Difluoroalkylphosphorylcholine compound and intermediate thereof

Abstract

Provided are a difluoroalkylphosphorylcholine compound and an intermediate thereof. Specifically provided is a compound represented by formula I or a salt thereof. The compound represented by formula I or a salt thereof exhibits good surface activity, good solubility and good environmental friendliness and biofriendliness, is easy to store at a high concentration and convenient to transport, and has good application prospects.

Description

Bisfluoro-chained phosphocholine compounds and intermediates thereof

[0001] This application claims priority to Chinese patent application 2024112943626, filed on September 14, 2024. This application incorporates the entirety of the aforementioned Chinese patent application. TECHNICAL FIELD

[0002] The present application relates to a bisfluoro-chained phosphocholine compound and intermediates thereof BACKGROUND

[0003] 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.), and are indispensable in the fields of materials, fire protection, electroplating, and textiles. With its extensive use, people have begun to focus on its environmental risks. Research has found that long-fluoroalkyl 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.

[0004] 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 effects; while short-chain fluorinated surfactants of the same type have better environmental effects, but the solution surface tension rises and the surface activity becomes poor, so substitutes often exhibit performance degradation or increased dosage. 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

[0005] The present application aims to overcome the defects of the prior art surfactants, such as strong biological toxicity, high environmental persistence and poor surface activity.

[0006] The present application solves the above technical problems by the following technical solutions.

[0007] The present application provides a compound as shown in formula I or a salt thereof,

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

[0009] R F1 and R F2 are each independently wherein each Y is independently *-CF2-**, *-OCF2-**, *-OCF(CF3)-** or *-CH(CF3)-**, and R F1 and / or R F2 At least one Y is *-OCF2-** or *-OCF(CF3)-**.

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

[0011] In some embodiments of the present application, R F1 and R F2 The ratio of the total number of fluorocarbon atoms to the total number of oxygen atoms is less than 3; for example, the ratio of the total number of fluorocarbon atoms to the total number of oxygen atoms is 1.0-2.8, preferably 1.25-2.67. The fluorocarbon atom refers to a carbon atom substituted by one or more fluorine atoms. The total number of fluorocarbon atoms refers to the sum of the number of fluorocarbon atoms in R F1 and the number of fluorocarbon atoms in R F2 . The total number of oxygen atoms refers to the sum of the number of oxygen atoms in R F1 and the number of oxygen atoms in R F2 .

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

[0013] ​In some embodiments of the application, R F1 and R F2 wherein the total number of oxygen atoms is greater than or equal to 3; for example, the total number of oxygen atoms is 3 to 8, and in further example, 3, 4, 5, 6, 7, or 8.

[0014] In some embodiments of the application, R F1 and R F2 wherein the total number of fluorocarbon atoms is greater than or equal to 6; the total number of fluorocarbon atoms plus the total number of oxygen atoms is greater than or equal to 10; for example, the total number of fluorocarbon atoms is 6 to 10, and the total number of fluorocarbon atoms plus the total number of oxygen atoms is 10 to 18.

[0015] In some embodiments of the application, R F1 and R F2 wherein the total number of fluorocarbon atoms is greater than or equal to 6; the total number of fluorocarbon atoms plus the total number of oxygen atoms is greater than or equal to 10; for example, the total number of fluorocarbon atoms is 6 to 10, and the total number of fluorocarbon atoms plus the total number of oxygen atoms is 10 to 18.

[0016] Preferably, the total number of fluorocarbon atoms is greater than or equal to 7; the total number of fluorocarbon atoms plus the total number of oxygen atoms is greater than or equal to 12; for example, the total number of fluorocarbon atoms is 7 to 10, and the total number of fluorocarbon atoms plus the total number of oxygen atoms is 12 to 18.

[0017] More preferably, the total number of fluorocarbon atoms is greater than or equal to 8, less than 12; the total number of fluorocarbon atoms plus the total number of oxygen atoms is greater than or equal to 13; for example, the total number of fluorocarbon atoms is 8 to 10, and the total number of fluorocarbon atoms plus the total number of oxygen atoms is 13 to 18.

[0018] In some embodiments of the application, R F1 and R F2 wherein at least one is for example, R F1 is or R F2 is wherein m is independently 1, 2, 3, or 4.

[0019] In some embodiments of the application, R F1 and R F2 are both for example, R F1 and R F2 are the same; m is independently 1, 2, 3, or 4.

[0020] In some embodiments of the application, is independently

[0021] In some embodiments of the present application, independently

[0022] In some embodiments of the present application, p is 2 or 3; preferably 3.

[0023] In some embodiments of the present application, R1and R2are independently methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or t-butyl; preferably methyl; more preferably, R1and R2are both methyl.

[0024] In some embodiments of the present application, the compound of Formula I is a compound of Formula I-1:

[0025] wherein R F1 and R F2 are independently described in any aspect of the present application.

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

[0027] wherein m and R F2 are independently described in any aspect of the present application.

[0028] In some embodiments of the present application, the compound of Formula I is a compound of Formula I-3:

[0029] wherein m and R F1 are independently described in any aspect of the present application.

[0030] In some embodiments of the present application, the compound of Formula I is any one of the following:

[0031] The present application provides a compound of Formula II,

[0032] wherein R F1 and n are independently described in any aspect of the present application.

[0033] The present application provides a compound, which is:

[0034] The term "salt" refers to a salt of a compound resulting from reaction of the compound 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, hydrochloride salts, sulfate salts, methanesulfonate salts, and the like.

[0035] On the basis of not violating the common knowledge in the art, the above-mentioned preferred conditions can be combined arbitrarily, i.e. to obtain each preferred example of the present application.

[0036] The reagents and raw materials used in the present application are commercially available.

[0037] The positive progress effect of the present application is that:

[0038] (1) The surfactant provided by the present application has better solubility, is easy to store at high concentration, and is convenient for transportation;

[0039] (2) The surfactant provided by the present application has excellent surface activity performance;

[0040] (3) The surfactant provided by the present application has low bioaccumulation and low toxicity chain segment, by introducing oxygen-containing fluorine chain segment into phosphocholine through simple substitution reaction and ring-opening reaction, by adjusting the oxygen atom and fluorocarbon number in the molecular structure, both the surfactant performance is improved and the toxicity is reduced, which is expected to be a candidate for replacing PFOS / PFOA. DETAILED DESCRIPTION

[0041] The present application will be further described by way of examples, but the present 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 instructions of the goods.

[0042] (I) Compound List

[0043] 1.1 Intermediate alcohol, compound list

[0044] Table 1

[0045] 1.2 Intermediate fluorophosphonate, compound list

[0046] Table 2

[0047] 1.3 Intermediate tertiary amine, compound list

[0048] Table 3

[0049] 1.4 Fluorine-containing phosphocholine, compound list

[0050] Table 4

[0051] Structure of the compound of the comparative example:

[0052] Table 5

[0053] Synthesis steps:

[0054] (1) Synthesis of OC2-OH

[0055] (1) Synthesis of OC2-OH

[0056] Experimental procedure: NaBH4(4.6 g, 120 mmol, 1.2 equiv.) was added to a three-necked flask, and nitrogen was exchanged three times. 100 mL of super dry tetrahydrofuran was added under the protection of nitrogen, and OC2-Me (26 g, 100 mmol, 1.0 equiv.) was slowly added dropwise under ice bath conditions. The temperature was raised to 70°C, and stirring was carried out overnight. The reaction was quenched by adding an aqueous solution of ammonium chloride dropwise, and filtration was carried out. Distillation was carried out to obtain 20.9 g of colorless liquid, with a yield of 90%.

[0057] 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).

[0058] (2) Synthesis of OC3-OH

[0059] Experimental procedure: NaBH4(9.2 g, 240 mmol, 1.2 equiv.) was added to a three-necked flask, and nitrogen was exchanged three times. 100 mL of super dry tetrahydrofuran was added under the protection of nitrogen, and OC3-Me (64.6 g, 198 mmol, 1.0 equiv.) was slowly added dropwise under ice bath conditions. The temperature was raised to 70°C, and stirring was carried out overnight. The reaction was quenched by adding an aqueous solution of ammonium chloride dropwise, and filtration was carried out. Distillation was carried out under reduced pressure (41-43°C / 8100 pa) to obtain 53.1 g of colorless liquid, with a yield of 90%.

[0060] NMR data: 1H 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).

[0061] (3) Synthesis of OC4-OH

[0062] Experimental procedure: NaBH4(3.5 g, 92 mmol, 1.2 equiv.) was added to a three-necked flask, which was purged with nitrogen three times, 60 mL of super dry tetrahydrofuran was added under the protection of nitrogen, OC4-Me (30.1 g, 77 mmol, 1.0 equiv.) was slowly added dropwise under ice bath condition, the temperature was raised to 70 °C, and stirred overnight, the reaction was completed. Quench with the addition of aqueous ammonium chloride solution, filtered, distilled under reduced pressure (40-42 °C / 306 pa), 25.6 g of colorless liquid was obtained, the yield was 92%.

[0063] 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).

[0064] (4) Synthesis of C61-OH

[0065] Experimental procedure: NaBH4(4.9 g, 129 mmol, 1.2 equiv.) was added to a 100 mL three-necked flask, which was 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, and stirred overnight, the reaction was completed. Quench with the addition of aqueous ammonium chloride solution, filtered, distilled under reduced pressure (38 °C / 3200 Pa), 27 g of colorless liquid was obtained, the yield was 79%.

[0066] NMR data: 1 H NMR (400 MHz, DMSO-d6) δ 6.33-6.26 (t, J = 6, 1H), 4.15-4.06 (m, 2H). 19F NMR (376 MHz, DMSO-d6) δ -80.2 (m, IF), -80.9 (m, 3F), -81.6 (m, 3F), -82.5 (m, IF), -129.5 (m, 2F), -134.3 (m, IF).

[0067] (5) Synthesis of C62-OH

[0068] 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, and then super dry tetrahydrofuran 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 completed. The reaction was quenched by dropwise addition of aqueous ammonium chloride solution, filtered, and distilled under reduced pressure (40 °C / 3200 Pa) to obtain 14 g of colorless liquid with a yield of 58%.

[0069] 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, IF), -86.6 (m, IF), -90.4 (m, 2F), -134.6 (m, IF).

[0070] (6) Synthesis of C72-OH

[0071] Experimental procedure: NaBH4(8.6 g, 228 mmol, 1.2 equiv.) was added into a 250 mL three-necked flask, which was purged with nitrogen for three times, and then super dry tetrahydrofuran 100 mL was added under the protection of nitrogen, C72-COF (61.0 g, 153 mmol, 1.0 equiv.) was slowly dropped into the three-necked flask using a dropping funnel under ice bath condition, the temperature was raised to 70 °C, and stirred overnight, the reaction was completed. The reaction was quenched by dropwise addition of aqueous ammonium chloride solution, filtered, and distilled under reduced pressure (50 - 53 °C / 3200 Pa) to obtain 46 g of colorless liquid with a yield of 79%.

[0072] NMR data: 1 H NMR (400 MHz, DMSO-d6) δ 6.27 (t, J = 6, 1H), 4.08 (m, 2H). 19F NMR (376 MHz, CD3OD) δ -54.1 (m, 3F), -79.1 (m, IF), -80.7 (m, 3F), -82.1 (m, IF), -82.4 (m, 3F), -134.9 (m, IF), -146.8 (m, IF).

[0073] C41-OH and C51-OH were prepared in the same way as described above.

[0074] (II) Synthesis of cyclic phosphates

[0075] (1) Synthesis of OC2-P

[0076] 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%.

[0077] NMR data: 1 H NMR (400 MHz, CDCl3) 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).

[0078] (2) Synthesis of OC3-P

[0079] 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%.

[0080] NMR data: 1 H NMR (400 MHz, CDCl3) 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).

[0081] (3) Synthesis of OC4-P

[0082] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then OC4-OH (10 g, 27 mmol, 1.0 equiv.), super dry tetrahydrofuran 50 mL, triethylamine (3.3 g, 33 mmol, 1.2 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (4.7 g, 33 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 °C / 300 pa) to obtain 7.7 g of colorless viscous liquid, with a yield of 60%.

[0083] NMR data: 1 H NMR (400 MHz, CDCl3) 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).

[0084] (4) Synthesis of 4:2-P

[0085] 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, 2-chloro-2-oxo-1,3,2-dioxaphospholane (7.7 g, 54 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 (92 °C / 133 Pa) to obtain 14.7 g of colorless liquid, with a yield of 70%.

[0086] NMR data: 1 H NMR (400 MHz, CDCl3) 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).

[0087] (5) Synthesis of 6:2-P

[0088] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen for three times, 6:2-FTOH (10 g, 27 mmol, 1.0 equiv.), super dry tetrahydrofuran 40 mL, triethylamine (3.6 g, 36 mmol, 1.3 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (5.1 g, 36 mmol, 1.3 equiv.) was slowly dropped under ice bath condition, the reaction was kept for 2 hours under ice bath, filtered, rotary evaporation, 11.6 g of light yellow viscous liquid was obtained, yield 91%.

[0089] NMR data: 1 H NMR (400 MHz, CDCl3) δ 4.51-4.34 (m, 6H), 2.62-2.50 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -53.5 (m, 2F), -55.6 (m, 2F), -57.8 (m, 3F), -81.5 (m, 2F).

[0090] (6) Synthesis of C61-P

[0091] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen for three times, 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, the reaction was kept for 2 hours under ice bath, filtered, distilled under reduced pressure (78 °C / 133 Pa), 5.2 g of colorless transparent liquid was obtained, yield 49%.

[0092] NMR data: 1 H NMR (400 MHz, CDCl3) 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 P NMR (162 MHz, CDCl3) δ 17.1.

[0093] (7) Synthesis of C62-P

[0094] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then C62-OH (8.0 g, 24 mmol, 1.0 equiv.), super dry tetrahydrofuran 30 mL, triethylamine (2.7 g, 27 mmol, 1.1 equiv.) were added under nitrogen protection, 2-chloro-2-oxo-1,3,2-dioxaphospholane (3.8 g, 27 mmol, 1.1 equiv.) was slowly dropped into the flask under ice bath condition, and the reaction was kept for 2 hours. Filtration, distillation under reduced pressure (86 °C / 133 Pa) to obtain 5.0 g of colorless transparent liquid, yield 48%.

[0095] NMR data: 1 H NMR (400 MHz, CDCl3) δ 4.70-4.37 (m, 6H). 19 F NMR (376 MHz, CDCl3) δ -55.4 (m, 3F), -82.4 (m, 3F), -86.2 (m, 1F), -86.6 (m, 1F), -90.6 (m, 2F), -136.1 (m, 1F). 31 P NMR (162 MHz, CDCl3) δ -17.1.

[0096] (8) Synthesis of C72-P

[0097] Experimental procedure: A 100 mL dry three-necked flask was purged with nitrogen three times, and then 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 slowly dropped into the flask under ice bath condition, and the reaction was kept for 2 hours. Filtration, distillation under reduced pressure (95 °C / 133 Pa) to obtain 8.5 g of yellowish viscous liquid, yield 70%.

[0098] NMR data: 1 H NMR (400 MHz, CDCl3) 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).

[0099] (9) Synthesis of C2-P

[0100] 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%.

[0101] 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).

[0102] The preparation of C2-P, C41-P and C51-P is the same as the above preparation steps.

[0103] (Three) Synthesis of tertiary amine (Amine)

[0104] (1) Synthesis of OC2-Amine

[0105] Experimental procedure: OC2-Me (100 g, 385 mmol, 1.2 eq), methanol 50 mL, 3- dimethylaminopropylamine (32.7 g, 321 mmol, 1.0 eq) were added to a 250 mL round-bottom flask, stirred at room temperature overnight, and distilled under reduced pressure to obtain a colorless liquid 100.7 g with a yield of 95%.

[0106] 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).

[0107] (2) OC3-Amine

[0108] 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%.

[0109] 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).

[0110] (3) Synthesis of OC4-Amine

[0111] 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%.

[0112] 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).

[0113] (4) Synthesis of C4-Amine

[0114] Experimental procedure: To a 250 mL round bottom flask was added C4-Me (73 g, 320 mmol, 1.2 equiv.), solvent 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 colorless liquid 70 g, yield 72%.

[0115] NMR data: 1H NMR (400 MHz, CD3OD) δ 4.58-4.31 (m, 2H), 4.53-4.43 (m, 2H), 4.43-4.31 (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).

[0116] (5) Synthesis of 6:2-Amine

[0117] Experimental procedure: Into a 250 mL three-necked flask, 3-dimethylaminopropylamine (12.3 g, 120 mmol, 1.2 equiv.), toluene 80 mL, triethylamine (12.1 g, 120 mmol, 1.2 equiv.), warm to 40 °C, slowly drop perfluorohexylethylsulfonyl chloride (46.7 g, 100 mmol, 1.0 equiv.), after drop, warm to 75 °C, reaction overnight. Recrystallization, white solid 36 g, yield 70%.

[0118] 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).

[0119] (6) Synthesis of C61-Amine

[0120] Experimental procedure: Into a 250 mL round bottom flask, C61-Me (102 g, 296.5 mmol, 1.2 equiv.), 60 mL methanol, 3-dimethylaminopropylamine (24 g, 235.8 mmol, 1.0 equiv.) under ice bath, stir at room temperature overnight, distillation under reduced pressure (46 °C / 133 pa), colorless liquid 68.4 g, yield 70%.

[0121] 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). 19F NMR (376 MHz, (CD3)2CO) δ -81.6 (ddq, J = 149, 19, 7 Hz, IF), -82.2 (t, J = 7 Hz, 3F), -83.4 (d, J = 2 Hz, 3F), -85.6 (dm, J = 149 Hz, IF), -130.6 (s, 2F), -133.2 (dd, J = 20, 7 Hz, IF).

[0122] (7) Synthesis of C62-Amine

[0123] Experimental procedure: To a 100 mL round bottom flask was added C62-Me (24.6 g, 68.3 mmol, 1.1 equiv.), methanol 20 mL, 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), obtained 20.6 g of liquid, yield 80%.

[0124] 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, IF), -90.3 (dd, J = 147, 8 Hz, IF), -92.0 (m, 2F), -134.1 (dd, J = 18, 8 Hz, IF).

[0125] (8) Synthesis of C72-Amine

[0126] Experimental procedure: To 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 111 g of colorless liquid, yield 92%.

[0127] 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). 19F NMR (376 MHz, CD3OD) δ -55.0 (m, 3F), -80.8 (m, IF), -81.5 (m, 3F), -84.1 (dd, J = 6, 1.5 Hz, 3F), -84.5 (m, IF), -133.9 (m, IF), -147.8 (m, IF).

[0128] C41-Amine and C51-Amine were prepared in the same manner as described above.

[0129] (iv) Synthesis of Choline Phosphate:

[0130] Example 1: Synthesis of OC2-P-OC2

[0131] Experimental procedure: To a 15 mL pressure tube 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.), warmed to 70 °C, and reacted for 48 h. Column chromatography was used for separation and purification, and 2.9 g of light yellow solid was obtained in 90% yield.

[0132] 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). 19 F 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. -1 : 3429, 1717, 1558, 1488, 1235, 1085, 1005, 964, 831, 682, 512.

[0133] Example 2: Synthesis of OC2-P-OC3

[0134] Experimental procedure: To a 15 mL pressure tube was added OC2-P (1.5 g, 4.6 mmol, 1.0 equiv.), super dry acetonitrile solvent 5 mL, OC2-Amine (2.4 g, 6 mmol, 1.3 equiv.), and reacted at 70 °C for 48 h. Column chromatography was used for isolation and purification, and 2.7 g of light yellow solid was obtained with a yield of 80%.

[0135] 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: 735.0583. IR (film) v / cm -1 : 3392, 1716, 1558, 1488, 1232, 1084, 1005, 984, 821, 688, 505.

[0136] Example 3: Synthesis of OC2-P-OC4

[0137] Experimental procedure: To a 15 mL pressure tube was added OC2-P (1.9 g, 5.5 mmol, 1.0 equiv.), anhydrous 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 to get yellow sticky solid product 3.7 g, yield 84%.

[0138] 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) calculated 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.

[0139] Example 4: Synthesis of OC3-P-OC2

[0140] 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 reacted at 70 °C for 48 h, column chromatography separation and purification to get white solid 4.5 g, yield 82%.

[0141] 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 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) calcd 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.

[0142] Example 5: Synthesis of OC3-P-OC3

[0143] 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 reacted at 70 °C for 48 h. Column chromatography was used for isolation and purification to give 5.2 g of white solid with 82% yield.

[0144] 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). 19F 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 cannot be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.8. HRMS - ESI (m / z) found C 17 H 20 O 11 N2F 18 P[M+H] + : 801.0512, Theoretical: 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.

[0145] Example 6: Synthesis of OC3-P-OC4

[0146] Experimental 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 separation and purification to get white solid 5.4 g, yield 85%.

[0147] 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). 13C 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) calculated 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.

[0148] Example 7: Synthesis of OC3-P-C4

[0149] 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%.

[0150] 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 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. 31P 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.

[0151] Example 8: Synthesis of OC3-P-C61

[0152] 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, C61-Amine (3.3 g, 8.0 mmol, 1.3 equiv.), and reacted at 70 °C for 48 h. Column chromatography separation and purification to get white solid 4.2 g, yield 82%.

[0153] 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, 1F), -82.2 (m, 2F), -82.9 (m, 3F), -84.0 (m, 3F), -86.3 (m, 1F), -131.2 (m, 2F), -134.2 (m, 1F). 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 the 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.

[0154] Example 9: OC3-P-C62

[0155] 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 was used for isolation and purification, and 4.6 g of white solid was obtained in 89% yield.

[0156] 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 -13394, 3161, 3011, 1711, 1551, 1481, 1460, 1416, 1376, 1227, 1070, 927, 959, 939, 903, 851, 747, 683, 617, 527, 489, 409.

[0157] Example 10: Synthesis of OC3-P-C72

[0158] 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 was used for isolation and purification to give 3.2 g of white solid in 72% yield.

[0159] 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). 19 F 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 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 -1.9. HRMS - ESI (m / z) calculated 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.

[0160] Example 11: Synthesis of OC4-P-OC2

[0161] 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 h. Column chromatography was used for isolation and purification to give light yellow solid 4.6 g, yield 99%.

[0162] 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). 19 F 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) calculated 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.

[0163] Example 12: Synthesis of OC4-P-OC3

[0164] 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 h. Column chromatography separation and purification to get light yellow solid 3.4 g, yield 71%.

[0165] 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). 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 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 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.

[0166] Example 13: Synthesis of OC4-P-OC4

[0167] 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 h. Column chromatography separation and purification to get light yellow solid 5.7 g, yield 77%.

[0168] 1H 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 159.2, 65.0, 64.0, 60.5, 52.5, 37.9, 23.5, the carbons corresponding to the CF3OCF2OCF2OCF2OCF2- group 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 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.

[0169] Example 14: Synthesis of 4:2-P-OC3

[0170] 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%.

[0171] White solid: 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). 19F 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 CNMR (100 MHz, CD3OD): δ 157.7, 63.5, 62.6, 58.9, 57.5, 51.0, 36.5, 31.7, 22.1, the carbon corresponding to CF3CF2CF2CF2- and CF3OCF2OCF2OCF2- groups cannot be identified due to the coupling effect of 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.

[0172] Example 15: Synthesis of C61-P-OC3

[0173] 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 hours. Column chromatography was used for separation and purification, and 8.2 g of white solid was obtained with a yield of 73%.

[0174] 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). 19F NMR (376 MHz, CD3OD) δ -54.5 (m, 2F), -56.8 (m, 2F), -58.6 (m, 3F), -81.4 (m, 2F), -82.0 (m, IF), -82.8 (m, 3F), -83.6 (m, 3F), -84.0 (m, IF), -131.1 (m, 2F), -135.5 (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 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) calcd for C 18 H 20 O9N2F 20 P[M+H] + : 819.0582, found: 819.0574. IR (film) v / cm -1 : 3395, 1717, 1558, 1488, 1239, 1088, 990, 932, 839, 808, 751, 689, 539.

[0175] Example 16: Synthesis of C62-P-OC3

[0176] 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%.

[0177] 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). 19F 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 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.

[0178] Example 17: Synthesis of C72-P-OC3

[0179] 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 separation and purification to get white solid 7.9 g, yield 74%.

[0180] 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). 19F 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 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.

[0181] Example 18: Synthesis of C72-P-C72

[0182] 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 separation and purification to get white solid 6.4 g, yield 80%.

[0183] 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 cannot 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.

[0184] The preparation of Examples 19-21 was identical to the procedure of Examples 1-18.

[0185] Example 22: Synthesis of OC3-P-C41

[0186] Experimental procedure: To a 48 mL pressure tube was added sequentially OC3-P (3 g, 7.4 mmol, 1.0 equiv.), C41-Amine (3.0 g, 9.6 mmol, 1.3 equiv.), super-dry acetonitrile (5 mL), and reacted at 70 °C for 48 h. The reaction was stopped. Rotatory evaporation, column chromatography, and 4.2 g of colorless sticky solid was obtained with 79% yield.

[0187] 1 H NMR (400 MHz, CD3OD) δ 4.28 (m, 4H), 3.65 (m, 2H), 3.42 (m, 4H), 3.17 (s, 6H), 2.07 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.6 (m, 2F), -56.2 (d, J = 8 Hz, 3F), -56.8 (m, 2F), -58.6 (t, J = 9 Hz, 3F), -82.2 (m, 2F), -83.9 (d, J = 2 Hz, 3F), -135.7 (m, 1F). 13C NMR (100 MHz, CD3OD) δ 159.8, 65.0, 64.0, 60.8, 52.5, 38.0, 23.5, the carbons corresponding to the CF3OCF2OCF2OCF2- group and CF3OCF(CF3)- cannot be identified due to the coupling effect of C-F. 31 P NMR (CD3OD, 162 MHz): δ -1.9. HRMS - ESI (m / z) calcd for C 16 H 20 O9N2F 16 P[M+H] + : 719.0645, found: 719.0659. IR (film) v / cm -1 : 3034, 1717, 1557, 1490, 1411, 1235, 1171, 1077, 977, 961, 912, 813, 731, 690, 650, 586, 506.

[0188] Example 23: Synthesis of OC3-P-C51

[0189] Experimental procedure: To a 48 mL pressure tube was added OC3-P (3 g, 7.4 mmol, 1.0 equiv.), C51-Amine (3.5 g, 9.6 mmol, 1.3 equiv.), super dry acetonitrile 5 mL, reacted at 70 °C for 48 h, end the reaction. Rotary evaporation, column chromatography, 4.5 g of colorless sticky solid was obtained, yield: 79%.

[0190] 1 H NMR (400 MHz, CD3OD) δ 4.28 (m, 4H), 3.65 (m, 2H), 3.43 (m, 4H), 3.17 (s, 6H), 2.10 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.6 (m, 2F), -56.8 (m, 2F), -58.6 (t, J = 9 Hz, 3F), -82.2 (m, 2F), -84.0 (d, J = 2 Hz, 3F), -85.6 - 86.0 (m, 1F), -88.2 (s, 3F), -90.2 - 90.6 (m, 1F), -134.3 (m, 1F). 13 C NMR (100 MHz, CD3OD) δ 160.0, 65.0, 64.1, 60.5, 52.5, 38.1, 23.5, the carbons corresponding to the CF3OCF2OCF2OCF2- group and CF3CF2OCF(CF3)- cannot be identified due to the coupling effect of C-F. 31P NMR (CD3OD, 162 MHz): δ -2.2. HRMS-ESI (m / z) calculated for C 17 H 20 O9N2F 18 P[M+H] + : 769.0619, found: 769.0629. IR (film) v / cm -1 : 3030, 1712, 1557, 1488, 1231, 1162, 1074, 983, 989, 911, 827, 651, 610, 511.

[0191] Example 24: Synthesis of C62-P-C62

[0192] Experimental procedure: To a 15 mL pressure tube was added C62-P (1.8 g, 4.1 mmol, 1.0 equiv.), C62-Amine (2.3 g, 5.3 mmol, 1.3 equiv.), super-dry acetonitrile 5 mL, and reacted at 70 °C for 36 h. The reaction was stopped and brown solid precipitated. Column chromatography gave 2.8 g of colorless sticky solid in 78% yield.

[0193] 1 H NMR (400 MHz, CD3OD) δ 4.48 (m, 2H), 4.26 (m, 2H), 3.65 (m, 2H), 3.42 (m, 4H), 3.17 (s, 6H), 2.07 (m, 2H). 19 F NMR (376 MHz, CD3OD) -57.0 (m, 6F), -83.6 (d, J = 4 Hz, 3F), -84.0 (d, J = 2 Hz, 3F), -86.0 - 86.5 (m, 2F), -88.0 - 88.5 (m, IF), -90.0 - 90.5 (m, IF), -91.9 (m, 2F), -92.0 (m, 2F), -134.2 (m, IF), -135.7 (m, IF). 13 C NMR (100 MHz, CD3OD): δ 159.9, 65.0, 64.1, 63.4, 60.5, 52.5, 38.1, 23.5, the carbons corresponding to the CF30CF2CF20CF(CF3)- group could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -2.2. HRMS-ESI (m / z) calculated for C 19 H 20 O9N2F 22 P[M+H] +: 869.0550, found: 869.0553. IR (film) v / cm -1 : 3370, 2923, 1653, 1561, 1482, 1197, 1124, 1036, 694, 613, 418.

[0194] Example 25 was prepared in the same manner as Example 1-18.

[0195] Example 26: Synthesis of OC2-P-C62

[0196] Experimental procedure: To a 48 mL pressure tube was added OC2-P (4 g, 11.8 mmol, 1.0 equiv.), C62-Amine (6.6 g, 15.3 mmol, 1.3 equiv.), super dry acetonitrile 6 mL, and reacted at 70 °C for 48 h. Rotovap, column chromatography to get 7.3 g of yellowish sticky solid, 80% yield.

[0197] 1 H NMR (400 MHz, CD3OD) δ 4.28 (m, 4H), 3.65 (m, 4H), 3.43 (m, 2H), 3.18 (s, 6H), 2.08 (m, 2H). 19 F NMR (376 MHz, CD3OD) -55.8 (m, 2F), -57.7 (t, J = 9 Hz, 3F), -59.3 (t, J = 9 Hz, 3F), -83.0 (m, 2F), -84.7 (d, J = 2 Hz, 3F), -87.0 (m, IF), -90.1 (m, IF), -92.6 (m, 2F), -134.9 (m, IF). 13 C NMR (100 MHz, CD3OD): δ 159.9, 65.1, 64.2, 60.5, 52.5, 38.1, 23.4, the carbons corresponding to the CF3OCF2OCF2- group and CF3OCF2CF2OCF(CF3)- groups could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -2.5. HRMS - ESI (m / z) calculated for C 17 H 20 O9N2F 18 P [M+H] + : 769.0614, found: 769.0602. IR (film) v / cm -1 : 3044, 1711, 1552, 1488, 1412, 1224, 1153, 1084, 1005, 965, 903, 797, 722, 641, 508.

[0198] Example 27: Synthesis of C2-P-C72

[0199] Experimental procedure: To a 15 mL pressure tube was added C2-P (1.4 g, 5 mmol, 1.0 equiv.), super-dry acetonitrile solvent 5 mL, C72-Amine (3.2 g, 6.6 mmol, 1.3 equiv.) sequentially, warmed to 70 °C, and reacted for 48 h. Column chromatography separation and purification yielded 2.4 g of light white solid with a yield of 62%.

[0200] 1 H NMR (400 MHz, CD3OD) δ 5.22 (m, 1H), 4.26 (m, 2H), 3.61 (m, 2H), 3.40 (m, 2H), 3.15 (s, 6H), 2.01 (m, 2H). 19 F NMR (376 MHz, CD3OD) δ -54.9 (m, 2F), -75.8 (m, 6F), -80.6 (dm, J = 142 Hz, 1F), -81.5 (m, 3F), -84.0 (m, 3F), -84.6 (dm, J = 142 Hz, 1F), -134.0 (m, 1F), -147.8 (m, 1F). 13 C NMR (100 MHz, CD3OD) δ 159.7, 72.5, 65.0, 64.1, 60.8, 52.4, 38.1, 23.4. The carbons corresponding to the (CF3)2group and CF3OCF(CF3)CF2OCF(CF3)- could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -3.2. IR (film) cm-1 -1 : 3434, 3032, 3004, 2963, 1711, 1561, 1280, 1241, 1196, 1161, 1105, 1069, 1013, 979, 898, 819, 688, 510. HRMS - ESI (m / z): calcd for C 17 H 19 N2O7F 19 P[M+H] + : 755.0621, found: 755.0607.

[0201] Example 28: Synthesis of OC3-P-OC3E

[0202] Experimental procedure: To a 48 mL pressure tube was added 6:2-P (5 g, 10.6 mmol, 1.0 equiv.), acetonitrile 10 mL, trimethylamine in tetrahydrofuran (10 mL, 20 mmol, 2.0 equiv.) and warmed to 70 °C for 48 h. Purification by column chromatography afforded 3.4 g of white solid in 60% yield.

[0203] 1 H NMR (400 MHz, CD3OD) δ 4.32-4.17 (m, 4H), 3.51-3.65 (m, 4H), 3.36 (m, 2H), 3.16 (s, 6H). 19 F NMR (376 MHz, CD3OD) δ -54.6 (m, 4F), -56.8 (m, 4F), -58.6 (m, 6F), -81.4 (m, 2F), -82.1 (m, 2F). 31 P NMR (CD3OD, 162 MHz): δ -1.8.

[0204] Comparative Example 1: Synthesis of 6:2-P-Me

[0205] Experimental procedure: To a 48 mL pressure tube was added 6:2-P (5 g, 10.6 mmol, 1.0 equiv.), acetonitrile 10 mL, trimethylamine in tetrahydrofuran (10 mL, 20 mmol, 2.0 equiv.) and warmed to 70 °C for 48 h. Purification by column chromatography afforded 3.4 g of white solid in 60% yield.

[0206] 1 H NMR (CD3OD, 400 MHz): δ 4.30-4.23 (m, 2H), 4.16 (m, 2H), 3.61 (m, 2H), 3.20 (s, 9H), 2.50-2.68 (m, 2H). 19 F NMR (CD3OD, 376 MHz): 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, 100 MHz): δ 66.1, 59.1, 57.41, 53.1, 31.8, the carbons corresponding to the CF3CF2CF2CF2CF2CF2- group could not be identified due to coupling effects of C-F. 31 P NMR (CD3OD, 162 MHz): δ -0.7. HRMS - ESI (m / z) calculated for C 13 H 18O4NF 13 P[M+H] + : 530.0760, found 530.0765. IR (film) V / cm -1 : 3424, 3037, 2952, 1663, 1492, 1247, 1192.

[0207] Comparative Example 2: Synthesis of C72-P-Me

[0208] Experimental procedure: To a 48 mL pressure tube was added C72-P (5 g, 10 mmol, 1.0 equiv.), acetonitrile 10 mL, trimethylamine in tetrahydrofuran (10 mL, 20 mmol, 2.0 equiv.) under ice bath condition, warmed to 70 °C for 48 h. Column chromatography was used for isolation and purification, afforded white solid 9.8 g, yield 90%.

[0209] 1 H NMR (CD3OD, 400 MHz): δ 4.57-4.41 (m, 2H), 4.33-4.20 (m, 2H), 3.62 (m, 2H), 3.19 (s, 9H), 19 F NMR (CD3OD, 376 MHz): 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, 100 MHz): δ 66.0, 62.0, 59.3, 53.2, the carbons corresponding to the CF3OCF(CF3)CF2OCF(CF3)- group could not be identified due to coupling effect of C-F. 31 P NMR (CD3OD, 162 MHz): δ -2.3. HRMS -ESI (m / z) calcd for C 12 H 16 O6F 13 P[M+H] + : 548.0494, found 548.0502. IR (film) V / cm -1 : 1315, 1239, 1160, 1193.

[0210] Comparative Example 3: Synthesis of 4:2-P-C4

[0211] Procedure: To a 48 mL pressure tube was added 4:2-P (2.8 g, 18.5 mmol, 1.0 equiv.), acetonitrile solvent 5 mL, C4-Amine (3.1 g, 24.1 mmol, 1.3 equiv.) and reacted at 70 °C for 48 h. Column chromatography was used for isolation and purification, and 3.7 g of white solid was obtained with a yield of 71% and a purity of 90% by NMR.

[0212] White solid: 1 H NMR (400 MHz, CD3OD) δ 4.26-4.17 (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). 19 F NMR (376 MHz, 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 (100 MHz, CD3OD): δ 158.1, 63.7, 62.6, 58.9, 57.4, 51.0, 36.5, 31.6, 22.1, the carbons corresponding to the CF3CF2CF2CF2- and CF3CF2CF2- 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) calculated for C 17 H 22 O5N2F 16 P[M+H] + : 669.1005, found: 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.

[0213] Method for testing surface tension:

[0214] In this experiment, the Germany The K100C automatic surface (interface) tension meter produced by the company is used to measure the surface tension of the solution containing fluorinated surfactant under room temperature conditions, and the unit is mN / m. After the solution is prepared, it is ultrasonicated to make the solute uniformly dispersed in the solvent, and then it is left overnight before the surface tension test. [Reference] EKissa. Fluorinated surfactants and repellents [M], Marcel Dekker Inc., New York, 2001.

[0215] Effect Example 1: Surface tension of fluorine-containing phosphocholine in aqueous solution at different concentrations:

[0216] Table 6 Note: The surface tension of the solution is tested by the K100C automatic surface / interface tension meter manufactured by the German Kruss company, which uses the platinum plate method for testing, and the test temperature is 22-26℃. Soluble > 10wt%; 1wt% < soluble < 10wt%; 0.01wt% < slightly soluble < 1wt%; insoluble < 0.01wt%. Among them, ① the implementation effect (solubility and surface tension) of examples 19, 20, 22 (C41-P-OC3, OC3-P-C41 and C2-P-OC4) is equivalent to OC3-P-C4 and OC2-P-OC3; ② the implementation effect (solubility and surface tension) of examples 21, 23, 25 (C51-P-OC3, OC3-P-C51 and C41-P-C62) is equivalent to 4:2-P-OC3, OC2-P-OC3 and OC3-P-OC2; ③ the implementation effect (solubility and surface tension) of example 24 (C62-P-C62) is equivalent to OC3-P-C72 and C72-P-OC3.

[0217] The specific double-chain fluorine-containing segment combined with the phosphocholine structure in the present application effectively improves the surface activity of the surfactant. For example, compared with Comparative Example 1 and Comparative Example 2, the surface tension of the double-chain compound (such as Example 18 at 0.01wt% and 0.001wt% concentration) is significantly reduced.

[0218] The short-chain fluorine-containing ether segment is also used in the present application, which effectively improves the surface activity of the surfactant. For example, compared with Comparative Example 3, the surface tension of the short-chain fluorine-containing ether segment introduced in the examples of the present application is significantly reduced; and the introduction of the fluorine ether segment improves the solubility of the surfactant.

[0219] In summary, the phosphocholine is combined with the specific fluorine-containing ether segment in the present application, and the double fluorine segment structure is used, which effectively improves the surface activity and solubility of the surfactant, and provides a surfactant with high comprehensive performance.

[0220] Table 7 Total number of fluorocarbon atoms and total number of oxygen atoms of compounds Note: Fluorocarbon atom refers to carbon atom substituted by one or more fluorine atoms.

[0221] As can be seen from Table 7, when R F1 +R F2 When the total number of fluorocarbon atoms plus the total number of oxygen atoms is the same, the low concentration performance is not much different, the more fluorocarbon atoms, the better the performance, wherein R F1 +R F2 In the middle, the total number of fluorocarbon atoms: the number of oxygen atoms is less than 3;

[0222] Solubility: As can be seen from Table 7, when the total number of RF1+RF2 fluorocarbon atoms is greater than or equal to 8, the total number of fluorocarbon atoms: the number of oxygen atoms in RF1+RF2 needs to be less than 3 to be soluble.

[0223] When R F1 +R F2 When the total number of fluorocarbon atoms is the same, R F1 +R F2 The greater the sum of the total number of fluorocarbon atoms and the number of oxygen atoms, the better the overall performance, for example:

[0224] (1) OC4-P-OC4, OC3-P-C72 and C72-P-OC3; or,

[0225] (2) OC3-P-OC4, OC4-P-OC3, OC3-P-C62, C62-P-OC3, OC3-P-C61 and C61-P-OC3; or,

[0226] (3) OC2-P-OC4, OC3-P-OC3, OC4-P-OC2 and 4:2-P-OC3; or,

[0227] (4) OC2-P-OC3, OC3-P-OC2, OC3-P-C4 and 4:2-P-C4.

[0228] In addition, in the present application, when the total number of fluorocarbon atoms is greater than or equal to 8, less than 12, and the sum of the total number of fluorocarbon atoms and the total number of oxygen atoms is greater than or equal to 13, the surface tension at a concentration of 0.001 wt% is less than 20 mN / m.

Claims

1. A compound of 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 F1 and R F2 are each independently wherein each Y is independently *-CF2-**, *-OCF2-**, *-OCF(CF3)-** or *-CH(CF3)-**, and R F1 and / or R F2 wherein 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 in the direction of; R1and R2are each independently C1-C6alkyl.

2. The compound of claim 1, or a salt thereof, wherein which satisfies one or more of the following conditions: (1) R F1 and R F2 The ratio of the total number of fluorine and carbon atoms to the total number of oxygen atoms is less than 3; for example, the ratio of the total number of fluorine and carbon atoms to the total number of oxygen atoms is 1.0 to 2.8, preferably 1.25 to 2.67; (2) R F1 and R F2 wherein the total number of fluorocarbon atoms is 12 or less, for example the total number of fluorocarbon atoms is 6 to 10, and further for example 6, 7, 8, 9 or 10; (3) R F1 and R F2 wherein the total number of oxygen atoms is 3 or more, for example the total number of oxygen atoms is 3 to 8, in further example 3, 4, 5, 6, 7 or 8; (4) R F1 and R F2 wherein the total number of fluorine and carbon atoms plus the total number of oxygen atoms is equal to or greater than 10; for example, the total number of fluorine and carbon atoms plus the total number of oxygen atoms is 10 to 18, for further example, 10, 11, 12, 13, 14, 15, 16, 17, or 18.

3. The compound of claim 2, or a salt thereof, wherein R F1 and R F2 wherein the total number of fluorocarbon atoms is equal to or greater than 6; the sum of the total number of fluorocarbon atoms and the total number of oxygen atoms is equal to or greater than 10; for example, the total number of fluorocarbon atoms is 6-10, and the sum of the total number of fluorocarbon atoms and the total number of oxygen atoms is 10-18. Preferably, the total number of fluorocarbon atoms is greater than or equal to 7; the total number of fluorocarbon atoms plus the total number of oxygen atoms is greater than or equal to 12; for example, the total number of fluorocarbon atoms is 7-10, and the total number of fluorocarbon atoms plus the total number of oxygen atoms is 12-18. More preferably, the total number of fluorocarbon atoms is greater than or equal to 8, less than 12; the total number of fluorocarbon atoms plus the total number of oxygen atoms is greater than or equal to 13; for example, the total number of fluorocarbon atoms is 8-10, and the total number of fluorocarbon atoms plus the total number of oxygen atoms is 13-18.

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 at the same time are For example R F1 and R F2 are the same.

5. The compound of claim 4, or a salt thereof, wherein independently of 6. The compound of claim 1, or a salt thereof, wherein which satisfies one or more of the following conditions: (1) p is 2 or 3; preferably 3; (2) R1and R2are each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl; preferably methyl; more preferably, R1and R2are both methyl; (3) are independently 7. The compound of claim 1, or a salt thereof, wherein The compound as shown in formula I is a compound of formula I-1: wherein R F1 and R F2 are independently as in any one of claims 1-6; Preferably, the compound of formula I is a compound of formula I-2: wherein m and R F2 independently of one another as in any of claims 1-6; or, the compound of Formula I is a compound of Formula I-3: wherein m and R F1 independently of one another as claimed in any of claims 1 to 6.

8. The compound of claim 1, or a salt thereof, wherein The compound of Formula I is any one of the following:

9. A compound as shown in Formula II, characterized in that, wherein R F1 and n are independently as described in any one of claims 1-8.

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

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