom replaced by one or more fluorine atoms. The total number of fluorinated carbon atoms refers to R... F1 The number of fluorine and carbon atoms in R F2 The sum of the number of fluorine and carbon atoms in it. The total number of oxygen atoms refers to R. F1 The number of oxygen atoms in R F2 The sum of the number of oxygen atoms in it.

[0012] In some embodiments of the present invention, R F1 and R F2 In this context, the total number of fluorocarbon atoms is less than or equal to 12; for example, 6, 7, 8, 9, or 10.

[0013] In some embodiments of the present invention, R F1 and R F2 In this context, the total number of oxygen atoms is greater than or equal to 3; for example, 3, 4, 5, 6, 7, or 8.

[0014] In some embodiments of the present invention, R F1 and R F2 In this context, the total number of fluorine-carbon atoms is greater than or equal to 6; the sum of the total number of fluorine-carbon atoms and the total number of oxygen atoms is greater than or equal to 10.

[0015] Preferably, the total number of fluorinated carbon atoms is greater than or equal to 7; the sum of the total number of fluorinated carbon atoms and the total number of oxygen atoms is greater than or equal to 12.

[0016] More preferably, the total number of fluorinated carbon atoms is greater than or equal to 8 and less than 12; the sum of the total number of fluorinated carbon atoms and the total number of oxygen atoms is greater than or equal to 13.

[0017] In some embodiments of the present invention, R F1 and R F2 Among them, at least one is For example, R F1 for or R F2 for Where m is independently 1, 2, 3 or 4.

[0018] In some embodiments of the present invention, R F1 and R F2 At the same time For example, R F1 and R F2 Same; m can be 1, 2, 3 or 4 independently.

[0019] In some embodiments of the present invention Independently

[0020] In some embodiments of the present invention Independently

[0021] In some embodiments of the present invention, p is 3.

[0022] In some embodiments of the present invention, R1 and R2 are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; preferably methyl; more preferably, R1 and R2 are both methyl.

[0023] In some embodiments of the present invention, the compound shown in Formula I is a compound of Formula I-1; or a compound of Formula I-II.

[0024]

[0025] Among them, R F1 and R F2 As mentioned above.

[0026] In some embodiments of the present invention, the compound shown in Formula I is a compound of Formula I-2:

[0027]

[0028] Where m and R F2 As mentioned above.

[0029] In some embodiments of the present application, the compound of Formula I is a compound of Formula I-3:

[0030]

[0031] wherein m and R F1 As described previously.

[0032] In some embodiments of the present application, the compound of Formula I is any one of the following:

[0033]

[0034]

[0035]

[0036] The present application provides a compound of Formula II,

[0037]

[0038] wherein R F1 and n are as described in any of the preceding embodiments.

[0039]

[0040] The term "salt" refers to a salt of a compound resulting from its reaction with an acid or a base. When the compound contains a relatively acidic functional group, a base addition salt can be obtained by contacting the free form of the compound with a sufficient amount of a base in a suitable inert solvent. Base addition salts include, but are not limited to, sodium salts, potassium salts, calcium salts, aluminum salts, magnesium salts, bismuth salts, ammonium salts, and the like. When the compound contains a relatively basic functional group, an acid addition salt can be obtained by contacting the free form of the compound with a sufficient amount of an acid in a suitable inert solvent. Acid addition salts include, but are not limited to, hydrochlorides, sulfates, methanesulfonates, and the like.

[0041] On the basis of not violating the common knowledge in the art, the above-mentioned preferred conditions can be combined arbitrarily, thereby obtaining various preferred examples of the present application.

[0042] The reagents and raw materials used in the present application are commercially available.

[0043] The positive progress effect of the present application is that:

[0044] (1) The surfactant provided by the present application has better solubility, is easy to store at high concentration, and is convenient for transportation;

[0045] (2) The surfactant provided by the present application has excellent surface activity performance;

[0046] (3) The surfactant provided by the application has low bioaccumulation and low toxicity chain segments, the oxygen-containing fluorine chain segments are introduced into the phosphocholine by simple substitution reaction and ring-opening reaction, the oxygen atoms and fluorocarbon numbers in the molecular structure are adjusted, the surfactant performance is improved, the toxicity is reduced, and the surfactant is expected to be a candidate for replacing PFOS / PFOA. DETAILED DESCRIPTION

[0047] The application will be further described in the following examples, but the application is not limited to the scope of the examples. The experimental methods in the following examples without specific conditions are selected according to conventional methods and conditions or according to the product instructions.

[0048] (I) Compound List

[0049] 1.1 Intermediate alcohol, compound list

[0050] Table 1

[0051]

[0052] 1.2 Intermediate fluorophosphonate, compound list

[0053] Table 2

[0054]

[0055]

[0056] 1.3 Intermediate tertiary amine, compound list

[0057] Table 3

[0058]

[0059] 1.4 Fluorine-containing phosphocholine, compound list

[0060] Table 4

[0061]

[0062]

[0063]

[0064] Structure of the compound of the comparative example:

[0065] Table 5

[0066]

[0067] Synthesis steps:

[0068] (I) Synthesis of alcohol

[0069] (1) Synthesis of OC2-OH

[0070]

[0071] Experimental procedure: NaBH4(4.6 g, 120 mmol, 1.2 equiv.) was added to a three-necked flask, purged with nitrogen three times, 100 mL of super dry tetrahydrofuran was added under the protection of nitrogen, OC2-Me (26 g, 100 mmol, 1.0 equiv.) was slowly added dropwise under ice bath condition, the temperature was raised to 70°C, stirred overnight, the reaction was completed. Quench with aqueous ammonium chloride solution, filter, distill, get colorless liquid 20.9 g, yield 90%.

[0072] NMR data: 1 H NMR (400 MHz, CDCl3) δ 3.92 (t, J = 10 Hz, 2H), 2.85 (s, 1H). 19 F NMR (376 MHz, CD3OD) δ -54.1 (m, 2F), -57.2 (t, J = 9 Hz, 3F), -82.9 (m, 2F).

[0073] (2) Synthesis of OC3-OH

[0074]

[0075] Experimental procedure: NaBH4(9.2 g, 240 mmol, 1.2 equiv.) was added to a three-necked flask, purged with nitrogen three times, 100 mL of super dry tetrahydrofuran was added under the protection of nitrogen, OC3-Me (64.6 g, 198 mmol, 1.0 equiv.) was slowly added dropwise under ice bath condition, the temperature was raised to 70°C, stirred overnight, the reaction was completed. Quench with aqueous ammonium chloride solution, filter, distill under reduced pressure (41-43°C / 8100 pa), get colorless liquid 53.1 g, yield 90%.

[0076] NMR data: 1 H NMR (400 MHz, DMSO-d6) δ 6.17 (t, J = 6 Hz, 1H), 3.86 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -53.4 (m, 2F), -55.9 (m, 2F), -57.4 (m, 3F), -82.0 (m, 2F).

[0077] (3) Synthesis of OC4-OH

[0078]

[0079] Experimental procedure: NaBH4(3.5 g, 92 mmol, 1.2 equiv.) was added to a three-necked flask, purged with nitrogen three times, 60 mL of super dry tetrahydrofuran was added under the protection of nitrogen, C61-Me (30.1 g, 77 mmol, 1.0 equiv.) was slowly added dropwise under ice bath condition, the temperature was raised to 70 °C, stirred overnight, the reaction was completed. Quench with aqueous ammonium chloride solution, filter, distill under reduced pressure (40-42 °C / 306 pa), 25.6 g of colorless liquid was obtained, yield 92%.

[0080] NMR data: 1 H NMR (400 MHz, DMSO-d6) δ 6.15 (t, J = 7 Hz, 1H), 3.83 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -53.2 (m, 2F), -55.2 (m, 2F), -55.7 (m, 2F), -57.2 (m, 3F), -81.8 (m, 2F).

[0081] (4) Synthesis of C61-OH

[0082]

[0083] Experimental procedure: NaBH4(4.9 g, 129 mmol, 1.2 equiv.) was added to a 100 mL three-necked flask, purged with nitrogen three times, 20 mL of super dry tetrahydrofuran was added under the protection of nitrogen, C61-Me (37.0 g, 108 mmol, 1.0 equiv.) was slowly added dropwise under ice bath condition, the temperature was raised to 70 °C, stirred overnight, the reaction was completed. Quench with aqueous ammonium chloride solution, filter, distill under reduced pressure (38 °C / 3200 Pa), 27 g of colorless liquid was obtained, yield 79%.

[0084] NMR data: 1 H NMR (400 MHz, DMSO-d6) δ 6.33-6.26 (t, J = 6, 1H), 4.15-4.06 (m, 2H). 19 F NMR (376 MHz, DMSO-d6) δ -80.2 (m, 1F), -80.9 (m, 3F), -81.6 (m, 3F), -82.5 (m, 1F), -129.5 (m, 2F), -134.3 (m, 1F).

[0085] (5) Synthesis of C62-OH

[0086]

[0087] Experimental procedure: NaBH4(3.3 g, 88 mmol, 1.2 equiv.) was added into a 100 mL three-necked flask, which was purged with nitrogen for three times. Then, super dry THF 20 mL was added under the protection of nitrogen. C62-Me (26.4 g, 73 mmol, 1.0 equiv.) was added slowly. The temperature was raised to 70 °C and stirred overnight. The reaction was quenched by adding aqueous ammonium chloride solution dropwise. Filtration was performed and distilled under reduced pressure (40 °C / 3200 Pa) to obtain 14 g of colorless liquid with a yield of 58%.

[0088] NMR data: 1 H NMR (400 MHz, DMSO-d6) δ 6.30 (t, J = 6, 1H), 4.15-4.05 (m, 2H). 19 F NMR (376 MHz, DMSO-d6) δ -54.7 (m, 3F), -81.4 (m, 3F), -84.6 (m, 1F), -86.6 (m, 1F), -90.4 (m, 2F), -134.6 (m, 1F).

[0089] (6) Synthesis of C72-OH

[0090]

[0091] Experimental procedure: NaBH4(3.3 g, 88 mmol, 1.2 equiv.) was added into a 100 mL three-necked flask, which was purged with nitrogen for three times. Then, super dry THF 20 mL was added under the protection of nitrogen. C62-Me (26.4 g, 73 mmol, 1.0 equiv.) was added slowly. The temperature was raised to 70 °C and stirred overnight. The reaction was quenched by adding aqueous ammonium chloride solution dropwise. Filtration was performed and distilled under reduced pressure (40 °C / 3200 Pa) to obtain 14 g of colorless liquid with a yield of 58%.

[0092] NMR data: 1 H NMR (400 MHz, DMSO-d6) δ 6.30 (t, J = 6, 1H), 4.15-4.05 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.1 (m, 3F), -79.1 (m, 1F), -80.7 (m, 3F), -82.1 (m, 1F), -82.4 (m, 3F).-134.9 (m, 1F), -146.8 (m, 1F).

[0093] The preparation of C41-OH and C51-OH is the same as the above preparation procedure.

[0094] (II) Synthesis of cyclic phosphates

[0095] (1) Synthesis of OC2-P

[0096]

[0097] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then OC2-OH (20 g, 86 mmol, 1.0 equiv.), super dry tetrahydrofuran 50 mL, triethylamine (10.4 g, 103 mmol, 1.2 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (14.7 g, 103 mmol, 1.2 equiv.) was slowly added dropwise under ice bath condition, and the reaction was kept for 2 hours under ice bath, filtered, and distilled under reduced pressure (100-102 °C / 600 pa) to obtain 23.3 g of colorless liquid with a yield of 80%.

[0098] NMR data: 1 H NMR (400 MHz, CD3OD) δ 4.55-4.41 (m, 6H). 19 F NMR (376 MHz, CD3OD) δ -54.0 (m, 2F), -57.0 (t, J = 9 Hz, 3F), -81.1 (m, 2F).

[0099] (2) Synthesis of OC3-P

[0100]

[0101] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then OC3-OH (15 g, 50 mmol, 1.0 equiv.), super dry tetrahydrofuran 50 mL, triethylamine (6.0 g, 59 mmol, 1.2 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (8.7 g, 60 mmol, 1.2 equiv.) was slowly added dropwise under ice bath condition, and the reaction was kept for 2 hours under ice bath, filtered, and distilled under reduced pressure (83 °C / 110 pa) to obtain 14.1 g of colorless viscous liquid with a yield of 70%.

[0102] NMR data: 1 H NMR (400 MHz, CD3OD) δ 4.58-4.41 (m, 6H). 19 F NMR (376 MHz, CD3OD) δ -53.5 (m, 2F), -55.6 (m, 2F), -57.0 (m, 3F), -81.5 (m, 2F).

[0103] (3) Synthesis of OC4-P

[0104]

[0105] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then 4:2-OH (15 g, 57 mmol, 1.0 equiv.), super dry tetrahydrofuran 50 mL, triethylamine (6.9 g, 68 mmol, 1.2 equiv.) were added under nitrogen protection, and 2-chloro-2-oxo-1,3,2-dioxaphospholane (7.7 g, 54 mmol, 1.2 equiv.) was slowly dropped into the flask under ice bath condition, and the reaction was kept for 2 hours, then filtered, and distilled under reduced pressure (92 °C / 133 Pa) to obtain 14.7 g of colorless liquid, with a yield of 70%.

[0106] NMR data: 1 H NMR (400 MHz, CD3OD) δ 4.54-4.40 (m, 6H). 19 F NMR (376 MHz, CD3OD) δ -53.5 (m, 2F), -55.2 (m, 2F), -55.7 (m, 2F), -57.2 (m, 3F), -81.2 (m, 2F).

[0107] (4) Synthesis of 4:2-P

[0108]

[0109] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then 4:2-OH (15 g, 57 mmol, 1.0 equiv.), super dry tetrahydrofuran 50 mL, triethylamine (6.9 g, 68 mmol, 1.2 equiv.) were added under nitrogen protection, and 2-chloro-2-oxo-1,3,2-dioxaphospholane (7.7 g, 54 mmol, 1.2 equiv.) was slowly dropped into the flask under ice bath condition, and the reaction was kept for 2 hours, then filtered, and distilled under reduced pressure (92 °C / 133 Pa) to obtain 14.7 g of colorless liquid, with a yield of 70%.

[0110] NMR data: 1 H NMR (400 MHz, CD3OD) δ 4.52-4.36 (m, 6H), 2.62-2.50 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -81.2 (m, 3F), -114.1 (m, 2F), -124.7 (m, 2F), -126.2 (m, 2F).

[0111] (5) Synthesis of 6:2-P

[0112]

[0113] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then C61-OH (8.0 g, 25 mmol, 1.0 equiv.), super dry tetrahydrofuran 30 mL, triethylamine (2.8 g, 28 mmol, 1.1 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (4.0 g, 28 mmol, 1.1 equiv.) was slowly dropped under ice bath condition, and the reaction was kept for 2 hours under ice bath condition. Filtration and rotary evaporation were performed to obtain 5.2 g of colorless transparent liquid with a yield of 49%.

[0114] NMR data: 1 H NMR (400 MHz, CD3OD) δ 4.67 ~ 4.39 (m, 6H). 19 F NMR (376 MHz, CD3OD) δ -81.3 (m, 3F), -81.8 (m, 1F), -82.2 (m, 1F), -82.4 (m, 3F), -129.7 (m, 2F), -135.9 (m, 1F).

[0115] (6) Synthesis of C61-P

[0116]

[0117] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then C61-OH (8.0 g, 25 mmol, 1.0 equiv.), super dry tetrahydrofuran 30 mL, triethylamine (2.8 g, 28 mmol, 1.1 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (4.0 g, 28 mmol, 1.1 equiv.) was slowly dropped under ice bath condition, and the reaction was kept for 2 hours under ice bath condition. Filtration and rotary evaporation were performed to obtain 5.2 g of colorless transparent liquid with a yield of 49%.

[0118] NMR data: 1 H NMR (400 MHz, CD3OD) δ 4.67 ~ 4.39 (m, 6H). 19 F NMR (376 MHz, CD3OD) δ -81.3 (m, 3F), -81.8 (m, 1F), -82.2 (m, 1F), -82.4 (m, 3F), -129.7 (m, 2F), -135.9 (m, 1F). 31 F NMR (376 MHz, CD3OD) δ -81.3 (m, 3F), -81.8 (m, 1F), -82.2 (m, 1F), -82.4 (m, 3F), -129.7 (m, 2F), -135.9 (m, 1F).

[0119] (7) Synthesis of C62-P

[0120]

[0121] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen for three times, C72-OH (10 g, 26 mmol, 1.0 equiv.), super dry tetrahydrofuran 40 mL, triethylamine (3.4 g, 34 mmol, 1.3 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (4.8 g, 34 mmol, 1.3 equiv.) was added dropwise slowly under ice bath condition, keep ice bath reaction for 2 hours. Filtration, distillation under reduced pressure (95 °C / 133 Pa), get yellowish viscous liquid 8.5 g, yield 70%.

[0122] NMR data: 1 H NMR (400 MHz, CD3OD) δ 4.70 ~ 3.81 (m, 6H). 19 F NMR (376 MHz, CD3OD) δ -53.5 (m, 3F), -80.0 (m, 3F), -80.4 (m, 2F), -81.1 (s, 1F), -82.6 (s, 3F). -136.1 (m, 1F), -146.23 (m, 1F). 31 P NMR (162 MHz, CD3OD) δ -17.1.

[0123] (8) Synthesis of C72-P

[0124]

[0125] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen for three times, C72-OH (10 g, 26 mmol, 1.0 equiv.), super dry tetrahydrofuran 40 mL, triethylamine (3.4 g, 34 mmol, 1.3 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (4.8 g, 34 mmol, 1.3 equiv.) was added dropwise slowly under ice bath condition, keep ice bath reaction for 2 hours. Filtration, distillation under reduced pressure (95 °C / 133 Pa), get yellowish viscous liquid 8.5 g, yield 70%.

[0126] NMR data: 1 H NMR (400 MHz, CD3OD) δ 4.70 ~ 3.81 (m, 6H). 19 F NMR (376 MHz, CD3OD) δ -53.5 (m, 3F), -80.0 (m, 3F), -80.4 (m, 2F), -81.1 (s, 1F), -82.6 (s, 3F). -136.1 (m, 1F), -146.23 (m, 1F).

[0127] (9) Synthesis of C2-P

[0128]

[0129] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then C2-OH (12.1 mL, 40 mmol, 1.0 equiv.), super dry tetrahydrofuran (30 mL), triethylamine (6.7 mL, 48 mmol, 1.2 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (7.4 mL, 80 mmol, 2.0 equiv.) was added dropwise slowly under ice bath, and the reaction was carried out at room temperature for 4 h. Filtration and distillation gave a transparent liquid 5.6 g with a yield of 51%.

[0130] NMR data: 1 H NMR (400 MHz, CDCl3) δ 5.20 (m, 1H), 4.46 (m, 4H). 19 F NMR (376 MHz, CDCl3) δ -75.0 (m, 6F).

[0131] The preparation of C2-P, C41-P and C51-P is the same as the above preparation procedure.

[0132] (Three) Synthesis of tertiary amine (Amine)

[0133] (1) Synthesis of OC2-Amine

[0134]

[0135] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then C2-OH (12.1 mL, 40 mmol, 1.0 equiv.), super dry tetrahydrofuran (30 mL), triethylamine (6.7 mL, 48 mmol, 1.2 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (7.4 mL, 80 mmol, 2.0 equiv.) was added dropwise slowly under ice bath, and the reaction was carried out at room temperature for 4 h. Filtration and distillation gave a transparent liquid 5.6 g with a yield of 51%.

[0136] NMR data: 1 H NMR (400 MHz, CD3OD): δ 3.14 (t, J = 7 Hz, 2H), 2.18 (m, 2H), 2.05 (s, 6H), 1.61-1.51 (m, 2H). 19 F NMR (376 MHz, CD3OD): δ -55.1 (m, 2F), -58.6 (m, 3F), -81.5 (m, 2F).

[0137] (2) OC3-Amine

[0138]

[0139] Experimental procedure: To a 250 mL round bottom flask was added OC3-Me (100 g, 307 mmol, 1.2 eq), solvent methanol 50 mL, 3-dimethylaminopropylamine (26 g, 255 mmol, 1.0 eq), stirred at room temperature overnight, distilled under reduced pressure (66-68 °C / 133 pa), to get colorless liquid 100 g, yield 99%.

[0140] NMR data: 1 H NMR (400 MHz, CD3OD): δ 3.19 (t, J = 7 Hz, 2H), 2.24 (m, 2H), 2.11 (s, 6H), 1.66-1.58 (m, 2H). 19 F NMR (376 MHz, CD3OD): δ -54.6 (m, 2F), -56.9 (m, 2F), -58.7 (m, 3F), -81.6 (m, 2F).

[0141] (3) Synthesis of OC4-Amine

[0142]

[0143] Experimental procedure: To a 250 mL round bottom flask was added OC4-Me (100 g, 255 mmol, 1.2 eq), solvent methanol 50 mL, 3-dimethylaminopropylamine (21.7 g, 213 mmol, 1.0 eq), stirred at room temperature overnight, distilled under reduced pressure, to get colorless liquid 93.5 g, yield 95%.

[0144] NMR data: 1 H NMR (400 MHz, CD3OD): δ 3.23 (t, J = 7 Hz, 2H), 2.29 (t, J = 7 Hz, 2H), 2.15 (s, 6H), 1.70-1.61 (m, 2H). 19 F NMR (376 MHz, CD3OD): δ -54.6 (m, 2F), -56.4 (m, 2F), -57.0 (m, 2F), -58.8 (m, 3F), -81.6 (m, 2F).

[0145] (4) Synthesis of C4-Amine

[0146]

[0147] Experimental procedure: Into a 250 mL round bottom flask was added C4-Me (73 g, 320 mmol, 1.2 equiv.), methanol 60 mL, 3-dimethylaminopropylamine (27.3 g, 267 mmol, 1.0 eq), stirred at room temperature overnight, distilled under reduced pressure (55-57 °C / 133 pa), to get a colorless liquid 70 g, yield 72%.

[0148] NMR data: 1 H NMR (400 MHz, CD3OD): δ 3.35-3.30 (m, 2H), 3.31 (t, J = 16 Hz, 2H), 2.72-2, 57 (m, 2H), 2.4 (t, J = 16 Hz, 2H), 2.25 (s, 6H), 1.79-1.69 (m, 2H). 19 F NMR (376 MHz, CD3OD): δ -53.5 (m, 3F), -80.0 (m, 3F), -80.4 (m, 2F), -81.1 (m, 1F), -82.6 (m, 3F), -136.1 (m, 1F), -146.2 (m, 1F).

[0149] (5) Synthesis of 6:2-Amine

[0150]

[0151] Experimental procedure: Into a 250 mL three necked flask was added 3-dimethylaminopropylamine (12.3 g, 120 mmol, 1.2 equiv.), toluene 80 mL, triethylamine (12.1 g, 120 mmol, 1.2 equiv.), warmed to 40 °C, added perfluorohexylethylsulfonyl chloride (46.7 g, 100 mmol, 1.0 equiv.) drop wise, after the addition was complete, warmed to 75 °C, reacted overnight. Recrystallized to get a white solid 36 g, yield 70%.

[0152] NMR data: 1 H NMR (400 MHz, CD3OD): δ 3.35-3.30 (m, 2H), 3.31 (t, J = 16 Hz, 2H), 2.72-2, 57 (m, 2H), 2.4 (t, J = 16 Hz, 2H), 2.25 (s, 6H), 1.79-1.69 (m, 2H).

[0153] (6) Synthesis of C61-Amine

[0154]

[0155] Experimental procedure: Into a 250 mL round bottom flask, was added C61-Me (102 g, 296.5 mmol, 1.2 equiv.), 60 mL of methanol, 3-dimethylaminopropylamine (24 g, 235.8 mmol, 1.0 equiv.) was added under ice bath, stirred at room temperature overnight, distilled under reduced pressure (46 °C / 133 pa), to get 68.4 g of colorless liquid, yield 70%.

[0156] NMR data: 1 H NMR (400 MHz, (CD3)2CO) δ 9.48 (s, 1H), 3.51-3.40 (m, 2H), 2.41 (t, J = 6 Hz, 2H), 2.20 (s, 6H), 1.74 (m, 2H). 19 F NMR (376 MHz, (CD3)2CO) δ -81.6 (ddq, J = 149, 19, 7 Hz, 1F), -82.2 (t, J = 7 Hz, 3F), -83.4 (d, J = 2 Hz, 3F), -85.6 (dm, J = 149 Hz, 1F), -130.6 (s, 2F), -133.2 (dd, J = 20, 7 Hz, 1F).

[0157] (7) Synthesis of C62-Amine

[0158]

[0159] Experimental procedure: Into a 100 mL round bottom flask, was added C62-Me (24.6 g, 68.3 mmol, 1.1 equiv.), 20 mL of methanol, 3-dimethylaminopropylamine (6.1 g, 59.6 mmol, 1.0 equiv.) was added under ice bath, stirred at room temperature overnight. Distilled under reduced pressure (48 °C / 133 pa), to get 20.6 g of liquid, yield 80%.

[0160] NMR data: 1 H NMR (400 MHz, CD3OD): δ 3.32-3.23 (m, 2H), 2.32-2.23 (m, 2H), 2.15 (s, 6H), 1.70-1.61 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -57.1 (t, J = 9 Hz, 3F), -84.2 (d, J = 2 Hz, 3F), -86.6 (dd, J = 147, 18 Hz, 1F), -90.3 (dd, J = 147, 8 Hz, 1F), -92.0 (m, 2F), -134.1 (dd, J = 18, 8 Hz, 1F).

[0161] (8) Synthesis of C72-Amine

[0162]

[0163] Experimental procedure: Into a 250 mL round bottom flask was added C72-Me (108.6 g, 265 mmol, 1.05 equiv.), methanol 60 mL, 3-dimethylaminopropylamine (25.7 g, 252.3 mmol, 1.0 equiv.) was added under ice bath, stirred at room temperature overnight, distilled under reduced pressure (62-64 °C / 133 pa), obtained colorless liquid liquid 111 g, yield 92%.

[0164] NMR data: 1 H NMR (400 MHz, CD3OD) δ 3.38-3.30 (m, 2H), 2.34 (t, J = 7.6 Hz, 2H), 2.22 (s, 6H), 1.77-1.69 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -55.0 (m, 3F), -80.8 (m, 1F), -81.5 (m, 3F), -84.1 (dd, J = 6, 1.5 Hz, 3F), -84.5 (m, 1F), -133.9 (m, 1F), -147.8 (m, 1F).

[0165] The preparation of C41-Amine and C51-Amine is the same as the above preparation procedure.

[0166] (Four) Synthesis of Choline Phosphate:

[0167] Example 1: Synthesis of OC2-P-OC2

[0168]

[0169] Experimental procedure: Into a 15 mL pressure bottle was added OC2-P (1.7 g, 5 mmol, 1.0 equiv.), super dry acetonitrile solvent 5 mL, OC2-Amine (2.1 g, 7.5 mmol, 1.5 equiv.), heated to 70 °C, reacted for 48 hours. Column chromatography separation and purification, obtained light yellow solid 2.9 g, yield 90%.

[0170] 1 H NMR (400 MHz, CD3OD) δ 4.33-4.22 (m, 4H), 3.71-3.62 (m, 2H), 3.46 (m, 2H), 3.39 (t, J = 7 Hz, 2H), 3.19 (s, 6H), 2.14-2.03 (m, 2H). 19F NMR (376 MHz, CD3OD) δ -55.1 (m, 4F), -58.6 (m, 6F), -81.5 (m, 2F), -82.2 (m, 2F). 13 C NMR (100 MHz, CD3OD): δ 157.8, 63.6, 62.7, 59.1, 51.0, 36.5, 22.0, the carbons corresponding to the CF3OCF2OCF2- group could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.9. HRMS - ESI (m / z) calcd for C 15 H 19 O9N2F 14 P[M+H] + : 669.0677, found: 669.0668. IR (film) v / cm -1 : 3429, 1717, 1558, 1488, 1235, 1085, 1005, 964, 831, 682, 512.

[0171] Example 2: Synthesis of OC2-P-OC3

[0172]

[0173] Experimental procedure: To a 15 mL pressure tube was added OC2-P (1.5 g, 4.6 mmol, 1.0 equiv.), 5 mL of super-dry acetonitrile solvent, OC2-Amine (2.4 g, 6 mmol, 1.3 equiv.), and reacted at 70 °C for 48 hours. Column chromatography was used for separation and purification, and 2.7 g of light yellow solid was obtained with a yield of 80%.

[0174] 1 H NMR (400 MHz, CD3OD) δ 4.33-4.22 (m, 4H), 3.66 (m, 2H), 3.45 (m, 2H), 3.38 (t, J = 7 Hz, 2H), 3.18 (s, 6H), 2.14-2.03 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.5 (m, 2F), -55.1 (m, 2F), -56.8 (m, 2F), -58.6 (m, 6F), -81.4 (m, 2F), -82.2 (m, 2F). 13 C NMR (100 MHz, CD3OD): δ 157.7, 63.6, 62.7, 59.6, 59.1, 51.0, 36.5, 22.1, the carbons corresponding to the CF3OCF2OCF2- and CF3OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F.31 P NMR (CD3OD, 162 MHz): δ -1.9. HRMS-ESI (m / z) calcd for C 16 H 20 O 10 N2F 16 P[M+H] + : 735.0595, theoric value: 735.0583. IR (film) v / cm -1 : 3392, 1716, 1558, 1488, 1232, 1084, 1005, 984, 821, 688, 505.

[0175] Example 3: Synthesis of OC2-P-OC4

[0176]

[0177] Experimental procedure: To a 15 mL pressure tube was added OC2-P (1.9 g, 5.5 mmol, 1.0 equiv.), super-dry acetonitrile solvent 5 mL, OC4-Amine (3.3 g, 7.2 mmol, 1.3 equiv.), and reacted at 70 °C for 48 h. Column chromatography separation and purification, the product was obtained as a yellow sticky solid 3.7 g, yield 84%.

[0178] 1 H NMR (400 MHz, CD3OD) δ 4.32-4.22 (m, 4H), 3.66 (m, 2H), 3.45 (m, 2H), 3.38 (t, J = 7 Hz, 2H), 3.18 (s, 6H), 2.13-2.03 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.50 (m, 2F), -55.1 (m, 2F), -56.3 (m, 2F), -56.9 (m, 2F), -58.6 (m, 3F), -58.7 (m, 3F), -81.4 (m, 2F), -82.2 (m, 2F). 13 C NMR (100 MHz, CD3OD): δ 157.7, 63.6, 62.6, 59.1, 51.0, 36.5, 22.1, the carbons corresponding to the CF3OCF2OCF2- and CF3OCF2OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.9. HRMS-ESI (m / z) calcd for C 17 H 20 O 11 N2F 18 P[M+H] +: 801.0512, Theoretical: 801.0500. IR (film) v / cm -1 : 3464, 1717, 1558, 1488, 1227, 1092, 999, 965, 832, 689, 509.

[0179] Example 4: Synthesis of OC3-P-OC2

[0180]

[0181] Experimental procedure: To a 48 mL pressure tube was added OC3-P (3 g, 7.4 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, OC2-Amine (3.3 g, 9.6 mmol, 1.3 equiv.), and the reaction was allowed to proceed at 70 °C for 48 h. The product was isolated and purified by column chromatography to give 4.5 g of white solid in 82% yield.

[0182] 1 H NMR (400 MHz, CD3OD) δ 4.36-4.17 (m, 4H), 3.69-3.57 (m, 2H), 3.49-3.39 (m, 2H), 3.39-3.32 (t, J = 7 Hz 2H), 3.16 (s, 6H), 2.11-1.99 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.5 (m, 2F), -55.7 (m, 2F), -56.8 (m, 2F), -58.6 (m, 2F), -58.6 (m, 2F), -81.5 (m, 2F), -82.4 (m, 2F). 13 C NMR (100 MHz, CD3OD): δ 157.8, 63.6, 62.5, 59.1, 51.0, 36.5, 22.1, the carbons corresponding to the CF3OCF2OCF2- and CF3OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.4. HRMS - ESI (m / z) calculated for C 16 H 20 O 10 N2F 16 P[M+H] + : 735.0585, Found: 735.0595. IR (film) v / cm -1 : 3058, 2894, 1714, 1558, 1485, 1413, 1374, 1227, 1084, 954, 926, 816, 771, 501.

[0183] Example 5: Synthesis of OC3-P-OC3

[0184]

[0185] Experimental procedure: To a 48 mL pressure tube was added OC3-P (3 g, 7.5 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, OC3-Amine (3.8 g, 9.8 mmol, 1.3 equiv.), and the reaction was allowed to proceed at 70 °C for 48 h. Column chromatography was used to isolate and purify the product, which was obtained as a white solid 5.2 g in 82% yield.

[0186] 1 H NMR (400 MHz, CD3OD) δ 4.32-4.17 (m, 4H), 3.65-3.60 (m, 2H), 3.47-3.39 (m, 2H), 3.39-3.32 (t, J = 7 Hz, 2H), 3.16 (s, 6H), 2.11-1.99 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.6 (m, 4F), -56.8 (m, 4F), -58.6 (m, 6F), -81.5 (m, 2F), -82.2 (m, 2F). 13 C NMR (100 MHz, CD3OD): δ 157.7, 63.5, 63.5, 62.6, 59.1, 51.0, 36.5, 22.0, the carbons corresponding to the CF3OCF2OCF2OCF2- group could not be identified due to coupling effects of C-F. 31 PNMR (CD3OD, 162 MHz): δ -1.8. HRMS - ESI (m / z) found C 17 H 20 O 11 N2F 18 P[M+H] + : 801.0512, theoric: 801.0509. IR (film) v / cm -1 : 3301, 3026, 2893, 1714, 1590, 1485, 1413, 1375, 1228, 1011, 955, 926, 818, 722, 689, 617, 583, 528, 504.

[0187] Example 6: Synthesis of OC3-P-OC4

[0188]

[0189] Procedure: To a 48 mL pressure tube was added OC3-P (3 g, 7.4 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, OC4-Amine (4.6 g, 9.6 mmol, 1.3 equiv.) and reacted at 70 °C for 48 h. Column chromatography was used for isolation and purification to give 5.4 g of white solid in 85% yield.

[0190] 1 H NMR (400 MHz, CD3OD) δ 4.36-4.14 (m, 4H), 3.69-3.57 (m, 2H), 3.49-3.39 (m, 2H), 3.39-3.32 (m, 2H), 3.16 (s, 6H), 2.14-1.98 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.5 (m, 4F), -56.3 (m, 2F), -56.8 (m, 4F), -58.6 (m, 3F), -58.6 (m 3F), -81.4 (m, 2F), -82.2 (m, 2F). 13 C NMR (100 MHz, CD3OD): δ 157.8, 63.6, 62.7, 59.0, 51.1, 51.1, 36.5, 22.0, the carbons corresponding to the CF3OCF2OCF2OCF2- and CF3OCF2OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.8. HRMS - ESI (m / z) calcd for C 18 H 20 O 12 N2F 20 P[M+H] + : 867.0416, found: 867.0429. IR (film) v / cm -1 : 3057, 2894, 1716, 1558, 1486, 1412, 1232, 1069, 975, 958, 926, 833, 772, 688, 529.

[0191] Example 7: Synthesis of OC3-P-C4

[0192]

[0193] Experimental procedure: To a 48 mL pressure tube was added OC3-P (4.0 g, 9.9 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, C4-Amine (3.8 g, 12.9 mmol, 1.3 equiv.) and reacted at 70 °C for 48 h. Column chromatography separation and purification to get white solid 5.6 g, yield 80%.

[0194] 1 H NMR (400 MHz, CD3OD) δ 4.31-4.20 (m, 4H), 3.68-3.57 (m, 2H), 3.47-3.35 (m, 4H), 3.16 (s, 6H), 2.12-1.99 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.5 (m, 2F), -56.8 (m, 2F), -58.6 (m, 3F), -82.2 (m, 2F), -82.3 (m, 3F), -122.0 (m, 2F), -128.5 (m, 2F). 13 C NMR (100 MHz, CD3OD): δ 158.1, 63.6, 63.6, 62.6, 59.0, 51.0, 36.5, 22.1, the carbon corresponding to CF3CF2CF2- and CF3OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.9. HRMS - ESI (m / z) calcd for C 16 H 20 O8N2F 16 P[M+H] + : 703.0690, found: 703.0696. IR (film) v / cm -1 : 3200, 3032, 1711, 1555, 1484, 1411, 1227, 1077, 1011, 960, 911, 824, 753, 711, 633, 586, 510.

[0195] Example 8: Synthesis of OC3-P-C61

[0196]

[0197] Experimental procedure: To a 48 mL pressure tube was added OC3-P (4.0 g, 9.9 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, C4-Amine (3.8 g, 12.9 mmol, 1.3 equiv.) and reacted at 70 °C for 48 h. Column chromatography separation and purification to get white solid 5.6 g, yield 80%.

[0198] 1 H NMR (400 MHz, CD3OD) δ 4.37-4.15 (m, 4H), 3.64 (m, 2H), 3.52-3.37 (m, 4H), 3.17 (s, 6H), 2.15-2.01 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.6 (m, 2F), -56.8 (m, 2F), -58.6 (m, 3F), -81.7 (m, IF), -82.2 (m, 2F), -82.9 (m, 3F), -84.0 (m, 3F), -86.3 (m, IF), -131.2 (m, 2F), -134.2 (m, IF). 13 C NMR (100 MHz, CD3OD): δ 158.2, 63.6, 63.6, 62.6, 59.1, 51.0, 36.6, 22.0, the carbons corresponding to CF3CF2CF2OCF(CF3)- and CF3OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.8. HRMS - ESI (m / z) calcd for C 18 H 20 O9N2F 20 P[M+H] + : 819.0591, found: 819.0582. IR (film) v / cm -1 : 3389, 3193, 3030, 1711, 1552, 1483, 1413, 1232, 1073, 990, 959, 869, 746, 615, 509.

[0199] Example 9: OC3-P-C62

[0200]

[0201] Experimental procedure: To a 48 mL pressure tube was added OC3-P (2.5 g, 6.2 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, C62-Amine (3.5 g, 8.0 mmol, 1.3 equiv.) and reacted at 70 °C for 48 h. Column chromatography separation and purification to get white solid 4.6 g, yield 89%.

[0202] 1 H NMR (400 MHz, CD3OD) δ 4.37-4.20 (m, 4H), 3.66 (m, 2H), 3.42-3.32 (m, 4H), 3.17 (s, 6H), 2.13-2.02 (m, 2H).19 F NMR (376 MHz, CD3OD) δ -54.6 (m, 2F), -56.8 (m, 2F), -58.7 (m, 3F), -80.6 (m, IF), -81.5 (m, 3F), -82.2 (m, 2F), -84.0 (m, 3F), -84.7 (m, IF), -134.0 (m, IF), -147.9 (m, IF). 13 C NMR (100 MHz, CD3OD): δ 158.4, 63.6, 63.6, 62.6, 59.0, 51.0, 36.6, 22.0, the carbons corresponding to the CF3OCF2CF2OCF(CF3)- and CF3OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.8. HRMS - ESI (m / z) calcd for C 18 H 20 O 10 N2F 20 P[M+H] + : 819.0538, found: 819.0531. IR (film) v / cm -1 : 3394, 3161, 3011, 1711, 1551, 1481, 1460, 1416, 1376, 1227, 1070, 927, 959, 939, 903, 851, 747, 683, 617, 527, 489, 409.

[0203] Example 10: Synthesis of OC3-P-C72

[0204]

[0205] Experimental procedure: To a 48 mL pressure tube was added starting material OC3-P (2 g, 4.9 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, C72-Amine (3.2 g, 6.4 mmol, 1.3 equiv.), and reacted at 70 °C for 48 h. Column chromatography separation and purification to get white solid 3.2 g, yield 72%.

[0206] 1 H NMR (400 MHz, CD3OD) δ 4.31-4.20 (m, 4H), 3.68-3.59 (m, 2H), 3.49-3.34 (m, 4H), 3.16 (s, 6H), 2.12-1.99 (m, 2H). 19F NMR (376 MHz, CD3OD) δ -54.5 (m, 2F), -54.9 (m, 2F), -56.8 (m, 2F), -58.6 (m, 3F), -80.5 (m, IF), -81.4 (m, 3F), -82.2 (m, 2F), -84.0 (m, 3F), -84.9 (m, IF), -134.2 (m, 2F), -147.9 (m, IF). 13 C NMR (100 MHz, CD3OD): δ 158.3, 63.6, 63.6, 62.6, 59.0, 51.0, 36.6, 22.0, the carbon corresponding to CF3OCF(CF3)CF2OCF(CF3)- and CF3OCF2OCF2OCF2- groups cannot be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.9. HRMS - ESI (m / z) calcd for C 19 H 20 O 10 N2F 22 P[M+H] + : 885.0503, found: 885.0499. IR (film) v / cm -1 : 3203, 3034, 1709, 1552, 1483, 1412, 1159, 1076, 982, 959, 911, 893, 825, 773, 740, 684, 647, 510.

[0207] Example 11: Synthesis of OC4-P-OC2

[0208]

[0209] Experimental procedure: To a 48 mL pressure tube was added OC4-P (2.7 g, 5.8 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, OC2-Amine (4.0 g, 8.7 mmol, 1.5 equiv.), and reacted at 70 °C for 48 hours. Column chromatography was used for separation and purification, and 4.6 g of light-colored solid was obtained with a yield of 99%.

[0210] 1 H NMR (400 MHz, CD3OD) δ 4.32-4.22 (m, 4H), 3.66 (m, 2H), 3.45 (m, 2H), 3.38 (t, J = 6.8 Hz, 2H), 3.18 (s, 6H), 2.14-2.03 (m, 2H). 19F NMR (376 MHz, CD3OD) δ -54.5 (m, 2F), -55.1 (m, 2F), -56.3 (m, 2F), -56.9 (m, 2F), -58.6 (m, 3F), -58.7 (m, 3F), -81.5 (m, 2F), -82.2 (m, 2F). 13 C NMR (100 MHz, CD3OD): δ 157.8, 63.5, 62.6, 59.1, 51.0, 36.5, 22.1, the carbons corresponding to the CF3OCF2OCF2- and CF3OCF2OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.9. HRMS - ESI (m / z) calcd for C 17 H 20 O 11 N2F 18 P[M+H] + : 801.0512, found: 801.0499. IR (film) v / cm -1 : 3413, 1716, 1557, 1486, 1231, 1090, 1012, 974, 829, 681, 507.

[0211] Example 12: Synthesis of OC4-P-OC3

[0212]

[0213] Experimental procedure: To a 48 mL pressure tube was added OC4-P (2.6 g, 5.5 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, OC3-Amine (3.3 g, 8.8 mmol, 1.6 equiv.), and reacted at 70 °C for 48 hours. Column chromatography was used for separation and purification, and 3.4 g of light-colored solid was obtained with a yield of 71%.

[0214] 1 H NMR (400 MHz, CD3OD) δ 4.32-4.22 (m, 4H), 3.66 (m, 2H), 3.45 (m, 2H), 3.38 (t, J = 7 Hz, 2H), 3.18 (s, 6H), 2.13-2.02 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.5 (m, 4F), -56.3 (m, 2F), -56.8 (m, 4F), -58.6 (m, 6F), -81.1 (m, 2F), -82.2 (m, 2F). 13C NMR (100 MHz, CD3OD): δ 157.7, 63.5, 62.6, 59.1, 51.0, 36.5, 22.1, the carbons corresponding to the CF3OCF2OCF2OCF2- and CF3OCF2OCF2OCF2OCF2- groups cannot be identified due to the coupling effect of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.9. HRMS - ESI (m / z) calculated for C 18 H 20 O 12 N2F 20 P[M+H] + : 867.0429, found: 867.0415. IR (film) v / cm -1 : 3391, 1716, 1557, 1485, 1231, 1070, 983, 822, 690, 504.

[0215] Example 13: Synthesis of OC4-P-OC4

[0216]

[0217] Experimental procedure: To a 48 mL pressure tube was added OC4-P (3.7 g, 7.9 mmol, 1.0 equiv.), acetonitrile solvent 15 mL, OC4-Amine (5.5 g, 11.9 mmol, 1.5 equiv.), and reacted at 70 °C for 48 hours. Column chromatography was used for separation and purification, and 5.7 g of light-colored solid was obtained with a yield of 77%.

[0218] 1 H NMR (400 MHz, CD3OD) δ 4.33-4.22 (m, 4H), 3.66 (m, 2H), 3.46 (m, 2H), 3.38 (t, J = 7 Hz, 2H), 3.19 (s, 6H), 2.14-2.03 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.5 (m, 4F), -56.4 (m, 4F), -56.9 (m, 4F), -58.7 (m, 6F), -58.7 (m, 2F), -81.4 (m, 2F), -82.2 (m, 2F). 13 C NMR (100 MHz, CD3OD): δ 157.7, 63.5, 62.6, 59.1, 51.0, 36.5, 22.1, the carbons corresponding to the CF3OCF2OCF2OCF2- and CF3OCF2OCF2OCF2OCF2- groups cannot be identified due to the coupling effect of C-F. 31P NMR (CD3OD, 162 MHz): δ -1.9. HRMS-ESI (m / z) calcd for C 19 H 20 O 13 N2F 22 P[M+H] + : 933.0346, found: 933.0331. IR (film) v / cm -1 : 3427, 1716, 1556, 1485, 1232, 1089, 998, 976.5, 835, 690, 508.

[0219] Example 14: Synthesis of 4:2-P-OC3

[0220]

[0221] Experimental procedure: To a 48 mL pressure tube was added 4:2-P (2.2 g, 14.6 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, OC3-Amine (7.5 g, 18.9 mmol, 1.3 equiv.), and reacted at 70 °C for 48 h. Column chromatography was used for isolation and purification, and 5.1 g of white solid was obtained with a yield of 64% and a NMR purity of 90%.

[0222] White solid: 1 H NMR (400 MHz, CD3OD) δ 4.31 ~ 4.10 (m, 4H), 3.67 ~ 3.60 (m, 2H), 3.47 ~ 3.29 (m, 4H), 3.16 (s, 6H), 2.67 ~ 2.50 (m, 2H), 2.12 ~ 1.99 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.5 (m, 2F), -56.8 (m, 2F), -58.6 (m, 3F), -81.4 (m, 10 Hz, 2F), -82.7 (m, 3F), -114.9 (m, 2F), -125.8 (m, 2F), 127.3 (m, 2F). 13 C NMR (100 MHz, CD3OD): δ 157.7, 63.5, 62.6, 58.9, 57.5, 51.0, 36.5, 31.7, 22.1, the carbons corresponding to the CF3CF2CF2CF2- and CF3OCF2OCF2OCF2- groups could not be identified due to coupling effects with C-F. 31 P NMR (CD3OD, 162 MHz): δ -0.7. HRMS-ESI (m / z) calcd for C 18 H 20 O8N2F 18 P[M+H]+ : 767.0815, found: 767.0821. IR (film) v / cm -1 : 3358, 3038, 1716, 1559, 1480, 1232, 1134, 1081, 1012, 983, 921, 874, 831, 787, 749, 710, 535, 484, 415.

[0223] Example 15: Synthesis of C61-P-OC3

[0224]

[0225] Experimental procedure: To a 48 mL pressure tube was added C61-P (4.3 g, 10.2 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, OC3-Amine (5.3 g, 13.3 mmol, 1.3 equiv.) and reacted at 70 °C for 48 h. Column chromatography was used for isolation and purification, and 8.2 g of white solid was obtained with a yield of 73%.

[0226] 1 H NMR (400 MHz, CD3OD) δ 4.58 ~ 4.39 (m, 2H), 4.34 ~ 4.17 (m, 2H), 3.71 ~ 3.57 (m, 2H), 3.51 ~ 3.34 (m, 4H), 3.17 (s, 6H), 2.15 ~ 2.01 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.5 (m, 2F), -56.8 (m, 2F), -58.6 (m, 3F), -81.4 (m, 2F), -82.0 (m, 1F), -82.8 (m, 3F), -83.6 (m, 3F), -84.0 (m, 1F), -131.1 (m, 2F), -135.5 (m, 1F). 13 C NMR (100 MHz, CD3OD): δ 159.2, 64.9, 64.0, 63.3, 60.5, 52.4, 37.9, 23.5, the carbons corresponding to CF3CF2CF2OCF(CF3)- and CF3OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -2.3. HRMS - ESI (m / z) calculated for C 18 H 20 O9N2F 20 P [M+H] + : 819.0582, found: 819.0574. IR (film) v / cm -13395, 1717, 1558, 1488, 1239, 1088, 990, 932, 839, 808, 751, 689, 539.

[0227] Example 16: Synthesis of C62-P-OC3

[0228]

[0229] Experimental procedure: To a 48 mL pressure tube was added C62-P (5.0 g, 11.4 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, OC3-Amine (5.8 g, 14.8 mmol, 1.3 equiv.), and reacted at 70 °C for 48 h. Column chromatography was used for isolation and purification, and 8.7 g of white solid was obtained with a yield of 81%.

[0230] 1 H NMR (400 MHz, CD3OD) δ 4.59-4.39 (m, 2H), 4.33-4.17 (m, 2H), 3.65 (m, 2H), 3.50-3.34 (m, 4H), 3.17 (s, 6H), 2.15-2.01 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.6 (m, 2F), -56.8 (m, 2F), -57.0 (m, 3F), -58.6 (m, 3F), -81.4 (m, 2F), -83.6 (m, 3F), -86.2 (m, IF), -88.3 (m, IF), -92.0 (m, 2F), -135.7 (m, IF). 13 C NMR (100 MHz, CD3OD): δ 159.2, 64.9, 64.0, 63.3, 60.5, 52.4, 37.9, 23.5, the carbons corresponding to the CF3OCF2CF2OCF(CF3)- and CF3OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -2.3. HRMS - ESI (m / z) calcd for C 18 H 20 O 10 N2F 20 P[M+H] + :835.0531, found: 835.0524. IR (film) v / cm -1 :3413, 1716, 1558, 1473, 1247, 1087, 984, 933, 844, 799, 684, 529.

[0231] Example 17: Synthesis of C72-P-OC3

[0232]

[0233] Experimental procedure: To a 48 mL pressure tube was added C72-P (5.9 g, 12.1 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, OC3-Amine (6.2 g, 15.7 mmol, 1.3 equiv.) and reacted at 70 °C for 48 h. Column chromatography was used for isolation and purification to give 7.9 g of white solid with a yield of 74%.

[0234] 1 H NMR (400 MHz, CD3OD) δ 4.59-4.39 (m, 2H), 4.33-4.17 (m, 2H), 3.65 (m, 2H), 3.50-3.34 (m, 4H), 3.18 (s, 6H), 2.15-2.01 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.6 (m, 2F), -54.9 (m, 3F), -56.8 (m, 2F), -58.6 (m, 3F), -80.1 (m, IF), -81.3 (m, 3F), -81.4 (m, 2F), -82.9 (m, IF), -83.6 (m, 3F), -135.2 (m, IF), -147.3 (m, IF). 13 C NMR (100 MHz, CD3OD): δ 159.2, 64.9, 64.0, 63.3, 60.5, 52.4, 37.9, 23.5, the carbons corresponding to the CF3OCF(CF3)CF2OCF(CF3)- and CF3OCF2OCF2OCF2- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -2.3. HRMS - ESI (m / z) calcd for C 19 H 20 O 10 N2F 22 P [M+H]+: 885.0499, found: 885.0493. IR (film) v / cm-1: 3437, 1717, 1557, 1488, 1237, 1086, 983, 933, 838, 773, 686, 538, 496. -1 :3437,1717,1557,1488,1237,1086,983,933,838,773,686,538,496.

[0235] Example 18: Synthesis of C72-P-C72

[0236]

[0237] Experimental procedure: To a 48 mL pressure tube was added C72-P (4.0 g, 8.2 mmol, 1.0 equiv.), acetonitrile 10 mL, C72-Amine (5.1 g, 10.7 mmol, 1.3 equiv.) and reacted at 70 °C for 48 h. Column chromatography was used for isolation and purification to give 6.4 g of white solid in 80% yield.

[0238] 1 H NMR (CD3OD, 400 MHz): δ 4.60-4.38 (m, 2H), 4.31-4.18 (m, 2H), 3.66 (m, 2H), 3.48-3.35 (m, 4H), 3.17 (s, 6H), 2.16-1.96 (m, 2H). 19 F NMR (CD3OD, 376 MHz): δ -54.9 (m, 6F), -82.6 (m, IF), -82.3 (m, 3F), -134.0 (m, IF), -135.3 (m, IF), -147.5 (m, 2F), 13 C NMR (CD3OD, 100 MHz): δ 158.4, 63.7, 62.7, 61.8, 59.0, 51.1, 36.6, 22.0, the carbons corresponding to the CF3OCF(CF3)CF2OCF(CF3)- group could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -2.3. HRMS - ESI (m / z) calcd for C 21 H 20 O9F 26 P[M+H] + : 969.0472, found 949.0486. IR (film) V / cm -1 : 3019, 1712, 1553, 1477, 1236, 1160, 1113, 1080, 1028, 983, 914, 842, 807, 740, 685, 647, 538, 486.

[0239] The preparation of examples 19-25 was identical to the procedure of examples 1-18.

[0240] Comparative example 1: synthesis of 6:2-P-Me

[0241]

[0242] Experimental procedure: Under ice bath conditions, 6:2-P (5 g, 10.6 mmol, 1.0 equiv.), 10 mL of acetonitrile, and a tetrahydrofuran solution of trimethylamine (10 mL, 20 mmol, 2.0 equiv.) were added to a 45 mL pressure-resistant flask. The mixture was heated to 70 °C and reacted for 48 hours. The product was purified by column chromatography to obtain 3.4 g of a white solid, with a yield of 60%.

[0243] 1 H NMR (CD3OD, 400MHz): δ4.30~4.23(m,2H), 4.16(m,2H), 3.61(m,2H), 3.20(s,9H), 2.50~2.68(m,2H). 19 F NMR (CD3OD, 376MHz): δ-82.5(m,3F),-114.6(m,2F),-123.2(m,2F),-124.0(m,2F),-124.8(m,2F),-127.4(m,2F). 13 C NMR (CD3OD, 100MHz): δ66.1, 59.1, 57.41, 53.1, 31.8. Due to the coupling effect of CF, the carbon corresponding to the CF3CF2CF2CF2CF2CF2- group cannot be identified. 31 PNMR (CD3OD, 162MHz): δ-0.7. HRMS-ESI (m / z) calculated value C 13 H 18 O4NF 13 P[M+H] + 530.0760, measured value 530.0765. IR (film) V / cm -1 :3424,3037,2952,1663,1492,1247,1192.

[0244] Comparative Example 2: Synthesis of C72-P-Me

[0245]

[0246] Experimental procedure: Under ice bath conditions, C72-P (5 g, 10 mmol, 1.0 equiv.), 10 mL of acetonitrile, and a tetrahydrofuran solution of trimethylamine (10 mL, 20 mmol, 2.0 equiv.) were added to a 48 mL pressure-resistant flask. The mixture was heated to 70 °C and reacted for 48 hours. The product was purified by column chromatography to obtain 9.8 g of a white solid, with a yield of 90%.

[0247] 1H NMR (CD3OD, 400MHz): δ4.57~4.41(m,2H), 4.33~4.20(m,2H), 3.62(m,2H), 3.19(s,9H), 19 F NMR (CD3OD, 376MHz): δ-55.0(m,3F),-80.2(m,1F),-81.3(m,3F),-82.9(m,1F),-83.6(m,3F),-135.2(m,1F),-147.3(m,1F), 13 C NMR (CD3OD, 100MHz): δ 66.0, 62.0, 59.3, 53.2. Due to the coupling effect of CF, the carbon corresponding to the CF3OCF(CF3)CF2OCF(CF3)- group cannot be identified. 31 PNMR (CD3OD, 162MHz): δ-2.3. HRMS-ESI (m / z) calculated value C 12 H 16 O6F 13 P[M+H] + :548.0494, measured value 548.0502. IR (film) V / cm -1 :1315,1239,1160,1193.

[0248] Synthesis of Comparative Example 3:4:2-P-C4

[0249]

[0250] Experimental procedure: Add 2.8 g of 4:2-P (18.5 mmol, 1.0 equiv.), 5 mL of acetonitrile solvent, and 3.1 g of C4-Amine (24.1 mmol, 1.3 equiv.) to a 48 mL pressure-resistant bottle, and react at 70 °C for 48 hours. Purify by column chromatography to obtain 3.7 g of a white solid, yield 71%, NMR purity 90%.

[0251] White solid: 1 H NMR (400MHz, CD3OD) δ4.26~4.17(m,4H),4.21~4.10(m,4H),3.65~3.62(m, 2H),3.46~3.40(m,4H),3.17(s,6H),2.53~2.72(m,2H),2.12~2.04(m,2H). 19FNMR(376MHz, CD3OD)δ-82.3(m,3F),-82.7(m,3F),-114.9(m,2F),-122.0(m,2F),-125.7(m,2F),-127.3(m,2F),-128.5(m,2F). 13 C NMR (100MHz, CD3OD): δ 158.1, 63.7, 62.6, 58.9, 57.4, 51.0, 36.5, 31.6, 22.1. Due to the coupling effect of CF, the carbons corresponding to the CF3CF2CF2CF2- and CF3CF2CF2- groups cannot be identified. 31 P NMR (CD3OD, 162MHz): δ-0.7. HRMS-ESI (m / z) calculated value C 17 H 22 O5N2F 16 P[M+H] + :669.1005, Measured value: 669.1001. IR(film) v / cm -1 :3242,2979,1711,1553,1481,1355,1224,1134,1081,975,974,830,785,749,710,634,595,526,484,412.

[0252] Methods for testing surface tension:

[0253] This experiment used German... The company's K100C fully automatic surface (interfacial) tensiometer measures the surface tension of a fluorinated surfactant solution using the platinum plate method at room temperature, with units of mN / m. After preparation, the solution is sonicated to ensure uniform dispersion of the solute in the solvent, then allowed to stand overnight before surface tension testing. [Reference] E. Kissa. Fluorinated surfactants and Repellents [M], Marcel Dekker Inc., New York, 2001.

[0254] Example 1: Surface tension of fluorinated choline phosphate in aqueous solutions of different concentrations:

[0255] Table 6

[0256]

[0257]

[0258] Note: Surface tension of the solution was tested using a K100C fully automatic surface / interfacial tensiometer manufactured by Krüss GmbH, Germany, employing the platinum plate method. The test temperature was 22–26°C. Soluble > 10 wt%; 1 wt% < soluble < 10 wt%; 0.01 wt% < slightly soluble < 1 wt%; sparingly soluble < 0.01 wt%.

[0259] *Among them, ① the implementation effects (solubility and surface tension) of Examples 19, 20, and 22 (C41-P-OC3, OC3-P-C41, and C2-P-OC4) are comparable to those of OC3-P-C4 and OC2-P-OC3; ② the implementation effects (solubility and surface tension) of Examples 21, 23, and 25 (C51-P-OC3, OC3-P-C51, and C41-P-C62) are comparable to those of 4:2-P-OC3, OC2-P-OC3, and OC3-P-OC2; ③ the implementation effects (solubility and surface tension) of Example 24 (C62-P-C62) are comparable to those of OC3-P-C72 and C72-P-OC3.

[0260] The present invention employs a specific double-chain fluorinated segment combined with a phosphocholine structure, which effectively improves the surface activity of surfactants. For example, compared with Comparative Examples 1 and 2, the surface tension of the double-chain compound (e.g., Example 18 at 0.01 wt% and 0.001 wt% concentrations) is significantly reduced.

[0261] The present invention also employs short-chain fluorinated ether segments, which effectively improves the surface activity of surfactants. For example, compared with Comparative Example 3, the present invention introduces short-chain fluorinated ether segments, resulting in a significant decrease in surface tension; and the introduction of fluorinated ether segments improves the solubility of surfactants.

[0262] In summary, this invention combines phosphocholine with a specific fluorinated ether segment and adopts a difluorinated segment structure, which effectively improves the surface activity and solubility of the surfactant, providing a surfactant with high overall performance.

[0263] Table 7 shows the total number of fluorine and carbon atoms and the total number of oxygen atoms in the compounds.

[0264]

[0265]

[0266] Note: Fluorocarbon atom refers to a carbon atom that has been replaced by one or more fluorine atoms.

[0267] As can be seen from Table 7, when R F1 +R F2 When the total number of fluorinated carbon atoms and the total number of oxygen atoms are the same, the performance at low concentrations is not significantly different; the more fluorinated carbon atoms present, the better the performance. Among these, R... F1+R F2 Total number of fluorinated carbon atoms: oxygen atoms less than 3;

[0268] When R F1 +R F2 When the total number of fluorinated carbon atoms is the same, R F1 +R F2 The greater the sum of the total number of carbon atoms and oxygen atoms in a medium, the better its overall performance. For example:

[0269] (1) OC4-P-OC4, OC3-P-C72 and C72-P-OC3; or,

[0270] (2) OC3-P-OC4, OC4-P-OC3, OC3-P-C62, C62-P-OC3, OC3-P-C61, and C61-P-OC3; or,

[0271] (3) OC2-P-OC4, OC3-P-OC3, OC4-P-OC2 and 4:2-P-OC3; or,

[0272] (4) OC2-P-OC3, OC3-P-OC2, OC3-P-C4 and 4:2-P-C4.

[0273] In addition, in this invention, compounds with a total number of fluorine and carbon atoms greater than or equal to 8 and less than 12, and a total number of fluorine and carbon atoms plus a total number of oxygen atoms greater than or equal to 13, all have a surface tension of less than 20 mN / m at a concentration of 0.001 wt%.

Claims

1. A compound as shown in formula I or a salt thereof, characterized in that, wherein n is 0, 1 or 2; p is 2, 3, 4, 5 or 6; R 1 and R 2 are independently C 1-C 6 alkyl. Preferably, the total number of fluorocarbon atoms is greater than or equal to 7; the total number of fluorocarbon atoms and the total number of oxygen atoms is greater than or equal to 12. R F1 and R F2 are each independently wherein each Y is independently F1 and / or R F2 at least one Y is *-OCF2-** or *-OCF(CF3)-**; m is independently 1, 2, 3, 4, or 5; the direction from the *" end to the "**" end is from the CF3 direction to the direction. More preferably, the total number of fluorocarbon atoms is greater than or equal to 8 and less than 12; the total number of fluorocarbon atoms and the total number of oxygen atoms is greater than or equal to 13.

2. The compound of claim 1, or a salt thereof, wherein R F1 and R F2 wherein the ratio of the total number of fluorine and carbon atoms to the total number of oxygen atoms is less than 3; wherein the total number of fluorine and carbon atoms is preferably 12 or less, such as 6, 7, 8, 9 or 10; and / or the total number of oxygen atoms is 3 or more, such as 3, 4, 5, 6, 7 or 8.

3. The compound of claim 2, or a salt thereof, wherein R F1 and R F2 wherein the total number of fluorocarbon atoms is greater than or equal to 6; the sum of the total number of fluorocarbon atoms and the total number of oxygen atoms is greater than or equal to 10; It satisfies one or more of the following conditions: (1) p is 3; 4. The compound of claim 1, or a salt thereof, wherein R F1 and R F2 at least one of which is for example R F1 is or R F2 is wherein m is independently 1, 2, 3 or 4; Preferably, R F1 and R F2 are the same. For example, R F1 and R F2 are the same.

5. The compound of claim 4, or a salt thereof, wherein independently 6. The compound of claim 1, or a salt thereof, wherein (2) R 1 and R 2 are independently methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl; preferably methyl; more preferably, R 1 and R 2 are both methyl; The compound as shown in formula I is a compound of formula I-1: Preferably, the compound as shown in formula I is a compound of formula I-2: (3) independently 7. The compound of claim 1, or a salt thereof, wherein Or, the compound as shown in formula I is a compound of formula I-3: wherein R F1 and R F2 as in any of claims 1 to 6; The compound as shown in formula I is any one of the following: wherein m and R F2 as claimed in any one of claims 1 to 6; 9.A compound as shown in formula II, characterized in that, wherein m and R F1 As claimed in any one of claims 1 to 6.

8. The compound of claim 1, or a salt thereof, wherein ​ ​ wherein R F1 and n are as described in any of claims 1-8.

10. A compound, characterized in that, It is any one of the following structures:

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