An imidazolium salt, a method for preparing the same, use thereof, and a method for preparing a fluoropolymer

Abstract

The application discloses an imidazole salt, a preparation method and application thereof, and a preparation method of a fluorine-containing polymer. The application provides a compound I or a compound II. The alkyl fluorine-containing aromatic hydrocarbon obtained by the preparation method has the advantages of high yield, high reaction region selectivity and various structures. The application provides a brand-new preparation method of a fluorine-containing polymer with a polyfluorine aromatic main chain. The fluorine-containing polymer obtained by the preparation method has the advantages of high yield, high number average molecular weight, single controllable polymer structure and narrow molecular weight distribution.

Description

Technical Field

[0001] This invention relates to an imidazole salt, its preparation method, its application, and a method for preparing fluoropolymers. Background Technology

[0002] Fluorinated aromatic rings are an important class of structures widely found in drug and material molecules. Of the 100 best-selling drugs globally in 2018, 51 were small molecule drugs, and 15 of them were fluorinated. Despite their importance, research on the functionalization of fluorinated aromatic rings and the introduction of these fragments into other molecules remains limited. In 2008, Nakao and Hiyam's group reported intermolecular alkenylation and alkylation reactions of polyfluoroaromatics catalyzed by a nickel-tricyclopentylphosphine system; however, the olefins used were limited to naphthylethylene and 1,3-phenylbutadiene, both specifically yielding branched products. Then, in 2018, Zhao et al. reported the rhodium-catalyzed hydroarylation of polyfluoroaromatics and acrylates, synthesizing a series of esters and amides containing polyfluoroaromatic fragments. Subsequently, in 2019, Shi Shiliang's group reported the intramolecular asymmetric hydroarylation of polyfluoroaromatics with alkenyl side chains. However, to date, no methods have been reported for preparing alkyl polyfluoroaromatics from polyfluoroaromatics and simple alkenes via intermolecular hydrogen arylation reactions. a) Normand, AT; Yen, SK; Huynh, HV; Hor, TSA; Cavell, K. J. O. Ganometallics, 2008, 27, 3153. b) Zhang, W.-B.; Yang, X.-T.; Ma, J.-B.; Su, Z.-M.; Shi, S.-L. J. M. C ...

[0003] Fluorinated polymers often possess excellent thermal stability, chemical stability, hydrophobicity, oleophobicity, and optoelectronic properties. For example, polytetrafluoroethylene (PTFE) is known as the "king of plastics" and is widely used in chemical, mechanical, electronic, electrical, aerospace, and military industries. However, current research on fluoropolymers mainly focuses on alkyl fluorinated derivatives, with less research on polymers containing aryl fluorine backbones. In 1992, Kane et al. reported the condensation polymerization of octafluorobiphenyl and bisphenol to synthesize polymers with aryl fluorine backbones. These polymers exhibit good hydrophobicity, heat resistance, and dielectric properties, making them suitable for aerospace and electronic packaging applications (see a) Irvin JA, Neef CJ, Kane KM, et al. Journal of Polymer Science Part A: Polymer Chemistry. 1992, 30, 1675. However, this condensation polymerization reaction produces a significant amount of hydrogen fluoride as a byproduct, causing substantial environmental pollution. Transition metal-catalyzed olefin hydroarylation is an ideal reaction for copolymerizing olefins and aromatics, both of which are readily available chemical raw materials. The reaction itself is achieved through the addition of aromatic hydrocarbons to olefins via C-H bonds, achieving 100% atom economy. However, applying olefin hydroarylation to polymerization also presents a series of challenges. The activation of aromatic C-H bonds generally involves high energy barriers and low reactivity, while polymerization requires extremely high reactivity and selectivity. Therefore, although transition metal-catalyzed olefin hydroarylation has been extensively studied over the past three decades, there are currently only very limited reports of its application in polymerization. Summary of the Invention

[0004] The technical problem this invention aims to solve is to overcome the inefficiency of existing catalytic systems in achieving the hydroarylation reaction of fluorinated aromatics and alkenes, as well as the copolymerization of fluorinated aromatics, alkenes, and alkynes. This invention provides an imidazole salt, its preparation method, its applications, and a method for preparing fluorinated polymers. The alkyl fluorinated aromatics obtained by the preparation method of this invention have advantages such as high yield, high regioselectivity, and diverse structures. Furthermore, this invention provides a novel method for preparing polyfluoroaryl backbone polymers; the fluorinated polymers obtained by this method have advantages such as high yield, high number-average molecular weight, simple and controllable polymer structure, and narrow molecular weight distribution.

[0005] The present invention solves the above-mentioned technical problems through the following technical solutions.

[0006] This invention provides a compound I or a compound II, the structure of which is shown below:

[0007]

[0008] Among them, Ar 1 Ar2 Ar 3 and Ar 4 Independently for C 6-10 Aromatic rings may be surrounded by one, two, or three R groups. Ar Replacement C 6-10 Aromatic rings;

[0009] R Ar Independently for C 1-6 Alkyl, -OC 1-6 Alkyl, C 3-6 Cycloalkyl, with 1, 2 or 3 R Ar-1 Replacement C 1-6 Alkyl group, with one, two or three R radicals Ar-2 Replacement -OC 1-6 Alkyl groups or those with one, two, or three R groups Ar-3 Replacement C 3-6 cycloalkyl;

[0010] R Ar-1 R Ar-2 and R Ar-3 Independently halogen or C 1-6 alkyl;

[0011] X - It is a monovalent anion.

[0012] In one embodiment, certain groups in compound I or compound II may be defined as follows, and other groups may be defined as described in any embodiment of the present invention (hereinafter referred to as "in one embodiment"): R Ar Independently for C 1-6 Alkyl or -OC 1-6 alkyl.

[0013] In one particular scheme, Ar 1 Ar 2 Ar 3 and Ar 4 same.

[0014] In one of the plans, X - For Cl - ,Br - I - Or BF4 - For example, Cl - .

[0015] In one particular scheme, Ar 1 Ar 2 Ar 3 and Ar 4 In, the C 6-10 Aromatic rings and the aforementioned rings are composed of one, two, or three R groups. ArReplacement C 6-10 C in the aromatic ring 6-10 The aromatic ring can be either a benzene ring or a naphthalene ring.

[0016] In one particular scheme, R Ar In, the C 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl or tert-butyl.

[0017] In one particular scheme, R Ar In the context, the -OC 1-6 The alkyl group is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; for example, methoxy.

[0018] In one particular scheme, R Ar It can be methyl, tert-butyl, or methoxy on its own.

[0019] In one particular scheme, Ar 1 Ar 2 Ar 3 and Ar 4 Independently For example, Ar 1 Ar 2 Ar 3 and Ar 4 Same, for

[0020] In one embodiment, compound I or compound II has the following structure:

[0021]

[0022] The present invention also provides a method for preparing compound I or compound II, comprising the following steps: reacting compound 0 with chloromethyl ethyl ether to obtain compound I;

[0023]

[0024] Alternatively, in a solvent, compound I reacts in the presence of a base to give compound II;

[0025]

[0026] In one embodiment, the reaction temperature in the preparation method of compound I is conventional in the art, for example, 90-110°C, or even 100°C.

[0027] In one embodiment, the reaction time in the preparation method of compound I is conventional in the art, for example, 8-14 hours, or even 12 hours.

[0028] In one embodiment, the molar ratio of compound 0 to chloromethyl ethyl ether is conventional in the art, for example, 1:10-30, or even 1:20.

[0029] In one embodiment, the base used in the preparation of compound II is conventional in the art, such as an organic base, an alkali metal salt of an alcohol, or potassium tert-butoxide.

[0030] In one embodiment, the solvent used in the preparation method of compound II is conventional in the art, such as an ether solvent; another example is a cyclic ether solvent, and yet another example is tetrahydrofuran.

[0031] In one embodiment, the molar ratio of compound I to the base in the preparation method of compound II is conventional in the art, for example, 1:1-2; for example, 1:1.5.

[0032] The present invention also provides the application of compound I or compound II as a ligand in a hydroarylation reaction; for example, the hydroarylation reaction is a hydroarylation reaction of fluorinated aromatic hydrocarbons with alkenes, or a hydroarylation reaction of fluorinated aromatic hydrocarbons with alkynes.

[0033] The present invention also provides a method for preparing compound A, comprising the following steps: in a solvent, in system 1 or system 2, compound III and compound IV are reacted as shown below; wherein system 1 is compound I', 1,5-cyclooctadiene nickel and a base; and system 2 is compound II' and 1,5-cyclooctadiene nickel;

[0034]

[0035] in,

[0036] The structure of compound I' or II' is as follows:

[0037]

[0038] Among them, Ar 1 Ar 2 Ar 3 Ar 4 and X - The definition is as stated above;

[0039] R 0 Independently for C 1-6 Alkyl or -OC 1-6 alkyl;

[0040] Cy A is C 6-10 Aromatic rings or 5-16 heterocyclic aromatic rings;

[0041] R 1 F and C independently 1-20 Alkyl, C 3-20 cycloalkyl, -OC 1-20 Alkyl, C 6-10 Aromatic rings, 5-16 heterocyclic aromatic rings, By 1, 2 or 3 R 1-2 Replacement C 1-20 Alkyl group, with one, two or three R radicals 1-3 Replacement C 3-20 Cycloalkyl, with 1, 2 or 3 R 1-4 Replacement OC 1-20 Alkyl group, with one, two or three R radicals 1-5 Replacement C 6-10 Aromatic rings may be surrounded by one, two, or three R groups. 1-6 Substituted 5- to 16-membered heteroaryl rings;

[0042] p is 1, 2, 3, 4, 5 or 6;

[0043] R 1-1 C 1-6 alkyl;

[0044] R 1-2 R 1-3 R 1-4 R 1-5 and R 1-6 Independently halogen or C 1-6 alkyl;

[0045] R 2 and R 3 Independently for H and C 1-20 Alkyl, C 3-20 cycloalkyl, C 3-20 Cycloalkenyl, 5-16 membered heterocyclic alkyl, -OC 1-20 Alkyl, -OC 3-20 cycloalkyl, C 6-10 Aromatic rings, 5-16 member heteroaryl rings, -SiR a R b R c , by 1, 2 or 3 R 2-1 Replacement C 1-20 Alkyl group, with one, two or three R radicals 2-2 Replacement C 3-20 Cycloalkyl, with 1, 2 or 3 R 2-3 Replacement C 3-20 Cycloalkenyl, with 1, 2 or 3 R 2-4 Substituted 5- to 16-membered heterocyclic alkyl groups, with one, two, or three R groups 2-5 Replacement -OC1-20 Alkyl group, with one, two or three R radicals 2-6 Replacement -OC 3-20 Cycloalkyl, with 1, 2 or 3 R 2-7 Replacement C 6-10 Aromatic rings may be surrounded by one, two, or three R groups. 2-8 Substituted 5- to 16-membered heteroaryl rings;

[0046] R 2-1 R 2-2 R 2-3 R 2-4 R 2-5 R 2-6 R 2-7 and R 2-8 Independently -OH, halogen, C 1-20 Alkyl, -OC 1-20 Alkyl, C 3-20 cycloalkyl, C 3-20 Cycloalkenyl, 5-16 membered heterocyclic alkyl, -OC 1-20 Alkyl, C 6-10 Aromatic rings, 5-16 member heteroaryl rings, -SiR a R b R c -NR d R e -O-SiR f R g R i Bpin or by 1, 2 or 3 R 2-1-1 Replacement C 6-10 Aromatic rings;

[0047] R a R b and R c Independently for H and C 1-20 Alkyl or C 6-10 Aromatic rings;

[0048] R d and R e Independently for H and C 1-20 Alkyl, C 6-10 Aromatic rings or -C 1-6 Alkylene-C 6-10 Aromatic rings;

[0049] R f R g and R i Independently for H and C 1-20 Alkyl or C 6-10 Aromatic rings;

[0050] R 2-1-1 Independently for C1-20 Alkyl or -OC 1-20 alkyl;

[0051] or R 2 and R 3 The carbon atom attached to it forms C 3-8 cycloalkyl or C 3-8 Bridged cycloalkyl;

[0052] The 5- to 16-membered heteroaromatic rings are 5- to 16-membered heteroaromatic rings with 1, 2, 3 or 4 heteroatoms selected from N, O and S.

[0053] The 5- to 16-membered heterocyclic alkyl group is independently a 5- to 16-membered heterocyclic alkyl group selected from one, two, or three heteroatoms of N, O, and S; and has one, two, three, or four heteroatoms.

[0054] In one particular scheme, R 1 F and C independently 1-20 Alkyl, -OC 1-20 Alkyl, C 6-10 Argan, Or by 1, 2 or 3 Rs 1-2 Replacement C 1-20 alkyl;

[0055] In a given scheme, p can be 1, 2, 3, or 4.

[0056] In one particular scheme, R 1-2 It is a halogen on its own.

[0057] In one particular scheme, R 2 For H or C 1-20 alkyl.

[0058] In one particular scheme, R 3 For H, C 1-20 Alkyl, C 3-20 cycloalkyl, C 3-20 Cycloalkenyl, -OC 1-20 Alkyl, -OC 3-20 cycloalkyl, C 6-10 Aromatic rings, -SiR a R b R c , by 1, 2 or 3 R 2-1 Replacement C 1-20 Alkyl groups or those with one, two, or three R groups 2-7 Replacement C 6-10 Aromatic ring.

[0059] In one particular scheme, R 2-1 and R2-7 Independent of halogen, C 1-20 Alkyl, -OC 1-20 Alkyl, 5-16 membered heterocyclic alkyl, C 6-10 Aromatic rings, 5-16 member heteroaryl rings, -SiR a R b R c -NR d R e -O-SiR f R g R i Bpin or by 1, 2 or 3 R 2-1-1 Replacement C 6-10 Aromatic ring.

[0060] In one particular scheme, R a R b and R c Independently for C 1-20 Alkyl or C 6-10 Aromatic ring.

[0061] In one particular scheme, R d and R e Independently for C 1-20 Alkyl or -C 1-6 Alkylene-C 6-10 Aromatic ring.

[0062] In one particular scheme, R f R g and R i Independently for C 1-20 alkyl.

[0063] In one particular scheme, R 2-1-1 Independently for -OC 1-20 alkyl.

[0064] In one particular scheme, R 0 In, the C 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl or tert-butyl.

[0065] In one particular scheme, R 0 In the context, the -OC 1-6 The alkyl group is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; for example, methoxy.

[0066] In a certain scheme, when Cy A is C 6-10 When aromatic rings are used, the C 6-10 The aromatic ring is a benzene ring.

[0067] In one embodiment, when Cy A is a 5- to 16-membered heteroaryl ring, the 5- to 16-membered heteroaryl ring is a 5- to 7-membered heteroaryl ring; for example, pyridine.

[0068] In one particular scheme, R 1 In, the C 1-20 Alkyl groups and those with one, two, or three R groups 1-2 Replacement C 1-20 C in alkyl 1-20 Alkyl groups are independently C 1-10 Alkyl; for example, C 1-6 Alkyl; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; for example, methyl.

[0069] In one particular scheme, R 1 In the context, the -OC 1-20 Alkyl group is -OC 1-10 Alkyl; for example, -OC 1-6 Alkyl; for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; for example, methoxy.

[0070] In one particular scheme, R 1 In, the C 6-10 The aromatic ring is a benzene ring.

[0071] In one particular scheme, R 1-1 In, the C 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl.

[0072] In one particular scheme, R 1-2 In this context, the halogen is independently F, Cl, Br, or I, for example, F.

[0073] In one particular scheme, R 2 In, the C 1-20 Alkyl groups are independently C 1-10 Alkyl; for example, C 1-6 Alkyl; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; for example, methyl.

[0074] In one particular scheme, R 3 In, the C 1-20 Alkyl groups and those with one, two, or three R groups 2-1 Replacement C 1-20 C in alkyl 1-20 Alkyl groups are independently C 1-10 Alkyl; for example, alkyl

[0075] In one particular scheme, R 3 In, the C 3-20 Cycloalkyl group is C 3-10 cycloalkyl; for example, cycloalkyl

[0076] In one particular scheme, R 3 In, the C 3-20 The cycloalkenyl group is C 3-10 Cycloalkenyl; for example,

[0077] In one particular scheme, R 3 In the context, the -OC 1-20 Alkyl group is -OC 1-10 Alkyl; for example, alkyl

[0078] In one particular scheme, R 3 In the context, the -OC 3-20 Cycloalkyl group is -OC 3-10 cycloalkyl; for example, cycloalkyl

[0079] In one particular scheme, R 3 In, the C 6-10 Aromatic rings and the aforementioned rings are composed of one, two, or three R groups. 2-7 Replacement C 6-10 C in the aromatic ring 6-10 The aromatic ring can be either a benzene ring or a naphthalene ring.

[0080] In one particular scheme, R 2-1 and R 2-7 In this context, the halogen is independently F, Cl, Br, or I, for example, F.

[0081] In one particular scheme, R 2-1 and R 2-7 In, the C 1-20 Alkyl groups are independently C 1-10 Alkyl; for example, C 1-6 Alkyl; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; for example, methyl.

[0082] In one particular scheme, R 2-1 and R 2-7 In the context, the -OC 1-20 Alkyl groups are independently -OC 1-10 Alkyl; for example, -OC 1-6 Alkyl; for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; for example, methoxy.

[0083] In one particular scheme, R2-1 and R 2-7 In, the C 6-10 Aromatic rings and 1, 2 or 3 R 2-1-1 Replacement C 6-10 C in the aromatic ring 6-10 The aromatic ring is a benzene ring.

[0084] In one particular scheme, R 2-1 and R 2-7 In this context, the 5- to 16-membered heteroaromatic rings are 5- to 13-membered heteroaromatic rings with one or two heteroatoms selected from N, O, and S, and the heteroatoms are selected from one or two.

[0085] In one particular scheme, R 2-1 and R 2-7 In this context, the 5- to 16-membered heterocyclic alkyl group is independently a 5- to 7-membered heterocyclic alkyl group selected from one, two, or three heteroatoms selected from N, O, and S; and the number of heteroatoms is one or two.

[0086] In one particular scheme, R a R b and R c In, the C 1-20 Alkyl groups are independently C 1-10 Alkyl; for example, C 1-6 Alkyl groups; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl or ethyl; and for example, the -SiR group. a R b R c for

[0087] In one particular scheme, R a R b and R c In, the C 6-10 The aromatic ring is a benzene ring.

[0088] In one particular scheme, R d and R e In, the C 1-20 Alkyl groups are independently C 1-10 Alkyl; for example, C 1-6 Alkyl; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; for example, methyl or ethyl.

[0089] In one particular scheme, R d and R e In the context, the -C 1-6 Alkylene-C 6-10 The aromatic ring is independently -C 1-3 Alkylene-C 6-10Aromatic ring; for example, benzyl.

[0090] In one particular scheme, R f R g and R i In, the C 1-20 Alkyl groups are independently C 1-10 Alkyl; for example, C 1-6 Alkyl; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; for example, methyl or tert-butyl.

[0091] In one particular scheme, R 2-1-1 In the context, the -OC 1-20 Alkyl groups are independently -OC 1-10 Alkyl; for example, -OC 1-6 Alkyl; for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; for example, methoxy.

[0092] In a certain scheme, when R 2 and R 3 The carbon atom attached to it forms C 3-8 When cycloalkyl, the C 3-8 Cycloalkyl group is C 3-6 Cycloalkyl.

[0093] In one particular scheme, R 3 In the context, the term refers to one, two, or three R's. 2-1 Replacement C 1-20 Alkyl is

[0094] In one particular scheme, R 3 In the context, the term refers to one, two, or three R's. 2-7 Replacement C 6-10 Argan

[0095] In one particular scheme, R 0 It is independently methyl, methoxy, or tert-butyl, for example, tert-butyl.

[0096] In one particular scheme, R 2 It is H or methyl;

[0097] R 3 It can be any of the following structures:

[0098]

[0099] Or, R 2 and R 3 The carbon atoms attached to it form In one embodiment, compound I' is one or more of the following compounds:

[0100]

[0101] In one embodiment, in compound I', X - For Cl - R 0 For tert-butyl, Ar 1 Ar 2 Ar 3 and Ar 4 Same, for

[0102] In one embodiment, compound II' is one or more of the following compounds:

[0103]

[0104] In one embodiment, in compound II', X - For Cl - R 0 For tert-butyl, Ar 1 Ar 2 Ar 3 and Ar 4 Same, for

[0105] In one embodiment, compound III is selected from any of the following compounds:

[0106]

[0107] In one embodiment, compound IV is selected from any of the following compounds:

[0108]

[0109] In one scheme, when Cy A has two or more F atoms in meta positions, Connect the position between two F atoms.

[0110] In one embodiment, the reaction is carried out under nitrogen protection.

[0111] In one embodiment, the base is conventional in the art, such as an organic base, an alkali metal salt of an alcohol, or potassium tert-butoxide.

[0112] In one embodiment, the solvent is conventional in the art, for example, a hydrocarbon solvent, or more specifically, an alkane solvent, or even n-heptane.

[0113] In one embodiment, the molar ratio of compound III to compound I is conventional in the art, for example, 1:0.01-0.07; or, for example, 1:0.02 or 1:0.05.

[0114] In one embodiment, the molar ratio of compound III to compound IV is conventional in the art, for example, 1:0.2-3; or, for another example, 1:0.3 or 1:2.

[0115] In one embodiment, the molar ratio of compound III to the base is conventional in the art, for example, 1:0.02-0.2; or, for example, 1:0.04 or 1:0.1.

[0116] In one embodiment, the molar ratio of compound III to nickel 1,5-cyclooctadiene is conventional in the art, for example, 1:0.02-0.1; or, for example, 1:0.02 or 1:0.05.

[0117] In one embodiment, the reaction temperature is conventional in the art, for example, 100-150°C; or, for another example, 130°C.

[0118] In one embodiment, the reaction time is conventional in the art, for example, 8-14 hours; or, for another example, 12 hours.

[0119] This invention also provides a method for preparing a polymer, comprising the following steps: in a solvent, in system 1 or system 2, compound V and compound VII are reacted as shown below; system 1 consists of compound I', 1,5-cyclooctadiene nickel, and a base; system 2 consists of compound II' and 1,5-cyclooctadiene nickel; and compound V is...

[0120]

[0121] Wherein, compound I' or compound II' is as described in any of the preceding embodiments;

[0122] n represents the degree of aggregation;

[0123] R 4 -(CH2) m -、-SiR j R k -、-SiR m R n -C 6-10 Aromatic ring-SiR p R q -、-C 6-30 Aromatic rings -, -C 6-30 Aromatic-C6-30 Aromatic rings - with 1, 2 or 3 Rs 4-1 Substituted -(CH2) m - by 1, 2 or 3 R 4-2 Substituted -SiR j R k - by 1, 2 or 3 R 4-3 Substituted -SiR m R n -C 6-10 Aromatic ring-SiR p R q - by 1, 2 or 3 R 4-4 Replacement -C 6-30 Aromatic rings - or surrounded by 1, 2 or 3 R 4-5 Replacement -C 6-30 Aromatic-C 6-30 Aromatic rings;

[0124] m is an integer from 1 to 20;

[0125] R j and R k and independently for C 1-6 Alkyl or -C 6-30 Aromatic rings;

[0126] R m and R n Independently for C 1-6 Alkyl or -C 6-30 Aromatic rings;

[0127] R p and R q Independently for C 1-6 Alkyl or -C 6-30 Aromatic rings;

[0128] R 4-1 R 4-2 R 4-3 R 4-4 and R 4-5 Independently -OH, C 1-20 Alkyl, C 3-20 cycloalkyl, C 3-20 Cycloalkenyl, 5-16 membered heterocyclic alkyl, -OC 1-20 Alkyl, C 6-10 Aromatic rings or 5-16 heterocyclic aromatic rings;

[0129] R 5 and R 6 Independently H or C 1-6 alkyl.

[0130] In one particular scheme, R 4-(CH2) m -、-SiR j R k -、-SiR m R n -C 6-10 Aromatic ring-SiR p R q -、-C 6-30 Aromatic rings -, -C 6-30 Aromatic-C 6-30 Aromatic rings - or surrounded by 1, 2 or 3 R 4-4 Replacement -C 6-30 Aromatic rings-.

[0131] In one scheme, m is 2, 4, or 6.

[0132] In one particular scheme, R 4 In the context, the -C 6-30 Aromatic rings - and 1, 2 or 3 R 4-4 Replacement -C 6-30 -C in aromatic rings 6-30 Aromatic ring - is - C 6-13 Aromatic rings; for example, aromatic rings.

[0133] In one particular scheme, R 4 In the context, the -C 6-30 Aromatic-C 6-30 Aromatic ring - is - C 6-10 Aromatic-C 6-10 Aromatic rings; for example, aromatic rings.

[0134] In one particular scheme, R j and R k In, the C 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl.

[0135] In one particular scheme, R m and R n In, the C 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl.

[0136] In one particular scheme, R p and R q The C 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl.

[0137] In one particular scheme, R 4-4 In, the C1-20 Alkyl groups are independently C 1-10 Alkyl; for example, n-octyl.

[0138] In one particular scheme, R 5 and R 6 In, the C 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl.

[0139] In one embodiment, compound VII is selected from any of the following structures: For example

[0140] In one embodiment, the reaction is carried out under nitrogen protection.

[0141] In one embodiment, the base is conventional in the art, such as an organic base, an alkali metal salt of an alcohol, or potassium tert-butoxide.

[0142] In one embodiment, the solvent is conventional in the art, for example, a hydrocarbon solvent, or more specifically, an alkane solvent, or even n-heptane.

[0143] In one embodiment, the molar ratio of compound V to compound I is conventional in the art, for example, 1:0.01-0.07; or, for another example, 1:0.05.

[0144] In one embodiment, the molar ratio of compound V to compound VII is conventional in the art, for example, 1:0.5-2; or, for another example, 1:1.

[0145] In one embodiment, the molar ratio of compound V to nickel 1,5-cyclooctadiene is conventional in the art, for example, 1:0.02-0.1; or, for another example, 1:0.05.

[0146] In one embodiment, the reaction temperature is conventional in the art, for example, 100-150°C; or, for another example, 130°C.

[0147] In one embodiment, the reaction time is conventional in the art, for example, 36-72 hours, or even 48 hours.

[0148] This invention also provides a method for preparing a polymer, comprising the following steps: in a solvent, in system 1 or system 2, compound V and compound IX are reacted as shown below; system 1 is compound I', 1,5-cyclooctadiene nickel, and a base; system 2 is compound II' and 1,5-cyclooctadiene nickel; the imidazole compound is compound I' and / or compound II'; and compound V is...

[0149]

[0150] Where n is the degree of aggregation;

[0151] R 7 -C 6-30 Aromatic rings -, -5 to 16-membered heteroaryl rings -, with 1, 2 or 3 R-rings 7-1 Replacement -C 6-30 Aromatic rings - or surrounded by 1, 2 or 3 R 7-2 Substituted -5 to 16-membered heteroaryl rings;

[0152] R 7-1 and R 7-2 Independently -OH, C 1-20 Alkyl, C 3-20 cycloalkyl, C 3-20 Cycloalkenyl, 5-16 membered heterocyclic alkyl, -OC 1-20 Alkyl, C 6-10 Aromatic rings, 5-16 heterocyclic aromatic rings;

[0153] The 5- to 16-membered heteroaromatic rings are 5- to 16-membered heteroaromatic rings with 1, 2, 3 or 4 heteroatoms selected from N, O and S.

[0154] n represents the degree of aggregation.

[0155] In one particular scheme, R 7 -C 6-30 Aromatic rings -, -5 to 16-membered heteroaryl rings - or surrounded by 1, 2 or 3 R-rings 7-1 Replacement -C 6-30 Aromatic ring.

[0156] In one particular scheme, R 7-1 Independently for C 1-20 alkyl.

[0157] In one particular scheme, R 7 In the context, the -C 6-30 Aromatic rings - and 1, 2 or 3 R 7-1 Replacement -C 6-30 -C in aromatic rings 6-30Aromatic ring - independently -C 6-14 Aromatic rings; for example, aromatic rings.

[0158] In one particular scheme, R 7 In this context, the -5 to 16-membered heteroaryl ring is a -5 to 7-membered heteroaryl ring.

[0159] In one embodiment, compound IX is selected from any of the following compounds:

[0160]

[0161] In one embodiment, the reaction is carried out under nitrogen protection.

[0162] In one embodiment, the base is conventional in the art, such as an organic base, an alkali metal salt of an alcohol, or potassium tert-butoxide.

[0163] In one embodiment, the solvent is conventional in the art, for example, a hydrocarbon solvent, or more specifically, an alkane solvent, or even n-heptane.

[0164] In one embodiment, the molar ratio of compound V to compound I is conventional in the art, for example, 1:0.01-0.07; or, for another example, 1:0.05.

[0165] In one embodiment, the molar ratio of compound V to compound IX is conventional in the art, for example, 1:0.2-3; or, for another example, 1:1.

[0166] In one embodiment, the molar ratio of compound V to the base is conventional in the art, for example, 1:0.02-0.2; or, for another example, 1:0.1.

[0167] In one embodiment, the molar ratio of compound V to nickel 1,5-cyclooctadiene is conventional in the art, for example, 1:0.02-0.1; or, for example, 1:0.02 or 1:0.05.

[0168] In one embodiment, the reaction temperature is conventional in the art, for example, 100-150°C; or, for another example, 100°C.

[0169] In one embodiment, the reaction time is conventional in the art, for example, 8-14 hours; or, for another example, 12 hours.

[0170] The present invention also provides a polyfluorinated compound or polyfluorinated polymer selected from any of the following structures:

[0171]

[0172]

[0173] Where n is the degree of aggregation;

[0174] The number-average molecular weight and molecular weight distribution of polymers 2-1 to 3-6 are shown in the table below:

[0175] polymer Molecular weight (3.4 kg / mol) Molecular weight distribution 2-1 3.4 1.38 2-2 6.0 1.70 2-3 4.3 1.49 2-4 19.1 1.81 2-5 3.0 1.16 2-6 21.8 1.57 2-9 3.1 1.21 2-10 5.9 1.26 2-11 6.7 1.08 2-12 3.4 1.24 2-13 6.2 2.62 3-1 16.4 2.96 3-2 16.3 4.37 3-3 15.3 2.76 3-4 6.4 1.39 3-5 26.2 3.96 3-6 11.9 1.76 .

[0176] In one approach, the number-average molecular weight and molecular weight distribution are obtained using gel permeation chromatography. For example, the method involves dissolving the polymer in anhydrous THF, using THF as the mobile phase and polystyrene as the reference, and then performing the test using gel permeation chromatography.

[0177] Unless otherwise specified, the terms used in this invention have the following meanings:

[0178] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0179] The term "alkyl" refers to an alkyl group having a specified number of carbon atoms (e.g., C10, C20, C30, C40, C50, C60, C7 ...60, C70, C60, C60, C70, C60, C70, C60 1-20 Alkyl groups are straight-chain or branched hydrocarbon groups. Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, and n-hexyl.

[0180] The term "cycloalkyl" refers to a compound having a specified number of carbon atoms (e.g., C10, C20, C30, C40, C50, C60, C70, C80, C9 ... 3-20 Cycloalkyl groups are cyclic hydrocarbon groups consisting only of carbon atoms. Cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0181] The term "aromatic ring" refers to a ring having a specified number of carbon atoms (e.g., C364). 6-10 Aryl groups are cyclic hydrocarbon groups consisting solely of carbon atoms, which can be monocyclic or polycyclic, and at least one group is aromatic (conforming to Hückel's rule). Aryl groups include, but are not limited to, phenyl and naphthyl groups.

[0182] The term "heteroaromatic ring" refers to a cyclic hydrocarbon group having a specified number of carbon atoms (e.g., 5-16), a specified number of heteroatoms (e.g., 1, 2, or 3), and a specified type of heteroatom (one or more of N, O, and S). It can be monocyclic or polycyclic, and at least one ring is aromatic (conforming to Hückel's rule). Heteroaromatic rings include, but are not limited to, furan rings, pyrrole rings, thiophene rings, pyrazole rings, imidazole rings, oxazole rings, thiazole rings, pyridine rings, pyrimidine rings, and indole rings.

[0183] The term "heterocyclic alkyl" refers to a compound having a specified number of carbon atoms (e.g., C10, C20, C30, C40, C50, C60, C7 ... 3-20 A saturated cyclic hydrocarbon group consisting of a specified number of heteroatoms (e.g., 1, 2, or 3) and a specified type of heteroatomide (one or more of N, O, and S). Heterocyclic alkyl groups include, but are not limited to, those containing heteroatoms. wait.

[0184] The term "cycloalkenyl" refers to a cycloalkenyl group having at least one double bond (such as a carbon-carbon double bond) and being able to be connected to the rest of the molecule via a single bond through any suitable carbon atom; for example, C1. 3-20 Cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, or cycloheptenyl.

[0185] Those skilled in the art will understand that, according to the conventions used in the art, the structural formulas of the descriptive groups described in this application... This refers to the fact that the corresponding group R is linked to other fragments or groups in the compound through this site.

[0186] The "-" at the end of a group indicates that the group is connected to other segments in the molecule through that site. For example, -OCH3 refers to a methyl group, where the oxygen atom is attached to the rest of the molecule.

[0187] When any variable (e.g., R) Ar When a variable appears multiple times in the definition of a compound, the definition at each position is independent of the definitions at the other positions; their meanings are independent and do not affect each other. Therefore, if a group is surrounded by one, two, or three R... Ar Group substitution, meaning that the group can be replaced by up to 3 R groups. Ar Replace, the position R Ar Definition and other positions R Ar The definitions are independent of each other. Furthermore, combinations of substituents and / or variables are only permitted if the combination produces a stable compound.

[0188] Without violating common sense in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0189] The reagents and raw materials used in this invention are all commercially available.

[0190] The positive and progressive effects of this invention are as follows:

[0191] (1) The imidazole salt of the present invention is suitable for the synthesis of alkyl fluorinated aromatics and fluorinated polymers, with high reaction efficiency and regioselectivity. This is of great significance for the development and synthesis of fluorinated drugs and the synthesis of new fluorinated materials.

[0192] (2) The alkyl fluorinated aromatic compounds prepared by the method of the present invention have high yields and high reaction regioselectivity, with most of them exceeding 99 / 1.

[0193] (3) The preparation method of the present invention has wide substrate applicability and is well applicable to various olefins. The synthesized alkyl fluorinated aromatic compounds have a variety of structures.

[0194] (4) This invention provides a novel method for preparing polyfluoroaryl main-chain polymers; the fluorinated polymers prepared by this method have high yield, high molecular weight, narrow molecular weight distribution, and a single and controllable polymer structure. Detailed Implementation

[0195] The present invention will be further illustrated by way of embodiments below, but the present invention is not limited to the scope of the embodiments described herein.

[0196] For experimental methods in the following examples where specific conditions are not specified, follow conventional methods and conditions, or select according to the product instructions.

[0197] The present invention will be further illustrated by way of embodiments below, but the present invention is not limited to the scope of the embodiments described herein.

[0198] For experimental methods in the following examples where specific conditions are not specified, follow conventional methods and conditions, or select according to the product instructions.

[0199] The molecular weight determination method involved in the following examples is as follows: the polymer is dissolved in anhydrous THF, THF is used as the mobile phase, polystyrene is used as the reference, and gel permeation chromatography (GPC) is used to determine its molecular weight and molecular weight distribution.

[0200] Example 1: Synthesis of compounds I-1 and II-1

[0201]

[0202] Step 1: Synthesis of 2,6-diphenylmethyl-4-(tert-butyl)aniline (intermediate 1):

[0203] 4-tert-butylaniline (14.9 g, 100 mmol), benzyl alcohol (36.8 g, 200 mmol), and a stir bar were added to a 500 mL round-bottom flask. The mixture was heated to 100 °C until all solids dissolved. ZnCl2 (6.8 g) was dissolved in concentrated hydrochloric acid (8.5 mL) and then slowly added dropwise to the above mixture. This process was exothermic, producing a large amount of white fumes in the round-bottom flask and water appearing on the flask walls. After the addition was complete, the reaction system was heated at 160 °C for 1 hour until the reaction system was completely solidified. After cooling to room temperature, the solids were dissolved in an appropriate amount of dichloromethane. The organic layer was washed with saturated ammonium chloride solution and saturated sodium chloride solution, respectively, and then dried with anhydrous sodium sulfate. The solvent was removed by rotary evaporation to obtain a gray crude product, which was washed with methanol and dried to obtain white intermediate 1 (43.0 g, yield 89%). 1H NMR (400MHz, CDCl3) δ7.31–7.25(m,8H),7.23–7.18(m,4H),7.09(m,8H),6.57(s,2H),5.45(s,2H),0.96(d,J=1.5Hz,9H). 13 C NMR (101MHz, CDCl3) δ143.0,140.1,139.6,129.6,128.6,128.5,126.7,125.6,52.8,34.1,31.4.

[0204] Step 2: Synthesis of 2-((2,6-diphenylmethyl-4-(tert-butyl)phenyl)imine)acenaphthene-1(2H)-one (intermediate 2):

[0205] In a 250 mL round-bottom flask, acenaphthene (3.64 g, 20.0 mmol) was added, and after purging with nitrogen three times, 80 mL of acetonitrile was added. The reaction mixture was heated to reflux for 1 hour, and 12 mL of acetic acid was added. After another 1 hour, intermediate 1 (9.63 g, 20.0 mmol) was added, and reflux was continued for 8 hours. After cooling to room temperature, the solvent was removed by rotary evaporation, 50 mL of ethanol was added, and reflux was continued for 2 hours. After cooling to room temperature, the mixture was filtered to obtain orange-yellow intermediate 2 (11.46 g, yield 89%). 1 H NMR(400MHz, CDCl3)δ8.01(t,J=7.5Hz,2H),7.74–7.64(m,2H),7.23(m,4H),7.16(m,2H),7.03(m,5H),6.99(s,2H), 6.84(d,J=7.5Hz,4H),6.59(t,J=7.6Hz,4H),6.42(t,J=7.3Hz,2H),6.00(d,J=7.1Hz,1H),5.44(s,2H),1.16(s,9H). 13 C NMR (101MHz, CDCl3) δ 189.9, 162.5, 146.7, 146.0, 143.2, 142.6, 142.0, 131.9, 131.2, 130.2, 130.0, 129.8, 129.5, 128.5, 128.2, 127.9, 127.6, 127.4, 127.2, 126.3, 125.6, 125.2, 123.9, 121.6, 52.5, 34.6, 31.5. HRMS (ESI) calculated C 48 H 40 NO[M+H] + m / z 646.3104, measured value 646.3100.

[0206] Step 3: N 1-(2,6-Diphenylmethyl-4-(tert-butyl)phenyl)-N 2 Synthesis of 1,2-diimine (intermediate 3): (2,6-diisopropylphenyl)acenaphthene-1,2-diimine

[0207] In a 250 mL round-bottom flask, intermediate 2 (11.40 g, 17.6 mmol), 2,6-diisopropylaniline (3.13 g, 17.6 mmol), and p-toluenesulfonic acid monohydrate (0.67 g, 3.5 mmol) were added, and the mixture was purged with nitrogen three times. 150 mL of toluene was added and the mixture was refluxed for 12 hours. After cooling to room temperature, the solvent was removed by rotary evaporation. Then, 50 mL of ethanol was added and the mixture was refluxed for 2 hours. After cooling to room temperature, the mixture was filtered to give yellow intermediate 3 (12.03 g, 85% yield). 1 H NMR(400MHz, CDCl3) δ7.66(d,J=8.2Hz,1H),7.49(d,J=8.2Hz,1H),7.29–7.22(m,7H),7. 18(m,3H),7.09(d,J=7.5Hz,4H),7.00(s,2H),6.91(d,J=7.5Hz,4H),6.85(t,J=7.7Hz,1H ),6.56(t,J=7.5Hz,4H),6.43(d,J=7.2Hz,1H),6.37(t,J=7.3Hz,2H),5.77(d,J=7.1Hz, 1H),5.66(s,2H),3.17(m,2H),1.29(d,J=6.8Hz,6H),1.19(s,9H),1.02(d,J=6.8Hz,6H). 13 C NMR (101MHz, CDCl3) δ 163.8, 162.2, 147.2, 146.9, 146.1, 143.9, 141.9, 140.1, 135.8, 131.7, 129.8, 129.7, 129.6, 128.7, 128.7, 128.6, 128.0, 127.8, 127.7, 127.00, 126.9, 126.1, 125.5, 125.3, 124.5, 124.3, 123.6, 122.9, 52.4, 34.5, 31.6, 28.6, 24.4, 23.8. HRMS (ESI) calculated C 60 H 57 N2[M+H] + m / z 805.4516, measured value 805.4511.

[0208] Step 4: Synthesis of 7-(2,6-diphenylmethyl-4-(tert-butyl)phenyl)-9-(2,6-diisopropylphenyl)-7H-acenaphthene[1,2-d]chloroimidazolium salt (compound I-1):

[0209] Intermediate 3 (9.66 g, 12.0 mmol) and chloromethyl ethyl ether (21 mL, 240 mmol) were added to a 150 mL pressure-resistant bottle. The mixture was reacted at 100 °C for 12 hours. After cooling to room temperature, the solvent was removed by rotary evaporation. The crude product was separated by column chromatography to obtain bright yellow compound I (6.92 g, yield 69%). 1 H NMR(400MHz, CDCl3)δ12.42(s,1H),7.81(d,J=8.2Hz,1H),7.64(m,2H),7.45–7.37(m,3H), 7.28(m,8H),7.20–7.15(m,2H),7.13(s,2H),7.08(dd,J=8.3,7.1Hz,1H),6.98(d,J=6.9Hz ,1H),6.79(d,J=7.4Hz,4H),6.72(t,J=7.6Hz,4H),6.62(t,J=7.3Hz,2H),6.26(d,J=6.9Hz ,1H),5.60(s,2H),2.71(m,2H),1.34(d,J=6.8Hz,6H),1.15(s,9H),1.07(d,J=6.8Hz,6H). 13 C NMR (101MHz, CDCl3) δ 154.2, 145.0, 143.1, 141.6, 141.1, 140.8, 138.1, 137.0, 132.04, 130.0, 129.8, 129.5, 129.3, 129.1, 129.0, 128.9, 128.6, 128.3, 127.4, 127.2, 126.8, 126.6, 124.9, 124.1, 122.5, 122.1, 121.9, 52.2, 35.1, 31.0, 29.4, 24.6, 23.8. HRMS (ESI) calculated C 61 H 57 N2 + [M] + m / z 817.4516, measured value 817.4508.

[0210] Step 5: Synthesis of 7-(2,6-diphenylmethyl-4-(tert-butyl)phenyl)-9-(2,6-diisopropylphenyl)-7H-acenaphthene[1,2-d]imidazol-8-ylide (compound II-1):

[0211] In a glove box, compound I (85.4 mg, 0.1 mmol) and potassium tert-butoxide (16.8 mg, 0.15 mmol) were added to an 8 mL vial, followed by 2.0 mL of anhydrous tetrahydrofuran. The mixture was stirred at room temperature for 4 hours. After the reaction was complete, the solvent was removed by vacuum extraction, followed by extraction with cyclohexane. The solvent was then removed by vacuum extraction to give compound II (64.8 mg, 79% yield) in yellow. 1 H NMR (400MHz, Benzene-d6) δ7.52(s,2H),7.40(d,J=7.5Hz,4H),7.36(d,J=7.7Hz,1H),7.27( d,J=7.8Hz,2H),7.14-7.19(m,6H),7.04(t,J=7.5Hz,4H),6.95(t,J=7.3Hz,2H),6.87–6.82( m,1H),6.77(d,J=6.8Hz,1H),6.71(t,J=7.4Hz,4H),6.68–6.59(m,3H),6.31(s,2H),6.11(d ,J=6.9Hz,1H),3.42-3.48(m,2H),1.29(d,J=6.8Hz,6H),1.15(s,9H),1.11(d,J=6.9Hz,6H).

[0212] Example 2: Synthesis of alkyl polyfluoroaromatic compounds (compound I-1 as ligand)

[0213]

[0214] General Method A: In a nitrogen-filled glove box, add compound I-1 (8.5 mg, 0.01 mmol, 2 mol%), potassium tert-butoxide (2.2 mg, 0.02 mmol, 4 mol%), and Ni(cod)₂ (2.8 mg, 0.01 mmol, 2 mol%) to an 8 mL vial, and finally add 1 mL of n-heptane. Stir at room temperature for 8 hours. Then add compound III (0.5 mmol) and compound IV (1.0 mmol), remove from the glove box, and react at 130 °C for 12 hours. After the reaction is complete, obtain the product directly by column chromatography.

[0215] General Method B: In a nitrogen-filled glove box, add compound I-1 (21.3 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (5.6 mg, 0.05 mmol, 10 mol%), and Ni(cod)₂ (6.9 mg, 0.025 mmol, 5 mol%) to an 8 mL vial, followed by 1 mL of n-heptane. Stir at room temperature for 8 hours. Then add compound III (0.5 mmol) and compound IV (1.0 mmol), remove from the glove box, and react at 130 °C for 12 hours. After the reaction is complete, obtain the product directly by column chromatography.

[0216] General Method C: In a nitrogen-filled glove box, add compound I-1 (21.3 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (5.6 mg, 0.05 mmol, 10 mol%), and Ni(cod)₂ (6.9 mg, 0.025 mmol, 5 mol%) to an 8 mL vial, followed by 1 mL of n-heptane. Stir at room temperature for 8 hours. Then add compound III (1.5 mmol) and compound IV (0.5 mmol), remove from the glove box, and react at 130 °C for 12 hours. After the reaction is complete, obtain the product directly by column chromatography.

[0217] The structural formula of the compound prepared in this embodiment is:

[0218]

[0219]

[0220] Compound 1-1: A colorless liquid was prepared by general method A in 97% yield. 1 H NMR (400MHz, CDCl3) δ2.68(t,J=7.6Hz,2H),2.23(t,J=2.0Hz,3H),1.56(m,2H),1.38–1.19(m,10H),0.88(t,J=6.9Hz,3H). 13 C NMR(101MHz,CDCl3)δ144.7(dm,J F =243.4),118.0(t,J=18.8Hz),113.3(t,J=19.2Hz),32.0,29.5,29.4,29.3,22.8,14.2,7.6–7.0(m). 19 F NMR (377MHz, CDCl3) δ-145.26 (ddd, J=22.1, 12.9, 2.0Hz, 2F), -146.72 (dd, J=22.1, 12.9Hz, 2F).

[0221] Compounds 1-2: Prepared as white solids by general method A, with a yield of 98%. 1 H NMR (400MHz, CDCl3) δ7.48(m,5H),2.78(t,J=7.0Hz,2H),1.65(m,2H),1.31(m,10H),0.90(t,J=6.3Hz,3H). 13 CNMR(101MHz,CDCl3)δ146.9(dm,J F =256.5Hz), 143.8 (dm, J) F =257.6Hz),130.3,129.0,128.7,128.0,120.4–120.0(m),118.3-118.0(m),32.0,29.5,29.4,29.3,23.0,22.8,14.2. 19 F NMR(377MHz, CDCl3)δ-145.03–-145.79(m,4F).

[0222] Compounds 1-3: Colorless liquids were prepared by general method B in 68% yield. 1 H NMR (400MHz, CDCl3) δ4.03(t,J=1.2Hz,3H),2.71–2.61(m,2H),1.56(m,2H),1.28(m,10H),0.88(t,J=6.9Hz,3H). 13 C NMR (101MHz, CDCl3) δ145.5 (dm, JF=243.4Hz), 141.2 (ddt, JF=247.5, 16.2, 4.0Hz), 136.4-13 6.2(m),114.3(t,JF=19.2Hz),62.3(t,JF=3.5Hz),32.0,29.6,29.4,29.3,22.8,22.5,14.2. 19 F NMR (377MHz, CDCl3) δ-146.24 (dd, J=21.7, 8.9Hz), -158.97 (dd, J=21.9, 9.0Hz).

[0223] Compounds 1-4: Colorless liquids were prepared by general method B in 88% yield. 1 H NMR (400MHz, CDCl3) δ2.68(t,J=7.6Hz,2H),1.64–1.52(m,2H),1.38–1.18(m,10H),0.88(t,J=6.9Hz,3H). 13CNMR(101MHz,CDCl3)δ145.2(dm,J F =245.4Hz), 139.5 (dm, J) F =252.5Hz), 137.5(dm,J) F =250.5Hz), 115.7(t,J F =19.0Hz),32.0,29.5,29.4,29.3,22.8,22.5,14.2. 19 F NMR (377MHz, CDCl3) δ-144.60 (dd, J=22.3, 8.0Hz, 2F), -158.58 (t, J=20.8Hz, 2F), -163.06–-163.44 (m, 1F).

[0224] Compounds 1-5: Colorless liquids were prepared by general method A in 91% yield. 1 H NMR (400MHz, CDCl3) δ2.77(t,J=7.6Hz,2H),1.68–1.56(m,2H),1.41–1.19(m,10H),0.88(t,J=6.8Hz,3H). 13 CNMR(101MHz,CDCl3)δ145.3(dm,J F =251.5Hz), 144.1(ddm,J F =259.6, 16.2 Hz), 126.0 (t, J) F =18.5Hz), 121.1(-CF3,J F =274.7Hz),107.6-107.1(m),32.0,30.0,29.4,29.3,29.2,29.1(m),23.3,22.8,14.2. 19 F NMR(377MHz, CDCl3)δ-56.20(td,J=21.5,6.8Hz,3F),-141.72–-141.89(m,2F),-142.38–-142.79(m,2F).

[0225] Compounds 1-6: Colorless liquids were prepared according to general method A in 75% yield. 1 H NMR (400MHz, CDCl3) δ6.95–6.67(m,1H),2.60(t,J=7.7Hz,2H),1.66–1.49(m,2H),1.28(m,10H),0.88(t,J=6.9Hz,3H). 13 C NMR(101MHz,CDCl3)δ147.0(ddm,JF =246.4,10.1Hz),145.9(ddm,J) F =246.4,10.1Hz),140.8(dtm,J) F =252.5,13.1Hz),138.8(dtm,J) F =251.5, 13.1 Hz), 126.2 (dm, J) F =15.2Hz),111.1(dt,J F =19.2,4.0Hz),32.0,30.0,29.5,29.4,29.3,28.6,22.8,14.2. 19 F NMR (377MHz, CDCl3) δ-140.64--146.74(m,1F),-144.29--144.56(m,1F),-156.62(td,J=5.0,1.0Hz 1F),-159.83(td,J=20.5,7.9Hz,1F).

[0226] Compounds 1-7: Colorless liquids were prepared by general method B in 73% yield. 1 H NMR (400MHz, CDCl3) δ2.80 (t, J = 7.7Hz, 2H), 1.71–1.57 (m, 2H), 1.30–1.26 (m, 10H), 0.88 (t, J = 6.8Hz, 3H). 13 CNMR(101MHz,CDCl3)δ143.4(dtm,J F =245.4, 16.2 Hz), 140.5 (dm, J) F =256.5,135.7(t,J) F =17.2Hz),31.9,29.4,29.3,29.2,28.7,23.9,22.8,14.2. 19 F NMR(377MHz, CDCl3)δ-91.83–-92.33(m,2F),-145.43–-145.99(m,2F).

[0227] Compounds 1-8: Prepared as yellow liquids by general method B, with a yield of 68%. 1 H NMR (400MHz, CDCl3) δ8.24(s,2H),2.69(t,J=7.6Hz,2H),1.61-1.55(m,2H),1.38–1.18(m,10H),0.86(t,J=6.8Hz,3H). 13 C NMR(101MHz,CDCl3)δ158.3(dd,JF =258.1,4.1Hz),133.8(dd,J F =22.4,6.1Hz),126.90(t,J) F =17.5Hz),31.9,29.4,29.3,29.2,28.9,22.7,22.2,14.2. 19 F NMR (377MHz, CDCl3) δ-130.91 (s, 2F).

[0228] Compounds 1-9: Prepared as yellow liquids by general method B, with a yield of 71%. 1 H NMR (400MHz, CDCl3) δ7.63–7.42(m,2H),3.91(s,3H),2.69(t,J=7.6Hz,2H),1.69–1.49(m,3H),1.39–1.17(m,10H),0.87(t,J=6.9Hz,3H). 13 C NMR(101MHz,CDCl3)δ165.4(t,J F =3.4Hz), 161.3(dd,J F =247.3,9.2Hz),129.8(t,J) F =9.7Hz), 123.9(t,J F =20.7Hz), 112.4(dd,J F =20.2,8.1Hz),52.6,32.0,29.5,29.40,29.38,29.3,22.8,14.2. 19 F NMR (377MHz, CDCl3) δ-114.65 (d, J = 7.1Hz, 2F).

[0229] Compounds 1-10: colorless liquids were prepared by general method C in 63% yield. 1 H NMR (400MHz, CDCl3) δ6.81–6.66(m,1H),2.63(t,J=7.6Hz,2H),1.59-1.52(m,2H),1.36–1.22(m,10H),0.88(t,J=6.8Hz,3H). 13 C NMR(101MHz,CDCl3)δ155.5(dm,J F =245.4Hz), 150.2(dm,J) F =248.5Hz), 148.9 (dm, J) F =249.4Hz), 137.2 (dm, J) F=248.5Hz)115.8(t,J F =22.4Hz),100.4(ddd,J F =29.0,21.2,3.8Hz),32.0,29.5,29.4,29.3,22.8,22.4,14.2. 19 F NMR (377MHz, CDCl3) δ-119.85 (t, J=11.3Hz, 1F), -137.2 (d, J=26.4Hz, 1F), -136.62 (ddd, J=21.9, 10.7, 4.8Hz, 1F). -165.96–-166.22 (m, 1F).

[0230] Compounds 1-11: A colorless liquid was prepared by general method C in 67% yield. 1 H NMR (400MHz, CDCl3) δ6.82–6.49(m,2H),2.60(t,J=7.6Hz,2H),1.58-1.51(m,2H),1.43–1.19(m,10H),0.88(t,J=6.8Hz,3H). 13 C NMR(101MHz,CDCl3)δ114.5(td,J F =21.0,4.6Hz),99.9(ddd,J F =29.9,25.2,1.5Hz),32.0,29.7,29.5,29.4,29.4,22.8,22.1(t,J F =1.8Hz). 19 F NMR(377MHz, CDCl3)δ-112.38–-112.53(m,1F),-113.29–-113.45(m,2F).

[0231] Compounds 1-12: colorless liquids were prepared by general method C in 85% yield. 1 H NMR (400MHz, CDCl3) δ6.89(ddd,J=9.8,8.6,4.9Hz,1H),2.78–2.65(m,2H),1.68–1.56(m,2H),1.37–1.21(m,10H),0.88(t,J F =6.9Hz, 3H). 13 C NMR(101MHz,CDCl3)δ145.9(dm,J F =248.5Hz), 145.0(dm,J) F =244.4Hz), 121.9(t,J F=18.5Hz), 103.4(t,J F =22.7Hz),32.0,29.38,29.4,29.3,23.1,22.8,14.2. 19 F NMR(377MHz, CDCl3)δ-140.06–-140.53(m,2F),-144.83–-145.35(m,2F).

[0232] Compounds 1-13: Colorless liquids were prepared by general method A in 94% yield. 1 H NMR (400MHz, CDCl3) δ2.71–2.59(m,2H),2.23(t,J=2.1Hz,3H),1.49–1.38(m,2H),0.97(s,9H). 13 C NMR(101MHz,CDCl3)δ145.2(dddd,J F =244.4,14.6,7.2,3.8Hz),144.8(dddd,J F =243.4,14.2,7.6,3.8Hz),118.77(t,J F =18.6Hz), 113.15(t,J F =19.2Hz),43.8,30.8,29.1,19.8–16.4(m),7.4. 19 F NMR (377MHz, CDCl3) δ-145.25 (ddd, J=22.0, 12.8, 2.0Hz, 2F), -147.50 (dd, J=22.0, 12.9Hz, 2F).

[0233] Compounds 1-14: Colorless liquids were prepared by general method A in 99% yield. 1 H NMR (400MHz, CDCl3) δ2.79–2.58(m,2H),2.23(t,J=2.0Hz,3H),1.83–1.60( m,5H),1.45(dt,J=10.1,6.8Hz,2H),1.30–1.12(m,4H),0.99–0.85(m,2H). 13 C NMR(101MHz,CDCl3)δ145.2(dm,J F =244.4Hz), 144.7 (dm, J) F =244.4Hz), 118.5(t,J F =18.7Hz), 113.2(t,J F=19.2Hz),37.7,37.2,33.3,26.8,26.5,20.3,7.3. 19 F NMR (377MHz, CDCl3) δ-145.23 (ddd, J=22.1, 12.8, 1.8Hz, 2F), -146.98 (dd, J=22.1, 12.8Hz, 2F).

[0234] Compounds 1-15: Colorless liquids were prepared by general method B in 88% yield. 1 H NMR (400MHz, CDCl3) δ7.35–7.27(m,2H),7.26–7.15(m,3H),2.84–2.61(m,4H),1.95(tt,J=9.2,6.9Hz,2H). 13 CNMR(101MHz,CDCl3)δ145.3(dm,J F =245.4Hz), 141.3, 139.5 (dm, J) F =251.5Hz), 137.8 (dm, J) F =250.5Hz),128.5,128.4,126.2,115.3(td,J F =18.9,3.8Hz),35.5,30.8,22.2. 19 F NMR (377MHz, CDCl3) δ-144.25 (dd, J=23.0, 8.9Hz, 2F), -158.04 (t, J=21.0Hz, 1F), -160.38–-166.23 (m, 2F).

[0235] Compounds 1-16: colorless liquids were prepared by general method B in 70% yield. 1 H NMR (400MHz, CDCl3) δ6.70-6.70(m,3H),3.87(s,3H),3.86(s,3H),2.80(t,J=7.7Hz,2H),2.70–2.60(m,2H),2.01–1.88(m,2H). 13 C NMR(101MHz,CDCl3)δ148.9,147.5,145.1(dm,J F =245.4Hz), 143.8 (dm, J) F =257.6Hz), 125.4(t,J F =18.2Hz), 121.0(-CF3,J F=274.7Hz),107.9-106.8(m)133.4,120.2,111.5,111.1,55.8,55.7,34.9,30.2,22.7. 19 F NMR (377MHz, CDCl3) δ-56.23 (t, J=21.5Hz, 3F), -141.43–-141.81 (m, 2F), -142.26 (td, J=15.8, 6.1Hz, 2F).

[0236] Compounds 1-17: A colorless liquid was prepared by general method B in 79% yield. 1 H NMR (400MHz, CDCl3) δ7.32-7.26(m,2H),7.22-7.17(m,3H),2.74(t,J=6.9Hz,2H),2.66(t,J=7.1Hz,2H),1.75–1.57(m,4H). 13 C NMR(101MHz,CDCl3)δ145.2(dm,J F =244.4Hz), 142.1, 139.6 (dm, J) F =252.5Hz), 137.5(dm,J) F =250.5Hz),128.51,128.50,126.0,115.4(td,J F =18.9,3.9Hz),35.6,31.0,28.9,22.3. 19 F NMR (377MHz, CDCl3) δ-144.32 (dd, J=22.5, 8.3Hz, 2F), -158.18 (t, J=20.8Hz, 1F), -163.00 (ddd, J=21.4, 8.4, 7.5Hz, 2F).

[0237] Compounds 1-18: A colorless liquid was prepared by general method C in 92% yield. 1 H NMR (400MHz, CDCl3) δ6.67(t,J=2.1Hz,2H),6.16(t,J=2.1Hz,2H),3.89(t,J=7.1Hz, 2H),2.70(t,J=7.6Hz,2H),1.82-1.75(m,2H),1.64–1.55(m,2H),1.37-1.32(m,6H). 13 C NMR(101MHz,CDCl3)δ145.1(dm,J F =245.4Hz), 139.5 (dm, J) F=252.5Hz), 137.5(dm,J) F =252.5Hz), 120.5, 115.5(td,J F =19.0,3.7Hz),107.9,49.6,31.6,29.3,29.1,28.9,26.7,22.4. 19 F NMR (377MHz, CDCl3) δ-144.47 (dd, J=23.2, 9.1Hz, 2F), -158.29 (t, J=21.0Hz, 1F), -163.08 (ddd, J=24.5, 10.4, 1.4Hz, 3F).

[0238] Compounds 1-19: Prepared as white solids by general method C, with a yield of 54%. 1 H NMR (400MHz, CDCl3) δ8.09(d,J=7.7Hz,2H),7.44(t,J=7.2Hz,2H),7.37(d,J=7.7Hz,2H),7.21(t,J=7.2Hz, 2H),4.28(t,J=7.1Hz,2H),2.61(t,J=7.4Hz,2H),2.00–1.76(m,2H),1.57–1.46(m,2H),1.42-1.33(m,4H). 13 C NMR(101MHz,CDCl3)δ145.1(dm,J F =245.4Hz), 139.5 (dm, J) F =252.5Hz), 137.5(dm,J) F =252.5Hz),140.5,125.7,123.0,120.5,118.9,115.32(t,J F =20.0Hz).108.7,43.1,29.2,28.99,28.95,27.1,22.3. 19 F NMR (377MHz, CDCl3) δ-144.47 (dd, J=23.5, 9.3Hz, 2F), -158.15 (t, J=21.1Hz, 1F), -162.37–-167.29 (m, 2F).

[0239] Compounds 1-20: colorless liquids were prepared by general method C in 73% yield. 1H NMR (400MHz, CDCl3) δ7.62(d,J=7.9Hz,1H),7.32(dd,J=8.2,0.6Hz,1H),7.23–7.15(m,1H),7.14–7.02(m,2H),6.47(dd, J=3.1,0.7Hz,1H),4.09(t,J=7.1Hz,2H),2.64(t,J=7.6Hz,2H),1.89–1.74(m,2H),1.54-1.51(m,2H),1.34–1.22(m,6H). 13 C NMR(101MHz,CDCl3)δ145.1(dm,J F =245.4Hz), 139.5 (dm, J) F =251.5Hz), 137.5 (dm, J) F =251.5Hz),136.1,128.7,127.8,121.4,121.0,119.3,109.4,101.0,46.4,30.3,29.3,29.1,29.0,27.0,22.3. 19 F NMR (377MHz, CDCl3) δ-144.47 (dd, J=23.2, 9.1Hz, 2F), -158.29 (t, J=21.0Hz, 1F), -163.08 (ddd, J=24.5, 10.4, 1.4Hz, 2F).

[0240] Compounds 1-21: A colorless liquid was prepared by general method B in 62% yield. 1 H NMR (400MHz, CDCl3) δ3.63(t,J=6.2Hz,2H),2.71(t,J=7.4Hz,2H),2.23(t,J =2.1Hz,3H),1.72–1.61(m,2H),1.59–1.50(m,2H),0.88(s,9H),0.04(s,6H). 13 C NMR (101MHz, CDCl3) 145.1 (dm, J F =244.4Hz), 144.7 (dm, J) F =244.4Hz), 117.8(t,J) F =18.7Hz), 113.4(t,J F =18.8Hz),62.7,32.3,26.1,25.8,22.6,18.5,7.5,-5.2. 19F NMR (377MHz, CDCl3) δ-145.16 (ddd, J=22.1, 12.9, 2.0Hz, 2F), -146.57 (dd, J=22.1, 12.9Hz, 2F).

[0241] Compounds 1-22: Prepared as a yellow liquid by general method B, with a yield of 75%. 1 H NMR(400MHz, CDCl3)δ7.39–7.28(m,8H),7.25-7.21(m,2H),3.55(s,4H),2.62(t ,J=6.9Hz,2H),2.45(t,J=5.9Hz,2H),2.24(t,J=2.0Hz,3H),1.64–1.48(m,4H). 13 C NMR(101MHz,CDCl3)δ145.1(dddd,J F =244.4,21.4,14.2,7.4,3.8Hz),144.8(dddd,J F =244.4,21.5,14.2,7.4,3.8Hz),139.9,128.9,128.3,127.0,117.8(t,J F =18.8Hz), 113.4(t,J F =19.3Hz),58.6,53.1,27.0,26.7–26.5(m),22.6,7.5. 19 F NMR (377MHz, CDCl3) δ-145.07 (dd, J=20.5, 12.9Hz, 2F), -146.44 (dd, J=22.1, 12.9Hz, 2F).

[0242] Compounds 1-23: A colorless liquid was prepared by reacting at 90°C for 12 hours according to general method A, with a yield of 95%. 1 HNMR (400MHz, CDCl3) δ5.69-5.63(m,2H),2.74(t,J=7.3Hz,2H),2.23(s,3H),2.17(d,J=17.1Hz ,1H),2.11–2.01(m,2H),1.82-1.79(m,1H),1.77–1.64(m,1H),1.55(m,3H),1.34–1.20(m,1H). 13 C NMR(101MHz,CDCl3)δ145.1(dm,J F =245.4Hz), 144.6(dm,J) F =245.4Hz),127.2,126.4,118.1(t,JF =18.5Hz), 113.3(t,J F =19.2Hz),36.2,33.4,31.7,28.7,25.2,20.3,7.5. 19 F NMR(377MHz, CDCl3)δ-145.12(dd,J=22.1,12.9Hz,2F),-146.88(dd,J=22.0,12.9Hz,2F).HRMS(EI)calculated for C 15 H 16 F4[M] + m / z 272.1183,found272.1181.IR(neat,cm -1 )3025,2916,1483,1277,1091,1058,880,651.

[0243] Compounds 1-24: Prepared as a yellow liquid by general method B, with a yield of 88%. 1 H NMR (400MHz, CDCl3) δ3.65(t,J=6.5Hz,2H),3.42(t,J=6.6Hz,2H),3.05(t,J=6.5Hz,2H),1.55–1.45(m,2H),1.35–1.23(m,2H),0.88(t,J=7.4Hz,3H). 13 C NMR(101MHz,CDCl3)δ145.8(dm,J F =242.4Hz), 144.2(dm,J F =264.6Hz), 122.9(t,J F =17.2Hz), 121.1(-CF3,J F =275.7Hz),108.5-107.7,71.0,68.4,31.8,24.1,19.4,13.8. 19 F NMR (377MHz, CDCl3) δ-51.57–-59.88(m,3F),-141.19–-142.65(m,4F).

[0244] Compounds 1-25: Prepared by general method B, yielding a yellow liquid in 83% yield. 1 H NMR (400MHz, CDCl3) δ3.52 (t, J = 6.5Hz, 2H), 2.92 (s, 2H), 2.24 (s, 3H), 1.13 (s, 9H). 13 C NMR(101MHz,CDCl3)δ145.2(dm,JF =244.4Hz), 144.8 (dm, J) F =243.4Hz), 114.8(t,J) F =18.6Hz), 113.9(t,J F =19.2Hz),73.3,60.3,27.5,24.8,7.5. 19 F NMR (377MHz, CDCl3) δ-145.18 (dd, J=21.7, 13.0Hz, 2F), -145.85 (dd, J=21.7, 13.0Hz, 2F).

[0245] Compounds 1-26: A yellow liquid was prepared by general method B in 92% yield. 1 H NMR (400MHz, CDCl3) δ3.67(t,J=6.6Hz,2H),3.36–3.16(m,1H),3.03(t,J=6.6Hz,2H),1.84-1.81(m,2H),1.68-1.67(m,2H),1.35–1.10(m,6H). 13 C NMR(101MHz,CDCl3)δ145.8(dm,J F =246.4Hz), 143.9(dm,J) F =261.6Hz), 123.0(t,J F =18.1Hz), 121.1(-CF3,J F =275.7Hz),108.1-107.4(m),77.8,65.4,32.2,25.9,24.7,24.0. 19 F NMR(377MHz, CDCl3)δ-56.29(t,J=22.0Hz,3F),-141.66–-141.58(m,2F),-141.78–-142.44(m,2F).

[0246] Compound 1-27: A colorless liquid was prepared by general method A in 66% yield. 1 H NMR (400MHz, CDCl3) δ2.76–2.57(m,2H),2.23(t,J=2.1Hz,3H),0.97(t,J=7.9Hz,9H),0.87–0.79(m,2H),0.58(q,J=7.9Hz,6H). 13 C NMR(101MHz,CDCl3)δ145.2(dddd,J F =244.4,14.6,7.2,3.8Hz),144.5(dddd,JF =243.4,14.2,7.7,3.8Hz),121.0(t,J F =18.7Hz), 112.9(t,J F =19.3Hz), 17.3, 12.5, 7.4, 3.2. 19 F NMR (377MHz, CDCl3) δ-145.25 (dd, J=22.1, 12.9Hz, 2F), -147.86 (dd, J=22.0, 12.9Hz, 2F).

[0247] Compounds 1-28: A colorless liquid was prepared by general method A in 92% yield. 1 H NMR (400MHz, CDCl3) δ7.56–7.44(m,2H),7.40–7.29(m,3H),2.74–2.56(m,2H),1.14–1.00(m,2H),0.33(s,6H). 13 CNMR(101MHz,CDCl3)δ144.8(dm,J F =244.4Hz), 139.4 (dm, J) F =251.5Hz), 138.1, 137.5 (dm, J) F =252.5Hz),133.6,129.3,128.0,118.1–117.6(m),17.1,16.3,-3.3. 19 F NMR (377MHz, CDCl3) δ-145.23 (dd, J=22.5, 8.3Hz, 2F), -158.93 (t, J=20.8Hz, 1F), -163.14–-163.28 (m, 2F).

[0248] Compounds 1-29: A white solid was prepared by general method A in 99% yield. 1 H NMR (400MHz, CDCl3) δ7.67–7.31(m,10H),2.90–2.68(m,2H),1.19(m,7.0Hz,2H),0.46–0.25(m,6H). 13 C NMR(101MHz,CDCl3)δ144.9(dm,J F =237.4Hz), 143.7 (dm, J) F =232.3Hz),138.2,133.6,130.3,129.2,128.9,128.6,128.0,17.6,16.2,-3.2. 19F NMR (377MHz, CDCl3) δ-145.40 (dd, J=22.3, 12.2Hz, 2F), -145.96 (dd, J=22.3, 12.3Hz, 2F).

[0249] Compounds 1-30: A colorless liquid was prepared by general method B in 69% yield. 1 H NMR (400MHz, CDCl3) δ2.70(t,J=7.5Hz,2H),2.23(t,J=2.1Hz,3H),1.64–1.53(m,2H),0.61–0.45(m,2H),-0.03(s,9H). 13 C NMR(101MHz,CDCl3)δ145.1(dm,J F =244.4Hz), 144.7 (dm, J) F =243.4Hz), 117.9(t,J F =18.8Hz), 113.3(t,J F =19.2Hz),26.5,24.2,16.6,7.5,-1.7. 19 F NMR (377MHz, CDCl3) δ-145.23 (ddd, J=22.2, 12.9, 2.0Hz, 2F), -146.59 (dd, J=22.2, 12.9Hz, 2F).

[0250] Compounds 1-31: A yellow liquid was prepared by general method B in 88% yield. 1 H NMR (400MHz, CDCl3) δ2.69(t,J=7.7Hz,2H),2.56–2.41(m,6H),2.22(s,3H),1.81–1.63(m,2H),0.99(t,J=7.1Hz,6H). 13 C NMR(101MHz,CDCl3)δ145.0(dddd,J F =244.4,21.4,14.2,7.4,3.8Hz),144.6(dddd,J F =244.4,21.5,14.2,7.4,3.8Hz),117.7(t,J F =18.7Hz), 113.3(t,J F =19.2Hz),52.4,46.9,26.9,22.4–20.5(m),11.7,7.3. 19F NMR (377MHz, CDCl3) δ-145.13 (dd, J=22.1, 12.9Hz, 2F), -146.57 (dd, J=22.1, 12.9Hz, 2F).

[0251] Compounds 1-32: A yellow liquid was prepared by general method B in 91% yield. 1 H NMR (400MHz, CDCl3) δ3.66(t,J=8.0Hz,4H),2.83(t,J=7.6Hz,2H),2.41–2.38(m,6H),1.87–1.72(m,2H). 13 CNMR(101MHz,CDCl3)δ145.3(dm,J F =251.4Hz), 144.0(dm,J) F =256.5Hz), 125.6(t,J F =18.4Hz), 121.1(-CF3,J F =275.7Hz),108.4–106.7(m),67.0,58.0,53.7,25.7,21.1. 19 FNMR (377MHz, CDCl3) δ-54.69–-58.45(m,3F),-141.19–-142.08(m,2F),-142.23–-142.99(m,2F).

[0252] Compounds 1-33: A yellow liquid was prepared by general method B in 49% yield. 1 H NMR (400MHz, CDCl3) δ3.64(t,J=6.3Hz,2H),2.77(t,J=7.5Hz,2H),2.21(t,J=2.0Hz,3H),1.93(s,1H),1.87–1.75(m,2H). 13 C NMR(101MHz,CDCl3)δ145.1(dm,J F =244.4Hz), 144.6(dm,J) F =244.4Hz), 117.1(t,J F =18.6Hz), 113.7(t,J) F =19.2Hz),61.9,32.1,19.2-19.0(m),7.4. 19 F NMR (377MHz, CDCl3) δ-144.88 (ddd, J=22.1, 12.8, 1.9Hz, 2F), -146.60 (dd, J=22.0, 12.9Hz, 2F).

[0253] Compounds 1-34: Prepared as white solids by general method B, with a yield of 76%. 1 H NMR (400MHz, CDCl3) δ7.31–7.21(m,3H),7.18-7.16(m,2H),3.07(t,J=8.0Hz,2H),2.90(t,J=8.0Hz,2H). 13 CNMR(101MHz,CDCl3)δ145.3(dm,J F =247.5Hz), 144.0(dm,J F =259.6Hz),139.8,128.8,128.4,126.9,124.8(t,J F =18.3Hz), 121.1(-CF3,J F =274.7Hz),108.8–107.0(m),35.1,25.3. 19 F NMR(377MHz, CDCl3)δ-56.20(t,J=21.6Hz,3F),-141.18–-141.69(m,2F),-142.22–-142.51(m,2F).

[0254] Compounds 1-35: Prepared as a white solid by general method B, in 69% yield. 1 H NMR (400MHz, CDCl3) δ7.09 (d, J = 8.5Hz, 2H), 6.93–6.76 (m, 2H), 3.80 (s, 3H), 3.04 (t, J = 7.8Hz, 2H), 2.86 (t, J = 7.8Hz 2H). 13 C NMR(101MHz,CDCl3)δ158.5,145.3(dm,J F =247.5Hz), 144.1 (dm, J) F =259.6Hz),131.9,129.4,124.9(t,J F =18.4Hz), 121.1(-CF3,J F =276.7Hz),114.1,108.7–106.8(m),55.3,34.2,25.6. 19 F NMR (377MHz, CDCl3) δ-56.20 (td, J=21.6, 2.9Hz, 3F), -141.24–-141.81 (m, 2F), -142.12–-142.59 (m, 2F).

[0255] Compounds 1-36: Prepared as a white solid by general method B, with a yield of 95%. 1 H NMR (400MHz, CDCl3) δ7.17–7.09(m,2H),7.02–6.93(m,2H),3.05(t,J=7.7Hz,2H),2.89(t,J=7.8Hz,2H). 13 CNMR (101MHz, CDCl3) δ 161.9 (d, J F =244.8Hz), 145.4 (dm, J) F =248.5Hz), 144.1(dm,J F =251.6Hz), 135.4(d,J) F =3.3Hz), 129.9(d,J F =8.0Hz), 124.4(t,J F =18.3Hz), 121.1(-CF3,J F =276.7Hz), 115.6(d,J) F =21.3Hz),109.0–107.1(m),34.2,25.4. 19 F NMR (377MHz, CDCl3) δ-56.22(t,J=21.9Hz,3F),-115.78–-116.75(m,1F),-140.69–-141.69(m,2F),-142.01–-142.96(m,2F).

[0256] Compounds 1-37: A white solid was prepared by general method B in 53% yield. 1 H NMR (400MHz, CDCl3) δ7.84–7.78(m,3H),7.64(s,1H),7.54–7.42(m,2H),7.35(dd,J=8.4,1.6Hz,1H),3.22–3.13(m,2H),3.13–3.04(m,2H). 13 C NMR(101MHz,CDCl3)δ145.4(dm,J F =248.5Hz), 144.0(dm,J F =258.6Hz),137.3,133.7,132.5 128.5,127.8,127.6,126.8,126.4,125.8,124.7(t,J F =18.3Hz), 121.1(-CF3,J F =273.7Hz),108.7–107.0(m),35.2,25.2.19 F NMR(377MHz, CDCl3)δ-56.19(t,J=22.0Hz,3F),-139.73–-141.26(m,2F),-141.80–-143.42(m,2F).

[0257] Compounds 1-38: A white solid was prepared by general method B in 89% yield. 1 H NMR (400MHz, CDCl3) δ7.23–7.08(m,4H),3.10–2.98(m,2H),2.95–2.84(m,2H),2.38(s,3H). 13 C NMR(101MHz,CDCl3)δ145.5(dm,J F =248.5Hz), 144.1(dm,J F =260.6Hz),138.1,136.1,130.7 129.0,127.1 126.4,125.0(t,J F =18.4Hz), 121.2(-CF3,J F =275.7Hz),109.2–106.8(m),32.7,24.1,19.0. 19 F NMR(377MHz, CDCl3)δ-56.20(t,J=22.1Hz,3F),-140.14–-141.79(m,2F),-141.91–-143.55(m,2F).

[0258] Compounds 1-39: A colorless liquid was prepared by general method B in 93% yield. 1 H NMR (400MHz, CDCl3) δ7.32–7.26(m,2H),7.24–7.16(m,3H),3.16–2.93(m,3H),1.32(d,J=6.7Hz,3H). 13 C NMR(101MHz,CDCl3)δ145.6(dm,J F =244.4Hz), 144.0(dm,J) F =256.6Hz),145.0,128.8,127.0,126.8,124.30(t,J F =18.2Hz), 121.1(-CF3,J F =274.7Hz),108.5–107.2(m),39.8,32.2,21.0. 19F NMR(377MHz, CDCl3)δ-56.24(t,J=21.7Hz,3F),-141.01–-141.36(m,2F),-141.45–-141.86(m,2F).

[0259] Compounds 1-40: A colorless liquid was prepared by general method B in 73% yield. 1 H NMR (400MHz, CDCl3) δ2.78(dd,J=13.1,5.9Hz,1H),2.58(dd,J=13.1,8.6Hz,1H),1.89–1.72(m,1H),1.46–1.18(m,6H),1.01–0.77(m,6H). 13 C NMR(101MHz,CDCl3)δ145.6(dm,J F =245.4Hz), 144.2(dm,J F =259.6Hz), 125.2(t,J F =18.5Hz), 121.2(-CF3,J F =275.7Hz),108.9–105.5(m),36.7,33.7,30.6,29.4,23.0,19.3,14.1. 19 F NMR(377MHz, CDCl3)δ-56.40(t,J=21.5Hz,3F),-141.18–-141.64(m,2F),-141.86–-142.31(m,2F).

[0260] Compounds 1-41: A colorless liquid was prepared by general method B in 93% yield. 1 H NMR (400MHz, CDCl3) δ7.31–7.22(m,2H),7.22–7.10(m,3H),2.79(dd,J=13.2,5.9Hz,1H),2.71–2.53(m,3H),2.26–2.08(m,1H),0.90(d,J=6.6Hz,3H). 13 C NMR(101MHz,CDCl3)δ145.4(dm,J F =245.4Hz), 143.9(dm,J) F =259.6Hz),140.0,129.1,128.5,126.4,121.1(-CF3,J F =271.7Hz),108.8–106.6(m),43.6,35.2,30.4,19.4. 19F NMR(377MHz, CDCl3)δ-56.35(t,J=22.0Hz,3F),-140.79–-141.31(m,2F),-141.53–-142.29(m,2F).

[0261] Compounds 1-42: A colorless liquid was prepared by general method B in 83% yield. 1 H NMR (400MHz, CDCl3) δ2.98–2.75(m,1H),2.56(dd,J=12.1,10.7Hz,1H),1.85–1.63(m,6H),1.32–1.05(m,6H),0.82(d,J=6.9Hz,3H). 13 C NMR(101MHz,CDCl3)δ145.6(dm,J F =245.4Hz), 144.2(dm,J F =256.5Hz), 125.9(t,J F =18.3Hz), 121.2(-CF3,J F =275.7Hz),108.5–106.5(m),43.2,38.9,30.6,28.9,27.9,26.9,26.9,26.8,15.7. 19 F NMR(377MHz, CDCl3)δ-56.23(t,J=21.8Hz,3F),-141.15–-141.66(m,2F),-141.74–-142.15(m,2F).

[0262] Compounds 1-43: A colorless liquid was prepared by general method B in 89% yield. 1 H NMR (400MHz, CDCl3) δ7.56–7.47(m,2H),7.43–7.32(m,3H),2.94–2.79(m,1H),2.56(dd, J=12.6,12.1Hz,1H),1.35–1.23(m,1H),0.96(d,J=7.4Hz,3H),0.39(s,3H),0.35(s,3H). 13 C NMR(101MHz,CDCl3)δ145.4(dm,J F =253.5Hz), 144.0(dm,J) F =252.6Hz),137.2,133.9,129.4,128.0,126.1(t,J F =18.3Hz), 121.1(-CF3,J F=275.7Hz),108.7–105.7(m),25.9,20.3,14.2,-4.5,-6.1. 19 F NMR (377MHz, CDCl3) δ-56.25 (t, J = 21.7Hz, 3F), -141.34–-141.79 (m, 2F), -141.83–-142.30 (m, 2F).

[0263] Compounds 1-44: A colorless liquid was prepared by general method B in 89% yield. 1 H NMR (400MHz, CDCl3) δ2.66 (d, J = 7.0Hz, 2H), 1.77–1.55 (m, 6H), 1.28–1.13 (m, 3H), 1.10–1.08 (dd, 2H). 13 C NMR(101MHz,CDCl3)δ145.5(dm,J F =245.4Hz), 144.1 (dm, J) F =259.6Hz), 124.8(t,J F =18.7Hz), 121.2(-CF3,J F =275.7Hz),109.2–106.3(m),38.2,33.0,30.8,26.3,26.2. 19 FNMR(377MHz, CDCl3)δ-54.22–-58.52(m,3F),-140.46–-141.42(m,2F),-141.70–-142.55(m,2F).

[0264] Compounds 1-45: A colorless liquid was prepared by general method B in 77% yield. 1 H NMR (500MHz, CDCl3) δ3.06–2.92(m,1H),2.49(s,1H),2.36(s,1H),2.21(t,J=2.0H z,3H),1.88–1.78(m,1H),1.76–1.65(m,2H),1.64–1.55(m,2H),1.39–1.23(m,3H). 13 C NMR(126MHz,CDCl3)δ145.4(dm,J F =248.2Hz), 144.8 (dm, J) F =243.2Hz), 122.0(t,J F =15.5Hz), 112.9(t,J F =19.4Hz), 41.7(t,J F=2.2Hz), 39.3(t,J F =1.6Hz), 39.0(t,J F =2.1Hz), 37.5(t,J F =3.9Hz), 36.7, 31.3, 28.5, 7.4. 19 F NMR (471MHz, CDCl3) δ-143.75 (dd, J=21.5, 12.0Hz, 2F), -145.35 (dd, J=21.6, 11.9Hz, 2F).

[0265] Example 3: Synthesis of Alkyl Polyfluoroaromatic Compounds

[0266] The structures of compounds I-2, I-3, I-4, I-5, I-6, I-7, and I-8 in the following examples are shown below:

[0267]

[0268] In step 1, under nitrogen-filled glove box, compound I-2 (8.1 mg, 0.01 mmol, 2 mol%), potassium tert-butoxide (2.2 mg, 0.02 mmol, 4 mol%), and Ni(cod)2 (2.8 mg, 0.01 mmol, 2 mol%) were added to an 8 mL vial, followed by 1 mL of n-heptane. The mixture was stirred at room temperature for 8 hours. Then, 2,3,5,6-tetrafluorotoluene (82.1 mg, 0.5 mmol, 1.0 equiv) and 1-octene (112.2 mg, 1.0 mmol, 2.0 equiv) were added. The mixture was then removed from the glove box and reacted at 130 °C for 12 hours. After the reaction, the crude system was concentrated by diatomaceous earth filtration. 1,1,2,2-tetrachloroethane was added as an internal standard, and the product was analyzed by 1H NMR spectroscopy. The NMR yield was 94%, and the regioselectivity was >99 / 1.

[0269] Sequence 2: In a nitrogen-filled glove box, compound I-3 (8.3 mg, 0.01 mmol, 2 mol%), potassium tert-butoxide (2.2 mg, 0.02 mmol, 4 mol%), and Ni(cod)₂ (2.8 mg, 0.01 mmol, 2 mol%) were added to an 8 mL vial, followed by 1 mL of n-heptane. The mixture was stirred at room temperature for 8 hours. Then, 2,3,5,6-tetrafluorotoluene (82.1 mg, 0.5 mmol, 1.0 equiv) and 1-octene (112.2 mg, 1.0 mmol, 2.0 equiv) were added. The mixture was then removed from the glove box and reacted at 130 °C for 12 hours. After the reaction, the crude system was concentrated by diatomaceous earth filtration. 1,1,2,2-tetrachloroethane was added as an internal standard, and the product was analyzed by 1H NMR spectroscopy. The NMR yield was 77%, and the regioselectivity was >99 / 1.

[0270] Sequence 3: In a nitrogen-filled glove box, compound I-4 (10.8 mg, 0.01 mmol, 2 mol%), potassium tert-butoxide (2.2 mg, 0.02 mmol, 4 mol%), and Ni(cod)₂ (2.8 mg, 0.01 mmol, 2 mol%) were added to an 8 mL vial, followed by 1 mL of n-heptane. The mixture was stirred at room temperature for 8 hours. Then, 2,3,5,6-tetrafluorotoluene (82.1 mg, 0.5 mmol, 1.0 equiv) and 1-octene (112.2 mg, 1.0 mmol, 2.0 equiv) were added. The mixture was then removed from the glove box and reacted at 130 °C for 12 hours. After the reaction, the crude system was concentrated by diatomaceous earth filtration. 1,1,2,2-tetrachloroethane was added as an internal standard, and the product was analyzed by 1H NMR spectroscopy. The NMR yield was 86%, and the regioselectivity was >99 / 1.

[0271] No. 4: In a nitrogen-filled glove box, compound I-5 (9.1 mg, 0.01 mmol, 2 mol%), potassium tert-butoxide (2.2 mg, 0.02 mmol, 4 mol%), and Ni(cod)₂ (2.8 mg, 0.01 mmol, 2 mol%) were added to an 8 mL vial, followed by 1 mL of n-heptane. The mixture was stirred at room temperature for 8 hours. Then, 2,3,5,6-tetrafluorotoluene (82.1 mg, 0.5 mmol, 1.0 equiv) and 1-octene (112.2 mg, 1.0 mmol, 2.0 equiv) were added. The mixture was then removed from the glove box and reacted at 130 °C for 12 hours. After the reaction, the crude system was concentrated by diatomaceous earth filtration. 1,1,2,2-tetrachloroethane was added as an internal standard, and the product was analyzed by 1H NMR spectroscopy. The NMR yield was 99%, and the regioselectivity was >99 / 1.

[0272] No. 5: In a nitrogen-filled glove box, compound I-6 (9.7 mg, 0.01 mmol, 2 mol%), potassium tert-butoxide (2.2 mg, 0.02 mmol, 4 mol%), and Ni(cod)₂ (2.8 mg, 0.01 mmol, 2 mol%) were added to an 8 mL vial, followed by 1 mL of n-heptane. The mixture was stirred at room temperature for 8 hours. Then, 2,3,5,6-tetrafluorotoluene (82.1 mg, 0.5 mmol, 1.0 equiv) and 1-octene (112.2 mg, 1.0 mmol, 2.0 equiv) were added. The mixture was then removed from the glove box and reacted at 130 °C for 12 hours. After the reaction, the crude system was concentrated by diatomaceous earth filtration. 1,1,2,2-tetrachloroethane was added as an internal standard, and the product was analyzed by 1H NMR spectroscopy. The NMR yield was 50%, and the regioselectivity was >99 / 1.

[0273] No. 6: In a nitrogen-filled glove box, compound I-7 (9.7 mg, 0.01 mmol, 2 mol%), potassium tert-butoxide (2.2 mg, 0.02 mmol, 4 mol%), and Ni(cod)₂ (2.8 mg, 0.01 mmol, 2 mol%) were added to an 8 mL vial, followed by 1 mL of n-heptane. The mixture was stirred at room temperature for 8 hours. Then, 2,3,5,6-tetrafluorotoluene (82.1 mg, 0.5 mmol, 1.0 equiv) and 1-octene (112.2 mg, 1.0 mmol, 2.0 equiv) were added. The mixture was then removed from the glove box and reacted at 130 °C for 12 hours. After the reaction, the crude system was concentrated by diatomaceous earth filtration. 1,1,2,2-tetrachloroethane was added as an internal standard, and the product was analyzed by 1H NMR spectroscopy. The NMR yield was 96%, and the regioselectivity was >99 / 1.

[0274] No. 7: In a nitrogen-filled glove box, compound I-8 (10.5 mg, 0.01 mmol, 2 mol%), potassium tert-butoxide (2.2 mg, 0.02 mmol, 4 mol%), and Ni(cod)₂ (2.8 mg, 0.01 mmol, 2 mol%) were added to an 8 mL vial, followed by 1 mL of n-heptane. The mixture was stirred at room temperature for 8 hours. Then, 2,3,5,6-tetrafluorotoluene (82.1 mg, 0.5 mmol, 1.0 equiv) and 1-octene (112.2 mg, 1.0 mmol, 2.0 equiv) were added. The mixture was then removed from the glove box and reacted at 130 °C for 12 hours. After the reaction, the crude system was concentrated by diatomaceous earth filtration. 1,1,2,2-tetrachloroethane was added as an internal standard, and the product was analyzed by 1H NMR spectroscopy. The NMR yield was 69%, and the regioselectivity was >99 / 1.

[0275] Example 4: Synthesis of olefin and polyfluoroaromatic copolymers

[0276] or,

[0277]

[0278] General Method A': In a nitrogen-filled glove box, add compound I (21.5 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (5.6 mg, 0.05 mmol, 10 mol%), and Ni(cod)₂ (6.9 mg, 0.025 mmol, 5 mol%) to an 8 mL vial, followed by 0.50 mL of n-heptane. Stir at room temperature for 8 hours. Then add compound V or VI (0.50 mmol) and compound VII (0.50 mmol). Remove from the glove box and react at 130 °C for 48 hours. After the reaction is complete, dissolve the reaction system in 5 mL of dichloromethane, add dropwise to 100 mL of methanol to precipitate, and finally centrifuge and vacuum dry to obtain the product.

[0279] General Method B': In a nitrogen-filled glove box, add compound I (21.5 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (5.6 mg, 0.05 mmol, 10 mol%), and Ni(cod)₂ (6.9 mg, 0.025 mmol, 5 mol%) to an 8 mL vial, followed by 0.10 mL of n-heptane. Stir at room temperature for 8 hours. Then add compound V or VI (0.50 mmol) and compound VII (0.50 mmol), remove from the glove box, and react at 130 °C for 48 hours. After the reaction is complete, dissolve the reaction system in 5 mL of dichloromethane, add dropwise to 100 mL of methanol to precipitate, and finally centrifuge and vacuum dry to obtain the product.

[0280] Polymer 2-1: A white solid was prepared according to general method A', with a yield of 89%, a number-average molecular weight of 3.4 kg / mol, and a molecular weight distribution of 1.38.

[0281] Polymer 2-2: A white solid was prepared according to general method B' with a yield of 99%, a number-average molecular weight of 6.0 kg / mol, and a molecular weight distribution of 1.70. 1 H NMR (400MHz, CDCl3) δ2.79 (t, J = 7.7Hz, 4H), 1.66 (s, 4H), 1.39 (s, 8H). 19 F NMR (377MHz, CDCl3) δ-139.87--139.78(m,4F),-144.19--144.14(m,4F). 13 CNMR(126MHz,CDCl3)δ145.1(dm,J F=243Hz), 143.9(dm,J F =252Hz), 123.0(t,J F =18.6Hz), 104.9(t,J F =17.3Hz),29.4,29.3,29.2,23.2.

[0282] Polymer 2-3: A white solid was prepared according to general method B', with a yield of 74%, a number-average molecular weight of 4.3 kg / mol, and a molecular weight distribution of 1.49. 1 H NMR (400MHz, CDCl3) δ2.79 (t, J = 7.8Hz, 4H), 1.67–1.63 (m, 4H), 1.44–1.24 (m, 12H). 19 F NMR (377MHz, CDCl3) δ-139.52--140.12(m,4F),-144.17--144.23(m,4F). 13 C NMR(126MHz,CDCl3)δ145.1(t,J F =244Hz), 144.1(dm,J F =251Hz), 107.7(t,J F =21.9Hz), 104.7(t,J F =16.4Hz),29.6,29.4,29.4,29.3,23.3.

[0283] Polymer 2-4: A white solid was prepared according to general method B', with a yield of 87%, a number-average molecular weight of 19.1 kg / mol, and a molecular weight distribution of 1.81. 1 H NMR (400MHz, CDCl3) δ2.81 (t, J = 8.7Hz, 4H), 1.09–0.85 (m, 4H), 0.16 (s, 6H). 19 F NMR (377MHz, CDCl3) δ-139.63 (dd, J=17.3, 9.5Hz, 4F), -145.22 (dd, J=21.0, 10.2Hz, 4F). 13 C NMR(126MHz,CDCl3)δ144.6(dm,J F =246Hz), 144.0(dm,J F =252Hz), 125.3(t,J F =18.4Hz), 104.72(t,J F =16.6Hz), 17.6, 15.5, -3.9.

[0284] Polymer 2-5: A white solid was prepared according to general method B', with a yield of 56%, a number-average molecular weight of 3.0 kg / mol, and a molecular weight distribution of 1.16. 1 H NMR (400MHz, CDCl3) δ3.05–2.42(m,4H),1.85(s,2H),1.59–1.26(m,4H),0.95(d,J=6.6Hz,6H). 19 F NMR(377MHz, CDCl3)δ-139.38–-139.95(m,4F),-142.74(s,4F). 13 C NMR(126MHz,CDCl3)δ145.3(dm,J F =246Hz), 144.0(dm,J F =252Hz), 122.0(t,J F =18.5Hz), 107.7(t,J) F =22.4Hz),34.2,34.2,33.8,33.8,30.7,30.4,19.5,19.3.

[0285] Polymer 2-6: A white solid was prepared according to general method B', with a yield of 87%, a number-average molecular weight of 21.8 kg / mol, and a molecular weight distribution of 1.57. 1 H NMR (400MHz, CDCl3) δ7.52(s,4H),2.97–2.58(m,4H),1.19–1.07(m,4H),0.34(s,12H). 19 F NMR (377MHz, CDCl3) δ-139.62–-139.90(m,4F),-144.80–-145.07(m,4F). 13 C NMR(126MHz,CDCl3)δ144.8(dm,J F =246Hz), 143.9(dm,J F =251Hz),139.1,133.0,125.3(t,J F =18.4Hz), 104.6(t,J F =17.1Hz), 17.8, 16.1, -3.3.

[0286] Polymer 2-7: Prepared according to general method B', a white solid with a yield of 95%, insoluble.

[0287] Polymer 2-8: Prepared according to general method B', a white solid with a yield of 96%, insoluble.

[0288] Polymer 2-9: A white solid was prepared according to general method B', with a yield of 69%, a number-average molecular weight of 3.1 kg / mol, and a molecular weight distribution of 1.21. 1 H NMR (400MHz, CDCl3) δ2.67 (t, J = 7.5Hz, 4H), 1.56 (t, J = 7.3Hz, 4H), 1.31 (s, 8H). 19 F NMR (377MHz, CDCl3) δ-146.41. 13 C NMR(126MHz,CDCl3)δ144.7(dm,J F =247Hz),118.7–117.3(m),103.4(t,J F =22.5Hz),29.4,29.3,29.3,22.8.

[0289] Polymer 2-10: A white solid was prepared according to general method B' with a yield of 97%, a number-average molecular weight of 5.9 kg / mol, and a molecular weight distribution of 1.26. 1 H NMR (400MHz, CDCl3) δ2.79 (t, J = 7.7Hz, 4H), 1.66 (s, 4H), 1.39 (s, 8H). 19 F NMR (377MHz, CDCl3) δ-139.87--139.78(m,4F),-144.19--144.14(m,4F). 13 CNMR(126MHz, CDCl3)δ29.4,29.3,29.2,23.2,123.0(t,J=18.6Hz),104.9(t,J=17.3Hz),143.9(dm,J F =252Hz), 145.1(dm,J F =243Hz).

[0290] Polymer 2-11: A white solid was prepared according to general method B', with a yield of 83%, a number-average molecular weight of 6.7 kg / mol, and a molecular weight distribution of 1.08. 1 H NMR (400MHz, CDCl3) δ7.49 (s, 4H), 2.65 (br, 4H), 1.06 (br, 4H), 0.30 (s, 12H). 19 F NMR (377MHz, CDCl3) δ-147.06 (s, 4F). 13 C NMR(126MHz,CDCl3)δ144.4(dm,J F=256Hz),139.3,133.0,120.2,17.3,16.2,-3.2.

[0291] Polymer 2-12: A white solid was prepared according to general method B', with a yield of 75%, a number-average molecular weight of 3.4 kg / mol, and a molecular weight distribution of 1.24. 1 H NMR (400MHz, CDCl3) δ2.67 (t, J = 7.6Hz, 4H), 1.63–1.53 (m, 4H), 1.34–1.27 (m, 12H). 19 F NMR(377MHz, CDCl3)δ-146.44(s,4F). 13 C NMR(126MHz,CDCl3)δ144.7(dm,J F =247Hz),118.0–118.0(m),103.41(t,J F =22.7Hz),29.6,29.5,29.4,29.3,22.8.

[0292] Polymer 2-13: A white solid was prepared according to general method A', with a yield of 69%, a number-average molecular weight of 6.2 kg / mol, and a molecular weight distribution of 2.62.

[0293] Example 5: Synthesis of copolymers of alkynes and polyfluoroaromatics

[0294] or,

[0295]

[0296] General Method C': In a nitrogen-filled glove box, add compound I (21.5 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (5.6 mg, 0.05 mmol, 10 mol%), and Ni(cod)₂ (6.9 mg, 0.025 mmol, 5 mol%) to an 8 mL vial, followed by 0.25 mL of n-heptane. Stir at room temperature for 8 hours. Then add compound V or VI (0.50 mmol) and compound IX (0.50 mmol), remove from the glove box, and react at 100 °C for 12 hours. After the reaction is complete, dissolve the reaction system in 5 mL of dichloromethane, add dropwise to 100 mL of methanol to precipitate, and finally centrifuge and vacuum dry to obtain the product.

[0297] Polymer 3-1: A yellow solid was prepared according to general method C' with a yield of 89%, a number-average molecular weight of 16.4 kg / mol, and a molecular weight distribution of 2.96. 1H NMR (400MHz, CDCl3) δ7.30 (s, 4H), 6.17 (s, 2H), 0.03 (s, 18H). 19 F NMR (377MHz, CDCl3) δ-138.71–-138.63(m,4F),-140.97–-141.34(m,4F). 13 C NMR(126MHz,CDCl3)δ144.2(dm,J F =252Hz), 143.7 (dm, J) F =244Hz),142.3,141.7,140.7,128.5,126.49(t,J F =18.3Hz), 106.0(t,J F =20.2Hz), 0.13.IR(neat,cm -1 )2957,2900,1590,1463,973,866,837,722.

[0298] Polymer 3-2: A brown solid was prepared according to general method C' with a yield of 94%, a number-average molecular weight of 16.3 kg / mol, and a molecular weight distribution of 4.37. 1 H NMR (400MHz, CDCl3) δ6.90(s,2H),6.16(s,2H),0.15(s,18H). 19 F NMR(377MHz, CDCl3)δ-138.14–-138.50(m,4F),-141.0–-141.09(m,4F). 13 C NMR(126MHz,CDCl3)δ144.0(dm,J F =252Hz), 143.6(dm,J F =250Hz),134.4,127.7,126.1(t,J F =18.1Hz), 106.3(t,J F =16.4Hz), -0.0.

[0299] Polymer 3-3: A light yellow solid was prepared according to the general method C', with a yield of 91%, a number-average molecular weight of 15.3 kg / mol, and a molecular weight distribution of 2.76. 1 H NMR (400MHz, CDCl3)7.34(t,J=7.9Hz,1H),7.26(s,2H),6.19(s,2H),-0.08(s,18H). 19F NMR (377MHz, CDCl3) δ-138.74–-138.83(m,4F),-140.79–-141.12(m,4F). 13 C NMR(126MHz,CDCl3)δ144.0(dm,J F =253Hz), 143.7(dm,J F =249Hz),142.2,141.9,140.8,126.4(t,J F =18.1Hz), 106.0(t,J F =17.0Hz). -0.3.

[0300] Polymer 3-4: A brown solid was prepared according to general method C', with a yield of 75%, a number-average molecular weight of 6.4 kg / mol, and a molecular weight distribution of 1.39. 1 H NMR (400MHz, CDCl3) δ6.84(s,2H),6.07(s,2H),0.12(s,18H). 19 F NMR(377MHz, CDCl3)δ-142.37(s,4F). 13 C NMR(126MHz,CDCl3)δ144.0(dm,J F =252Hz), 143.5(dm,J F =252Hz),143.4,142.3,135.0,127.3,123.3,105.0(t,J F =22.6Hz), 0.0.

[0301] Polymer 3-5: A yellow solid was prepared according to general method C', with a yield of 93%, a number-average molecular weight of 26.2 kg / mol, and a molecular weight distribution of 3.96. 1 H NMR (400MHz, CDCl3) δ7.64(d,J=7.8Hz,2H),7.31(s,2H),7.19(d,J=7.9Hz,2H),6.20(s,2H),1.99 (s,4H),1.19–1.13(m,4H),1.10–0.94(m,16H),0.77(t,J=7.1Hz,6H),0.59(s,4H),0.01(s,18H). 19 F NMR(377MHz, CDCl3)δ-138.86(s,2F),-141.30(s,2F). 13 C NMR(126MHz,CDCl3)δ151.0,144.2(dm,J F=253Hz), 143.7(dm,J F =244Hz),143.7,140.8,140.2,127.4,126.74(t,J F =17.9Hz),123.3,119.7,105.8,55.6,40.7,31.8,30.1,29.4,29.3,23.9,22.7,14.1,0.2.

[0302] Polymer 3-6: A yellow solid was prepared according to general method C', with a yield of 60%, a number-average molecular weight of 11.9 kg / mol, and a molecular weight distribution of 1.76. 1 H NMR (400MHz, CDCl3) δ7.60(d,J=7.9Hz,2H),7.28(s,2H),7.14(d,J=7.8Hz,2H),6.10(s,2H),1.96 (s,4H),1.19(q,J=7.2Hz,4H),1.13–0.95(m,16H),0.83–0.79(m,6H),0.58(s,4H),0.00(s,18H). 19 F NMR (377MHz, CDCl3) δ-142.86 (s, 4F). 13 CNMR(126MHz,CDCl3)δ150.8,144.3,143.7(dm,J F =249Hz),140.7,139.8,127.3,123.6,123.3,119.5,55.5,40.8,31.9,30.1,29.4,29.3,23.8,22.7,14.2,0.2.

Claims

1. A compound I or compound II, the structure of which is shown below: in, Ar 1 Ar 2 Ar 3 and Ar 4 Independently for C 6-10 Aromatic rings may be surrounded by one, two, or three R groups. Ar Replacement C 6-10 Aromatic rings; R Ar Independently for C 1-6 Alkyl or -OC 1-6 alkyl; X - For Cl - ,Br - I - Or BF4 - .

2. The compound I or compound II as described in claim 1, characterized in that, It meets one or more of the following conditions: (1)Ar 1 Ar 2 Ar 3 Japanese Ar 4 Homologous; (2)X - For Cl - .

3. The compound I or compound II as described in claim 1, characterized in that, It meets one or more of the following conditions: (1)Ar 1 Ar 2 Ar 3 and Ar 4 In, the C 6-10 Aromatic rings and the aforementioned rings are composed of one, two, or three R groups. Ar Replacement C 6-10 C in the aromatic ring 6-10 The aromatic ring can be either a benzene ring or a naphthalene ring independently; (2)R Ar In, the C 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; (3)R Ar In the context, the -OC 1-6 The alkyl group is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy.

4. The compound I or compound II as described in claim 3, characterized in that, It meets one or more of the following conditions: (1)R Ar In, the C 1-6 The alkyl group is independently methyl or tert-butyl; (2)R Ar In the context, the -OC 1-6 The alkyl group is independently methoxy.

5. The compound I or compound II as described in claim 1, characterized in that, R Ar It can be methyl, tert-butyl, or methoxy on its own.

6. The compound I or compound II as described in claim 1, characterized in that, Ar 1 Ar 2 Ar 3 and Ar 4 Independently 7. Compound I or Compound II as described in claim 6, characterized in that, Ar 1 Ar 2 Ar 3 and Ar 4 Same, for 8. The compound I or compound II as described in claim 1, characterized in that, Compound I or Compound II has the following structure:

9. A method for preparing compound I or compound II as described in any one of claims 1-8, characterized in that, It includes the following steps: reacting compound 0 with chloromethyl ethyl ether to obtain compound I; Alternatively, in a solvent, compound I reacts in the presence of a base to give compound II; 10. The method for preparing compound I or compound II as described in claim 9, characterized in that, The preparation method satisfies one or more of the following conditions: (1) In the preparation method of compound I, the reaction temperature is 90-110℃; (2) In the preparation method of compound I, the reaction time is 8-14 h; (3) The molar ratio of compound 0 to chloromethyl ethyl ether is 1:10-30; (4) In the preparation method of compound II, the base is an organic base; (5) In the preparation method of compound II, the solvent is an ether solvent; (6) In the preparation method of compound II, the molar ratio of compound I to the base is 1:1-2.

11. The method for preparing compound I or compound II as described in claim 10, characterized in that, The preparation method satisfies one or more of the following conditions: (1) In the preparation method of compound I, the reaction temperature is 100℃; (2) In the preparation method of compound I, the reaction time is 12h; (3) The molar ratio of compound 0 to chloromethyl ethyl ether is 1:20; (4) In the preparation method of compound II, the base is an alkali metal salt of an alcohol; (5) In the preparation method of compound II, the solvent is a cyclic ether solvent; (6) In the preparation method of compound II, the molar ratio of compound I to the base is 1:1.

5.

12. The method for preparing compound I or compound II as described in claim 11, characterized in that, The preparation method satisfies one or more of the following conditions: (1) In the preparation method of compound II, the base is potassium tert-butoxide; (2) In the preparation method of compound II, the solvent is tetrahydrofuran.

13. A method for preparing compound A, characterized in that, It includes the following steps: In a solvent, in system 1 or system 2, compound III and compound IV are reacted as shown below; system 1 consists of compound I', 1,5-cyclooctadiene nickel, and a base; system 2 consists of compound II' and 1,5-cyclooctadiene nickel. The structure of compound I' or II' is as follows: Ar 1 Ar 2 Ar 3 Ar 4 and X - The definition is as described in any one of claims 1-8; R 0 Independently for C 1-6 Alkyl or -OC 1-6 alkyl; Cy A is C 6-10 Aromatic rings or 5-16 heterocyclic aromatic rings; R 1 F and C independently 1-20 Alkyl, -OC 1-20 Alkyl, C 6-10 Argan, Or by 1, 2 or 3 Rs 1-2 Replacement C 1-20 alkyl; p is 1, 2, 3 or 4; R 1-1 C 1-6 alkyl; R 1-2 Halogens are independent of each other; R 2 Independently H or C 1-20 alkyl; R 3 Independently for C 1-20 Alkyl, C 3-20 cycloalkyl, C 3-20 Cycloalkenyl, -OC 1-20 Alkyl, -OC 3-20 cycloalkyl, C 6-10 Aromatic rings, -SiR a R b R c , by 1, 2 or 3 R 2-1 Replacement C 1-20 Alkyl groups or those with one, two, or three R groups 2-7 Replacement C 6-10 Aromatic rings; R 2-1 Independently -OH, 5- to 16-membered heterocyclic alkyl, C 6-10 Aromatic rings, 5-16 member heteroaryl rings, -SiR a R b R c -NR d R e -O-SiR f R g R i Or by 1, 2 or 3 R 2-1-1 Replacement C 6-10 Aromatic rings; R 2-7 Independent of halogen, C 1-20 Alkyl or -OC 1-20 alkyl; R a R b and R c Independently for C 1-20 Alkyl or C 6-10 Aromatic rings; R d and R e Independently for C 1-20 Alkyl or -C 1-6 Alkylene-C 6-10 Aromatic rings; R f R g and R i Independently for C 1-20 alkyl; R 2-1-1 Independently for -OC 1-20 alkyl; or R 2 and R 3 The carbon atom attached to it forms C 3-8 cycloalkyl or C 3-8 Bridged cycloalkyl; The 5- to 16-membered heteroaromatic rings are independently N-type heteroatoms with a single heteroatom. The 5- to 16-membered heterocyclic alkyl group is independently selected from one or two types of heteroatoms, namely N and O; the number of heteroatoms is one or two 5- to 16-membered heterocyclic alkyl groups.

14. The method for preparing compound A according to claim 13, characterized in that, It meets one or more of the following conditions: (1) The reaction was carried out under nitrogen protection; (2) The alkali is an organic alkali; (3) The solvent is a hydrocarbon solvent; (4) The molar ratio of compound III to compound I is 1:0.01-0.07; (5) The molar ratio of compound III to compound IV is 1:0.2-3; (6) The molar ratio of compound III to the base is 1:0.02-0.2; (7) The molar ratio of compound III to nickel 1,5-cyclooctadiene is 1:0.02-0.1; (8) The reaction temperature of the above reaction is 100-150℃; (9) The reaction time is 8-14 hours.

15. The method for preparing compound A according to claim 14, characterized in that, It meets one or more of the following conditions: (1) The base is an alkali metal salt of an alcohol; (2) The solvent is an alkane solvent; (3) The molar ratio of compound III to compound I is 1:0.02 or 1:0.05; (4) The molar ratio of compound III to compound IV is 1:0.1:0.3 or 1:2; (5) The molar ratio of compound III to the base is 1:0.04 or 1:0.1; (6) The molar ratio of compound III to nickel 1,5-cyclooctadiene is 1:0.02 or 1:0.05; (7) The reaction temperature of the above reaction is 130℃; (8) The reaction time is 12 hours.

16. The method for preparing compound A according to claim 15, characterized in that, It meets one or more of the following conditions: (1) The base is potassium tert-butoxide; (2) The solvent is n-heptane.

17. The method for preparing compound A according to any one of claims 13-16, characterized in that, It meets one or more of the following conditions: (1)R 0 In, the C 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; (2)R 0 In the context, the -OC 1-6 The alkyl group is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; (3) When Cy A is C 6-10 When aromatic rings are used, the C 6-10 The aromatic ring is a benzene ring; (4) When Cy A is a 5- to 16-membered heteroaryl ring, the 5- to 16-membered heteroaryl ring is a 5- to 7-membered heteroaryl ring; (5)R 1 In, the C 1-20 Alkyl groups and those with one, two, or three R groups 1-2 Replacement C 1-20 C in alkyl 1-20 Alkyl groups are independently C 1-10 alkyl; (6)R 1 In the context, the -OC 1-20 Alkyl group is -OC 1-10 alkyl; (7)R 1 In, the C 6-10 The aromatic ring is a benzene ring; (8)R 1-1 In, the C 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; (9)R 1-2 In this context, the halogen is independently F, Cl, Br, or I; (10)R 2 In, the C 1-20 Alkyl groups are independently C 1-10 alkyl; (11)R 3 In, the C 1-20 Alkyl groups and those with one, two, or three R groups 2-1 Replacement C 1-20 C in alkyl 1-20 Alkyl groups are independently C 1-10 alkyl; (12)R 3 In, the C 3-20 Cycloalkyl group is C 3-10 cycloalkyl; (13)R 3 In, the C 3-20 The cycloalkenyl group is C 3-10 Cycloalkenyl; (14)R 3 In the context, the -OC 1-20 Alkyl group is -OC 1-10 alkyl; (15)R 3 In the context, the -OC 3-20 Cycloalkyl group is -OC 3-10 cycloalkyl; (16)R 3 In, the C 6-10 Aromatic rings and the aforementioned rings are composed of one, two, or three R groups. 2-7 Replacement C 6-10 C in the aromatic ring 6-10 The aromatic ring can be either a benzene ring or a naphthalene ring independently; (17)R 2-7 In this context, the halogen is independently F, Cl, Br, or I; (18)R 2-7 In, the C 1-20 Alkyl groups are independently C 1-10 alkyl; (19)R 2-7 In the context, the -OC 1-20 Alkyl groups are independently -OC 1-10 alkyl; (20)R 2-1 In, the C 6-10 Aromatic rings and 1, 2 or 3 R 2-1-1 Replacement C 6-10 C in the aromatic ring 6-10 The aromatic ring is a benzene ring; (21)R 2-1 In this context, the 5- to 16-membered heteroaromatic rings are independently 5- to 13-membered heteroaromatic rings with N as the heteroatom type and one heteroatom. (22)R 2-1 In this context, the 5- to 16-membered heterocyclic alkyl group is independently selected from one or two heteroatom types selected from N and O; the number of heteroatoms is one or two; and it is a 5- to 7-membered heterocyclic alkyl group. (23)R a R b and R c In, the C 1-20 Alkyl groups are independently C 1-10 alkyl; (24)R a R b and R c In, the C 6-10 The aromatic ring is a benzene ring; (25)R d and R e In, the C 1-20 Alkyl groups are independently C 1-10 alkyl; (26)R d and R e In the context, the -C 1-6 Alkylene-C 6-10 The aromatic ring is independently -C 1-3 Alkylene-C 6-10 Aromatic rings; (27)R f R g and R i In, the C 1-20 Alkyl groups are independently C 1-10 alkyl; (28)R 2-1-1 In the context, the -OC 1-20 Alkyl groups are independently -OC 1-10 alkyl; (29) When R 2 and R 3 The carbon atom attached to it forms C 3-8 When cycloalkyl, the C 3-8 Cycloalkyl group is C 3-6 Cycloalkyl.

18. The method for preparing compound A according to claim 17, characterized in that, It meets one or more of the following conditions: (1)R 0 In, the C 1-6 The alkyl group is independently methyl or tert-butyl; (2)R 0 In the context, the -OC 1-6 The alkyl group is independently a methoxy group; (3) When Cy A is a 5- to 16-membered heteroaryl ring, the 5- to 16-membered heteroaryl ring is pyridine; (4)R 1 In, the C 1-20 Alkyl groups and those with one, two, or three R groups 1-2 Replacement C 1-20 C in alkyl 1-20 Alkyl groups are independently C 1-6 alkyl; (5)R 1 In the context, the -OC 1-20 Alkyl group is -OC 1-6 alkyl; (6)R 1-1 In, the C 1-6 Alkyl groups are independently methyl groups; (7)R 1-2 In this context, the halogen is independently F; (8)R 2 In, the C 1-20 Alkyl groups are independently C 1-6 alkyl; (9)R 3 In, the C 1-20 Alkyl groups and those with one, two, or three R groups 2-1 Replacement C 1-20 C in alkyl 1-20 The alkyl group is independently methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, or n-heptyl; (10)R 3 In, the C 3-20 cycloalkyl is (11)R 3 In, the C 3-20 Cycloalkenyl is (12)R 3 In the context, the -OC 1-20 Alkyl is (13)R 3 In the context, the -OC 3-20 cycloalkyl is (14)R 2-7 In this context, the halogen is independently F; (15)R 2-7 In, the C 1-20 Alkyl groups are independently C 1-6 alkyl; (16)R 2-7 In the context, the -OC 1-20 Alkyl groups are independently -OC 1-6 alkyl; (17)R a R b and R c In, the C 1-20 Alkyl groups are independently C 1-6 alkyl; (18)R d and R e In, the C 1-20 Alkyl groups are independently C 1-6 alkyl; (19)R d and R e In the context, the -C 1-6 Alkylene-C 6-10 The aromatic ring is independently benzyl; (20)R f R g and R i In, the C 1-20 Alkyl groups are independently C 1-6 alkyl; (21)R 2-1-1 In the context, the -OC 1-20 Alkyl groups are independently -OC 1-6 alkyl.

19. The method for preparing compound A as described in claim 18, characterized in that, It meets one or more of the following conditions: (1)R 1 In, the C 1-20 Alkyl groups and those with one, two, or three R groups 1-2 Replacement C 1-20 C in alkyl 1-20 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; (2)R 1 In the context, the -OC 1-20 The alkyl group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; (3)R 2 In, the C 1-20 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; (4)R 2-7 In, the C 1-20 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; (5)R 2-7 In the context, the -OC 1-20 The alkyl group is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; (6)R a R b and R c In, the C 1-20 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; (7)R d and R e In, the C 1-20 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; (8)R f R g and R i In, the C 1-20 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; (9)R 2-1-1 In the context, the -OC 1-20 The alkyl group is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy.

20. The method for preparing compound A according to claim 19, characterized in that, It meets one or more of the following conditions: (1)R 1 In, the C 1-20 Alkyl groups and those with one, two, or three R groups 1-2 Replacement C 1-20 C in alkyl 1-20 Alkyl groups are independently methyl groups; (2)R 1 In the context, the -OC 1-20 The alkyl group is a methoxy group; (3)R 2 In, the C 1-20 Alkyl groups are independently methyl groups; (4)R 2-7 In, the C 1-20 Alkyl groups are independently methyl groups; (5)R 2-7 In the context, the -OC 1-20 The alkyl group is independently a methoxy group; (6)R a R b and R c In, the C 1-20 The alkyl group is independently methyl or ethyl; (7)R d and R e In, the C 1-20 The alkyl group is independently methyl or ethyl; (8)R f R g and R i In, the C 1-20 The alkyl group is independently methyl or tert-butyl; (9)R 2-1-1 In the context, the -OC 1-20 The alkyl group is independently methoxy.

21. The method for preparing compound A according to claim 13, characterized in that, The -SiR a R b R c for 22. The method for preparing compound A according to claim 17, characterized in that, It meets one or more of the following conditions: (i)R 3 In the context, the term refers to one, two, or three R's. 2-1 Replacement C 1-20 Alkyl is (ii)R 3 In the context, the term refers to one, two, or three R's. 2-7 Replacement C 6-10 Argan 23. The method for preparing compound A according to claim 13, characterized in that, It satisfies one or more of the following conditions: (1) R 0 It is independently methyl, methoxy, or tert-butyl; (2)R 2 It is H or methyl; R 3 Choose from any of the following structures: ； Or, R 2 and R 3 The carbon atoms attached to it form (3) The compound I' is one or more of the following compounds: (4) In compound I', X - For Cl - R 0 For tert-butyl, Ar 1 Ar 2 Ar 3 and Ar 4 Same, for (5) Compound II' is one or more of the following compounds: (6) In compound II', X - For Cl - R 0 For tert-butyl, Ar 1 Ar 2 Ar 3 and Ar 4 Same, for (7) When Cy A has two or more F atoms in meta positions, Connect the position between two F atoms.

24. The method for preparing compound A according to claim 23, characterized in that, R 0 It is independently tert-butyl.

25. The method for preparing compound A according to claim 23, characterized in that, It meets one or two of the following conditions: (i) Compound III is selected from any of the following compounds: (ii) Compound IV is selected from any of the following compounds:

26. A method for preparing a polymer, comprising the following steps: In a solvent, in system 1 or system 2, compound V and compound VII are reacted as shown below; system 1 consists of compound I', 1,5-cyclooctadiene nickel, and a base; system 2 consists of compound II' and 1,5-cyclooctadiene nickel; and compound V is... Wherein, compound I' or compound II' is as described in any one of claims 13-23; Compound VII is selected from any of the following structures: Choose from any of the following structures: Choose from any of the following structures: n represents the degree of aggregation; The number-average molecular weight and molecular weight distribution of polymers 2-1 to 2-13 are as follows:

27. The method for preparing the polymer according to claim 26, characterized in that, The number-average molecular weight and molecular weight distribution were obtained using gel permeation chromatography.

28. The method for preparing the polymer according to claim 26, characterized in that, The test method involves dissolving the polymer in anhydrous THF, using THF as the mobile phase and polystyrene as the reference, and performing the test using gel permeation chromatography.

29. The method for preparing the polymer according to claim 26, characterized in that, It meets one or more of the following conditions: (1) The reaction was carried out under nitrogen protection; (2) The alkali is an organic alkali; (3) The solvent is a hydrocarbon solvent; (4) The molar ratio of compound V to compound I is 1:0.01-0.07; (5) The molar ratio of compound V to compound VII is 1:0.5-2; (6) The molar ratio of compound V to nickel 1,5-cyclooctadiene is 1:0.02-0.1; (7) The reaction temperature is 100-150℃; (8) The reaction time is 36-72h.

30. The method for preparing the polymer according to claim 29, characterized in that, It meets one or more of the following conditions: (1) The base is an alkali metal salt of an alcohol; (2) The solvent is an alkane solvent; (3) The molar ratio of compound V to compound I is 1:0.05; (4) The molar ratio of compound V to compound VII is 1:1; (5) The molar ratio of compound V to nickel 1,5-cyclooctadiene is 1:0.05; (6) The reaction temperature of the above reaction is 130℃; (7) The reaction time is 48 hours.

31. The method for preparing the polymer according to claim 30, characterized in that, It meets one or more of the following conditions: (1) The base is potassium tert-butoxide; (2) The solvent is n-heptane.

32. A method for preparing a polymer, characterized in that, It includes the following steps: In a solvent, in system 1 or system 2, compound V and compound IX are reacted as shown below; system 1 consists of compound I', 1,5-cyclooctadiene nickel, and a base; system 2 consists of compound II' and 1,5-cyclooctadiene nickel; and compound V is... Compound IX is selected from any of the following compounds: Choose from any of the following structures: Choose from any of the following structures: Where n is the degree of aggregation; The number-average molecular weight and molecular weight distribution of polymers 3-1 to 3-6 are as follows: 。 33. The method for preparing the polymer according to claim 32, characterized in that, The number-average molecular weight and molecular weight distribution were obtained using gel permeation chromatography.

34. The method for preparing the polymer according to claim 33, characterized in that, The test method involves dissolving the polymer in anhydrous THF, using THF as the mobile phase and polystyrene as the reference, and performing the test using gel permeation chromatography.

35. The method for preparing the polymer according to claim 32, characterized in that, It meets one or more of the following conditions: (1) The reaction was carried out under nitrogen protection; (2) The alkali is an organic alkali; (3) The solvent is a hydrocarbon solvent; (4) The molar ratio of compound V to compound I is 1:0.01-0.07; (5) The molar ratio of compound V to compound IX is 1:0.2-3; (6) The molar ratio of compound V to the base is 1:0.02-0.2; (7) The molar ratio of compound V to nickel 1,5-cyclooctadiene is 1:0.02-0.1; (8) The reaction temperature of the above reaction is 100-150℃; (9) The reaction time is 8-14 hours.

36. The method for preparing the polymer according to claim 35, characterized in that, It meets one or more of the following conditions: (1) The base is an alkali metal salt of an alcohol; (2) The solvent is an alkane solvent; (3) The molar ratio of compound V to compound I is 1:0.05; (4) The molar ratio of compound V to compound IX is 1:1; (5) The molar ratio of compound V to the base is 1:0.1; (6) The molar ratio of compound V to nickel 1,5-cyclooctadiene is 1:0.02 or 1:0.05; (7) The reaction temperature is 100℃; (8) The reaction time is 12 hours.

37. The method for preparing the polymer according to claim 36, characterized in that, It meets one or more of the following conditions: (1) The base is potassium tert-butoxide; (2) The solvent is n-heptane.

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