CN118290355A

CN118290355A - Application of difluoro sulfimide as catalyst

Info

Publication number: CN118290355A
Application number: CN202410403513.0A
Authority: CN
Inventors: 董佳家; 江营
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 2019-12-31
Filing date: 2019-12-31
Publication date: 2024-07-05
Also published as: CN113121799B; CN115141159B; CN113121799A; CN115141159A

Abstract

The invention discloses an application of difluoro sulfimide as a catalyst. The invention takes the difluoro sulfimide as the catalyst to efficiently catalyze the Friedel-Crafts reaction, the esterification reaction, the lactone ring-opening polymerization reaction, the silyl ether polymerization reaction, the reduction etherification of carbonyl compounds, the alkynyl hydrolysis and other reactions, and has mild reaction conditions and high atom economy.

Description

Application of difluoro sulfimide as catalyst

This patent application is a divisional application of patent application number 202210754232.0, the application date of which is 2019, 12 and 31, and the name of which is "application of bisfluorosulfonyl imide as a catalyst".

Technical Field

The invention relates to an application of bis-fluoro-sulfimide as a catalyst.

Background

The structure of the difluoro-sulfonyl imide (HN (SO ₂F)₂) is analyzed, negative charges on N atoms are dispersed to the whole O-S-N framework through resonance effect under the strong electron-withdrawing effect of the fluoro-sulfonyl group to generate high delocalization, SO that the stability of FSO ₂)₂N^- is greatly enhanced, and the fluoro-sulfonyl group has larger steric hindrance and strong electron-withdrawing effect, SO that the coordination capability of the ions is greatly reduced.

The difluoro sulfimide belongs to nitrogen-containing superacid, is a novel super strong Bronsted acid, and has the strength of more than concentrated sulfuric acid. Among known superacids, sulfuric acid, trifluoromethanesulfonic acid, fluorosulfonic acid and the like are widely used as catalysts in the synthesis of intermediates such as medicines, pesticides, polymers and the like.

The application of the difluoro-sulfonyl imide as a catalyst in organic synthesis is not found at present, mainly because commercial production of the acid is not realized at present, and the synthetic route is not mature. At present, a large amount of fluorosulfonic acid is generally required to be used as a solvent in the synthesis of the bisfluorosulfonyl imide, the fluorosulfonic acid is high in price, the synthesis cost is high, in addition, the boiling point of the fluorosulfonic acid is very close to that of the bisfluorosulfonyl imide, and the separation and purification of a product are difficult.

In the acidification process of potassium (or sodium) difluoro-sulfonyl imide studied in the prior stage, the applicant finds that the difluoro-sulfonyl imide can be obtained by rapid and simple separation with very high yield under the condition of using concentrated sulfuric acid as acid and sulfur dioxide as solvent at low temperature, the price is low, the post-treatment is simple, the separation and purification are easy, and the synthetic route has the possibility of industrialized production.

Disclosure of Invention

The invention aims to overcome the defect of narrower application field of the prior difluoro-sulfonyl imide, and provides the application of the difluoro-sulfonyl imide as a catalyst.

The invention provides an application of difluoro sulfimide as a catalyst in the preparation of polylactone shown in a formula (I), which comprises the following steps:

In a solvent, under the action of bisfluorosulfonyl imide, a compound shown in a formula (I-A) and a compound shown in a formula (I-B) are subjected to polymerization reaction to obtain polylactone shown in the formula (I);

Wherein n ₁ is an integer of 1 to 7;

R ¹ is C1-C16 alkyl or- (CH ₂)_n2-Ar,n₂ is an integer from 1 to 6, ar is C6-C10 aryl or R ^A substituted C6-C10 aryl, R ^A is halogen, C1-C6 alkyl or C1-C6 alkoxy;

m ₁ is an integer from 50 to 200.

Preferably, n ₁ is 1,2 or 3, for example 3.

Preferably, in R ¹, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably, C1-C6 alkyl.

Preferably, in R ¹, n ₂ may be 1,2 or 3, for example 3.

Preferably, in Ar, the C6-C10 aryl group and the C6-C10 aryl group of the R ^A -substituted C6-C10 aryl group are independently phenyl.

Preferably, in Ar, the number of R ^A substituted in the C6-C10 aryl substituted by R ^A is 1-3 (for example 1), and each R ^A is the same or different.

Preferably, in R ^A, the halogen is fluorine, chlorine, bromine or iodine.

Preferably, in R ^A, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in R ^A, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.

Preferably, in R ¹, ar is phenyl or R ^A substituted phenyl.

Preferably, the compound represented by the formula (I-B) is

In the preparation of the polylactone represented by the formula (I), the amount of the bisfluorosulfonyl imide is preferably 0.1% to 10% (e.g., 0.1%) of the molar amount of the compound represented by the formula (I-A).

In the preparation of the polylactone represented by the formula (I), the ratio of the compound represented by the formula (I-A) to the compound represented by the formula (I-B) may be a ratio commonly used in the art for such reactions, for example, the molar ratio of the compound represented by the formula (I-A) to the compound represented by the formula (I-B) is (50-200): 1, and still more example, 100:1.

In the preparation of the polylactone shown in the formula (I), the solvent can be one or more solvents commonly used in the reaction in the field, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc.; and for example dichloromethane.

In the preparation of the polylactone of formula (I), the temperature of the polymerization reaction may be a temperature commonly used in such reactions in the art, for example, 20℃to the reflux temperature of the solvent, for example, room temperature.

In the preparation of the polylactone of formula (I), the progress of the polymerization reaction can be generally monitored by detection methods conventional in the art (such as TLC, HPLC or GC), and the endpoint of the reaction is generally determined by the disappearance of the compound of formula (I-A). The polymerization time is preferably 4 to 12 hours.

The invention also provides an application of the difluoro sulfimide in preparing silicone oil shown in a formula (II) as a catalyst, which comprises the following steps:

under the action of bisfluorosulfonyl imide, a compound shown as a formula (II-A) and a compound shown as a formula (II-B) are subjected to polymerization reaction to obtain silicone oil shown as a formula (II);

Wherein R ²、R³、R⁴ and R ⁵ are independently C1-C16 alkyl or C6-C10 aryl;

m ₂ is an integer from 50 to 200.

Preferably, in R ²、R³、R⁴ or R ⁵, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl, isopropyl).

Preferably, in R ²、R³、R⁴ or R ⁵, the C6-C10 aryl group may be phenyl.

Preferably, R ²、R³、R⁴ and R ⁵ are independently C1-C10 alkyl, further independently C1-C6 alkyl (e.g., C1-C3 alkyl, further e.g., methyl, ethyl, n-propyl, or isopropyl). More preferably, R ²、R³、R⁴ and R ⁵ are both C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl, and further such as methyl.

In the preparation of the silicone oil represented by the formula (II), the amount of the bisfluorosulfonyl imide is preferably 1% to 10% (e.g., 4%) of the molar amount of the compound represented by the formula (II-A).

In the preparation of the silicone oil represented by the formula (II), the ratio of the compound represented by the formula (II-A) to the compound represented by the formula (II-B) may be a ratio commonly used in the art for such reactions, for example, the molar ratio of the compound represented by the formula (II-A) to the compound represented by the formula (II-B) is (30-200): 1, and further, for example, 39.9:1.

In the preparation of the silicone oil represented by the formula (II), the polymerization reaction may be carried out in a solvent-free or solvent-free solvent, and the solvent may be one or more solvents commonly used in such a reaction in the art, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc. Preferably, the polymerization is carried out in the absence of a solvent.

In the preparation of the silicone oil represented by formula (II), the temperature of the polymerization reaction may be a temperature commonly used in such a reaction in the art, for example, 20 ℃ to the reflux temperature of the solvent, for example, room temperature.

In the preparation of the silicone oil of formula (II), the progress of the polymerization reaction can be generally monitored by detection methods conventional in the art (such as TLC, HPLC or GC), and the end point of the reaction is generally the point at which the compound of formula (II-A) disappears. The polymerization time is preferably 2 to 12 hours.

The invention also provides an application of the difluoro sulfimide in preparing tetrazole compounds shown in a formula (III) as a catalyst, which comprises the following steps:

Under the action of difluoro-sulfonyl imide in a solvent, a compound shown as a formula (III-A), an orthoformate compound shown as a formula (III-B) and sodium azide react to obtain a tetrazole compound shown as a formula (III);

Wherein R ⁶ is C1-C16 alkyl, C6-C10 aryl or R ^B substituted C6-C10 aryl, R ^B is halogen or C2-C4 alkynyl;

R ^6-1 is methyl or ethyl.

Preferably, in R ⁶, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably, C1-C6 alkyl.

Preferably, in R ⁶, the C6-C10 aryl group and the C6-C10 aryl group in the R ^B substituted C6-C10 aryl group may independently be phenyl.

Preferably, in R ⁶, the number of substitution of R ^B in the C6-C10 aryl substituted by R ^B is 1-3 (for example, 1), and each R ^B is the same or different.

Preferably, in R ^B, the halogen may be fluorine, chlorine, bromine or iodine, for example bromine.

Preferably, in R ^B, the C2-C4 alkynyl group may be an ethynyl group.

Preferably, R ⁶ is R ^B substituted phenyl, R ^B is halogen or ethynyl, e.g., R ⁶ is

In the preparation of the tetrazole compound of formula (III), the amount of the bis-fluorosulfonyl imide is preferably 1% to 10% (e.g., 5%) of the molar amount of the compound of formula (III-A).

In the preparation of the tetrazole compound represented by formula (III), the ratio of the compound represented by formula (III-a) to the orthoformate compound represented by formula (III-B) may be a ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by formula (III-a) to the orthoformate compound represented by formula (III-B) is 1: (1-2), for example 1:1.2.

In the preparation of the tetrazole compound represented by formula (III), the ratio of the compound represented by formula (III-a) to the sodium azide may be a ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by formula (III-a) to the sodium azide is 1: (1-3), for example 1:1 or 1:1.1.

In the preparation of the tetrazole compound represented by formula (III), the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents, and alkane solvents; for example, glycerol, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc.; and for example glycerol.

In the preparation of the tetrazole compound of formula (III), the temperature of the reaction may be a temperature commonly used in such a reaction in the art, for example, 20℃to the reflux temperature of the solvent, for example, room temperature.

In the preparation of the tetrazole compound of formula (III), the progress of the reaction can be generally monitored by a detection method conventional in the art (such as TLC, HPLC or GC), and the end point of the reaction is generally the point when the compound of formula (III-A) disappears. The reaction time is preferably 2 to 12 hours.

The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (IV) as a catalyst, which comprises the following steps:

in Sup>A solvent, under the action of bisfluorosulfonyl imide, performing an addition reaction between Sup>A compound shown in formulSup>A (IV-A) and Sup>A compound shown in formulSup>A (IV-B) to obtain Sup>A compound shown in formulSup>A (IV);

Wherein,

X is NH, S or O;

R ⁷、R⁸ and R ⁹ are independently C1-C16 alkyl, C6-C10 aryl, R ^C substituted C6-C10 aryl or R ^C is halogen, C1-C6 alkyl or C1-C6 alkoxy.

Preferably, in R ⁷、R⁸ or R ⁹, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).

Preferably, in R ⁷、R⁸ or R ⁹, the C6-C10 aryl group and the C6-C10 aryl group of the R ^C substituted C6-C10 aryl group are independently phenyl.

Preferably, in R ⁷、R⁸ or R ⁹, the number of substitutions of R ^C in the benzyl group substituted by R ^C may be 1 to 3 (for example, 1), and each R ^C may be the same or different.

Preferably, in R ^C, the halogen is fluorine, chlorine, bromine or iodine.

Preferably, in R ^C, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in R ^C, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.

Preferably, R ⁷ and R ⁸ are independently C1-C16 alkyl, for example C1-C10 alkyl, further for example C1-C6 alkyl (for example C1-C3 alkyl, further for example methyl, ethyl, n-propyl or isopropyl).

Preferably, R ⁹ is

Preferably, X is NH.

Preferably, the compound represented by the formulSup>A (IV-A) is

Preferably, the compound represented by the formula (IV-B) is

In the preparation of the compound represented by the formulSup>A (IV), the amount of the bisfluorosulfonyl imide is preferably 1% to 10% (e.g., 5%) of the molar amount of the compound represented by the formulSup>A (IV-A).

In the preparation of the compound represented by the formulSup>A (IV), the ratio of the compound represented by the formulSup>A (IV-A) to the compound represented by the formulSup>A (IV-B) may be Sup>A ratio of the amounts commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formulSup>A (IV-A) to the compound represented by the formulSup>A (IV-B) is 1 (1-10), for example, 1:1.

In the preparation of the compound represented by formula (IV), the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., and for example, acetonitrile.

In the preparation of the compound of formula (IV), the temperature of the addition reaction may be a temperature commonly used in such reactions in the art, for example 20 ℃ to the reflux temperature of the solvent, for example room temperature.

In the preparation of the compound of formulSup>A (IV), the progress of the addition reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and the endpoint of the reaction is generally taken as the disappearance of the compound of formulSup>A (IV-Sup>A). The time of the addition reaction is preferably 10 minutes to 12 hours, for example 0.5 hours.

The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (V) as a catalyst, which comprises the following steps:

performing Friedel-crafts reaction on Sup>A compound shown as Sup>A formulSup>A (V-A) and Sup>A compound shown as Sup>A formulSup>A (V-B) in Sup>A solvent under the action of difluoro sulfimide to obtain the compound shown as the formulSup>A (V);

Wherein Y is halogen,

R ¹⁰ is C1-C16 alkyl, benzyl, C6-C10 aryl, R ^D substituted C6-C10 aryl or R ^E substituted benzyl, R ^D and R ^E are independently halogen, C1-C6 alkyl or C1-C6 alkoxy;

r ¹¹ is C1-C6 alkyl or C1-C6 alkoxy.

Preferably, in Y, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine, bromine or iodine.

Preferably, in R ¹⁰, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).

Preferably, in R ¹⁰, the C6-C10 aryl group and the C6-C10 aryl group of the R ^D substituted C6-C10 aryl group are independently phenyl.

Preferably, in R ¹⁰, the number of substitution of R ^D in the C6-C10 aryl substituted by R ^D is 1-3 (for example, 1), and each R ^D is the same or different.

Preferably, in R ¹⁰, the number of substitutions of R ^E in the benzyl group substituted by R ^E may be 1 to 3 (for example, 1), and each R ^E may be the same or different.

Preferably, in R ^D or R ^E, the halogen is fluorine, chlorine, bromine or iodine.

Preferably, in R ^D、R^E or R ¹¹, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in R ^D、R^E or R ¹¹, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy.

Preferably, R ^D、R^E and R ¹¹ are independently C1-C6 alkoxy.

Preferably Y is

Preferably, R ¹⁰ is benzyl, phenyl, R ^D substituted phenyl or R ^E substituted benzyl, R ^D and R ^E are independently C1-C6 alkoxy.

Preferably, the compound represented by the formulSup>A (V-A) is

Preferably, the compound represented by the formula (V-B) is

In the preparation of the compound represented by the formula (V), the amount of the bisfluorosulfonyl imide is preferably 0.1% to 10% (e.g., 5%) of the molar amount of the compound represented by the formula (V-B).

In the preparation of the compound represented by the formulSup>A (V), the ratio of the compound represented by the formulSup>A (V-A) to the compound represented by the formulSup>A (V-B) may be Sup>A ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formulSup>A (V-A) to the compound represented by the formulSup>A (V-B) is (1-10): 1, for example, 1:1.

In the preparation of the compound represented by formula (V), the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., and for example, dichloromethane.

In the preparation of the compound of formula (V), the temperature of the friedel-crafts reaction may be a temperature commonly used in such reactions in the art, for example 20 ℃ to the reflux temperature of the solvent, for example room temperature.

In the preparation of the compound of formula (V), the progress of the Friedel-crafts reaction can be generally monitored by detection methods conventional in the art (such as TLC, HPLC or GC), and the endpoint of the reaction is generally taken as the disappearance of the compound of formula (V-B). The time of the friedel-crafts reaction is preferably 5 minutes to 12 hours, for example 0.5 hours.

The invention also provides an application of the difluoro sulfimide in preparing a compound shown in a formula (VI) as a catalyst, which comprises the following steps:

in a solvent, under the action of bisfluorosulfonyl imide, a compound shown in a formula (VI-A) and water are subjected to hydrolysis reaction to obtain the compound shown in the formula (VI);

Wherein R ¹² is C1-C16 alkyl, C6-C10 aryl or R ^F substituted C6-C10 aryl, R ^F is amino.

Preferably, in R ¹², the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).

Preferably, in R ¹², the C6-C10 aryl group and the C6-C10 aryl group of the R ^F substituted C6-C10 aryl group are independently phenyl.

Preferably, in R ¹², the number of substitution of R ^F in the C6-C10 aryl substituted by R ^F is 1-3 (for example, 1), and each R ^F is the same or different.

Preferably, R ¹² is phenyl or amino-substituted phenyl.

In the preparation of the compound of formula (VI), the amount of the bis-fluorosulfonyl imide is preferably 5% to 30% (e.g., 10%) of the molar amount of the compound of formula (VI-A).

In the preparation of the compound of formula (VI), the ratio of the compound of formula (VI-A) to water may be a ratio commonly used in such reactions in the art, for example, the molar ratio of the compound of formula (VI-A) to water may be 1 (1-10), for example, 1:2.9.

In the preparation of the compound represented by formula (VI), the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., and for example, 1, 4-dioxane.

In the preparation of the compound of formula (VI), the temperature of the hydrolysis reaction may be a temperature commonly used in such reactions in the art, for example 20 ℃ to the reflux temperature of the solvent, for example 100 ℃.

In the preparation of the compound of formula (VI), the progress of the hydrolysis reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and the endpoint of the reaction is generally determined by the disappearance of the compound of formula (VI-a). The hydrolysis reaction time is preferably 2 to 12 hours, for example 8 hours.

The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (VII) as a catalyst, which comprises the following steps:

In a solvent, under the action of difluoro-sulfonyl imide, a compound shown as a formula (VII-A) reacts with allyl trimethyl silane to obtain the compound shown as the formula (VII);

Wherein R ¹³ and R ¹⁴ are independently C1-C16 alkyl, C6-C10 aryl or R ^G substituted C6-C10 aryl, R ^G is halogen, C1-C6 alkyl or C1-C6 alkoxy.

Preferably, in R ¹³ or R ¹⁴, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).

Preferably, in R ¹³ or R ¹⁴, the C6-C10 aryl group and the C6-C10 aryl group of the R ^G substituted C6-C10 aryl group are independently phenyl.

Preferably, in R ^G, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine.

Preferably, in R ^G, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in R ^G, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.

Preferably, in R ¹³ or R ¹⁴, the number of the substitutions of R ^G in the C6-C10 aryl substituted by R ^G is 1-3 (for example, 1), and each R ^G is the same or different.

Preferably, R ¹³ and R ¹⁴ are independently phenyl or R ^G substituted phenyl, R ^G is C1-C3 alkoxy.

Preferably, the compound represented by the formula (VII-A) is

In the preparation of the compound represented by the formula (VII), the amount of the bisfluorosulfonyl imide is preferably 5% to 30%, for example, 10% of the molar amount of the compound represented by the formula (VII-A).

In the preparation of the compound represented by the formula (VII), the ratio of the compound represented by the formula (VII-A) to the allyltrimethylsilane may be a ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (VII-A) to the allyltrimethylsilane is 1 (1-10), for example, 1:1.2.

In the preparation of the compound represented by formula (VII), the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., and for example, dichloromethane.

In the preparation of the compound of formula (VII), the temperature of the reaction may be a temperature commonly used in such reactions in the art, for example, -20 ℃ to room temperature, for example room temperature.

In the preparation of the compound of formula (VII), the progress of the reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and the endpoint of the reaction is generally taken as the disappearance of the compound of formula (VII-A). The reaction time is preferably 2 to 12 hours, for example 2 hours.

The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (VIII) as a catalyst, which comprises the following steps:

Under the action of bisfluorosulfonyl imide, a compound shown as a formula (VIII-A), a compound shown as a formula (VIII-B) and a compound shown as a formula (VIII-C) react to obtain a compound shown as a formula (VIII);

Wherein R ¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹ and R ²⁰ are independently H, C C16 alkyl, C6C 10 aryl or R ^H substituted C6C 10 aryl, R ^H is halogen, C1C 6 alkyl or C1C 6 alkoxy.

Preferably, in R ¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹ or R ²⁰, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).

Preferably, in R ¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹ or R ²⁰, the C6-C10 aryl group and the C6-C10 aryl group of the R ^H substituted C6-C10 aryl group are independently phenyl.

Preferably, in R ^H, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine.

Preferably, in R ^H, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in R ^H, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.

Preferably, in R ¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹ or R ²⁰, the number of the substitutions of R ^H in the C6-C10 aryl substituted by R ^H is 1-3 (for example, 1), and each R ^H is the same or different.

Preferably, R ¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹ and R ²⁰ are independently H, C C6 alkyl, phenyl or R ^H substituted phenyl, R ^H is halogen, C1C 3 alkyl or C1C 3 alkoxy.

Preferably, the compound represented by the formula (VIII-A) is

Preferably, the compound represented by the formula (VIII-B) is

Preferably, the compound represented by the formula (VIII-C) is

In the preparation of the compound represented by the formula (VIII), the amount of the bisfluorosulfonyl imide is preferably 1% to 100%, for example 10% to 50%, still more for example 30% of the molar amount of the compound represented by the formula (VIII-B).

In the preparation of the compound represented by the formula (VIII), the ratio of the compound represented by the formula (VIII-A) to the compound represented by the formula (VIII-B) may be a ratio of the amounts commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (VII-A) to the compound represented by the formula (VIII-B) is (1-2): 1, for example, 1.1:1 or 1.3:1.

In the preparation of the compound represented by the formula (VIII), the ratio of the compound represented by the formula (VIII-A) to the compound represented by the formula (VIII-C) may be a ratio of the amounts commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (VII-A) to the compound represented by the formula (VIII-C) is 1: (1-3), e.g., 1:1.3, 1:1.8, or 1:2.

In the preparation of the compound represented by the formula (VIII), the reaction may be carried out in a solvent-free or solvent-free solvent, and the solvent may be one or more solvents commonly used in such a reaction in the art, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc. Preferably, the reaction is carried out in the absence of a solvent.

In the preparation of the compound of formula (VIII), the temperature of the reaction may be a temperature commonly used in such reactions in the art, for example, room temperature to 50 ℃, for example, room temperature.

In the preparation of the compound of formula (VIII), the progress of the reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and the endpoint of the reaction is generally taken as the disappearance of the compound of formula (VIII-B). The reaction time is preferably 2 to 12 hours.

The invention also provides an application of the difluoro sulfimide as a catalyst in a rearrangement reaction of a compound shown as a formula (IX), which comprises the following steps:

In a solvent, under the action of bisfluorosulfonyl imide, carrying out rearrangement reaction on a compound shown as a formula (IX) to obtain a compound shown as a formula (IX-A) and/or a compound shown as a formula (IX-B);

Wherein R ²¹ is C1-C16 alkyl, C6-C10 aryl or R ^I substituted C6-C10 aryl, R ^I is halogen, C1-C6 alkyl or C1-C6 alkoxy.

Preferably, in R ²¹, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).

Preferably, in R ²¹, the C6-C10 aryl group and the C6-C10 aryl group of the R ^I substituted C6-C10 aryl group are independently phenyl.

Preferably, in R ^I, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine.

Preferably, in R ^I, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in R ^I, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.

Preferably, in R ²¹, the number of substitution of R ^I in the C6-C10 aryl substituted by R ^I is 1-3 (for example, 1), and each R ^I is the same or different.

Preferably, R ²¹ is C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl, or isopropyl).

In the rearrangement reaction of the compound represented by the formula (IX), the amount of the bisfluorosulfonyl imide is preferably 20% to 150%, for example, 100% to 150%, still more for example, 123% or 124% of the molar amount of the compound represented by the formula (IX).

In the rearrangement reaction of the compound represented by the formula (IX), the rearrangement reaction may be carried out in a solvent-free or solvent-free solvent, and the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc. Preferably, the rearrangement reaction is carried out in the absence of a solvent.

In the rearrangement reaction of the compound represented by the formula (IX), the temperature of the rearrangement reaction may be a temperature commonly used in such a reaction in the art, for example, 20℃to 150℃such as room temperature, 60 ℃.

In the rearrangement reaction of the compound of formula (IX), the progress of the rearrangement reaction can be generally monitored by a detection method conventional in the art (for example, TLC, HPLC or GC), and the end point of the reaction is generally the point when the compound of formula (IX) disappears. The time of the rearrangement reaction is preferably 2 to 12 hours, for example 3 hours.

The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (X) as a catalyst, which comprises the following steps:

Under the action of bisfluorosulfonyl imide, a compound shown as a formula (X-A) reacts with a compound shown as a formula (X-B) to obtain a compound shown as a formula (X);

Wherein R ²² is H, C-C16 alkyl, C6-C10 aryl or R ^J substituted C6-C10 aryl; r ²³ is C1-C16 alkyl, C6-C10 aryl or R ^K -substituted C6-C10 aryl, R ^J and R ^K are independently halogen, C1-C6 alkyl or C1-C6 alkoxy.

Preferably, in R ²² or R ²³, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).

Preferably, in R ²² or R ²³, the C6-C10 aryl, the R ^J substituted C6-C10 aryl, and the C6-C10 aryl in the R ^K substituted C6-C10 aryl are independently phenyl.

Preferably, in R ^J or R ^K, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.

Preferably, in R ^J or R ^K, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in R ^J or R ^K, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy.

Preferably, in R ²², the number of substitution of R ^J in the C6-C10 aryl substituted by R ^J is 1-3 (for example, 1), and each R ^J is the same or different.

Preferably, in R ²³, the number of substitution of R ^K in the C6-C10 aryl substituted by R ^K is 1-3 (for example, 1), and each R ^K is the same or different.

Preferably, R ²² is phenyl or R ^J substituted phenyl.

Preferably, R ²³ is C1-C16 alkyl, for example C1-C10 alkyl, further for example C1-C6 alkyl (for example C1-C3 alkyl, further for example methyl, ethyl, n-propyl or isopropyl).

In the preparation of the compound represented by the formula (X), the amount of the bisfluorosulfonyl imide is preferably 0.1% to 10%, for example, 10% of the molar amount of the compound represented by the formula (X-A).

In the preparation of the compound represented by the formula (X), the ratio of the compound represented by the formula (X-A) to the compound represented by the formula (X-B) may be a ratio of the amounts commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (X-A) to the compound represented by the formula (X-B) is 1 (1-10), for example, 1:5.5.

In the preparation of the compound represented by the formula (X), the reaction may be carried out in a solvent-free or solvent-free solvent, and the solvent may be one or more solvents commonly used in such a reaction in the art, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents and alkane solvents; for example, toluene, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., and for example, toluene. Preferably, the reaction is carried out in the absence of a solvent.

In the preparation of the compound of formula (X), the temperature of the reaction may be a temperature commonly used in the art for such reactions, e.g., room temperature-the reflux temperature of the solvent used, e.g., 85 ℃.

In the preparation of the compound of formula (X), the progress of the reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and the endpoint of the reaction is generally determined by the disappearance of the compound of formula (X-A). The reaction time is preferably 2 to 12 hours, for example 12 hours.

The invention also provides an application of the difluoro sulfimide as a catalyst in the reduction etherification reaction of a carbonyl compound shown in a formula (XI-A), which comprises the following steps:

In a solvent, under the action of difluoro sulfimide and silane compounds shown as a formula (XI-B), carbonyl compounds shown as a formula (XI-A) undergo a reduction etherification reaction to prepare compounds shown as a formula (XI);

Wherein R ²⁴ and R ²⁵ are independently H, C C16 alkyl, C6C 10 aryl or R ^L substituted C6C 10 aryl, R ^L is halogen, C1C 6 alkyl or C1C 6 alkoxy; r ^24-1 is C1-C3 alkyl.

Preferably, in R ²⁴ or R ²⁵, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).

Preferably, in R ²⁴ or R ²⁵, the C6-C10 aryl group and the C6-C10 aryl group of the R ^L substituted C6-C10 aryl group are independently phenyl.

Preferably, in R ^L, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine.

Preferably, in R ^L, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in R ^L, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.

Preferably, in R ²⁴ or R ²⁵, the number of the substitutions of R ^L in the C6-C10 aryl substituted by R ^L is 1-3 (for example, 1), and each R ^L is the same or different.

Preferably, R ²⁴ and R ²⁵ are independently H, phenyl or R ^L substituted phenyl.

Preferably, R ^24-1 is methyl, ethyl, n-propyl or isopropyl.

Preferably, the carbonyl compound represented by the formula (XI-A) is

In the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the amount of the bisfluorosulfonyl imide is preferably 0.1% to 10%, for example, 0.1% to 5%, still for example, 1% of the molar amount of the carbonyl compound represented by the formula (XI-A).

In the reduction etherification reaction of the carbonyl compound shown in the formula (XI-A), the silane compound shown in the formula (XI-B) can be used in the common use amount in the field of such reactions, for example, the molar ratio of the carbonyl compound shown in the formula (XI-A) to the silane compound shown in the formula (XI-B) is 1 (1-2), for example, 1:1.12 and 1:1.10.

In the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the solvent may be one or more solvents commonly used in such a reaction in the art, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., for example, methylene chloride.

In the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the temperature of the reductive etherification reaction may be a temperature commonly used in such a reaction in the art, for example, 0 to room temperature, for example, room temperature.

In the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the progress of the reductive etherification reaction may be generally monitored by a detection method conventional in the art (such as TLC, HPLC or GC), and the end point of the reaction is generally the point when the carbonyl compound represented by the formula (XI-A) disappears. The time for the reductive etherification reaction is preferably 5 minutes to 12 hours, for example, 0.5 hours, 1 hour.

The invention also provides a preparation method of the silicon bis (fluorosulfonyl) imide shown in the formula (XII), which comprises the following steps:

reacting a compound shown as a formula (XII-A) with bis (fluorosulfonyl) imide to obtain bis (fluorosulfonyl) imide silicon ester shown as a formula (XII);

Wherein Z is H, halogen, C1-C16 alkyl, C6-C10 aryl or R ^N -substituted C6-C10 aryl, R ²⁶、R²⁷ and R ²⁸ are independently C1-C16 alkyl, C6-C10 aryl, R ^M -substituted C6-C10 aryl or R ²⁹、R³⁰ and R ³¹ are independently C1-C6 alkyl, R ^M and R ^N are independently halogen, C1-C6 alkyl or C1-C6 alkoxy.

Preferably, Z, R ²⁶、R²⁷ or R ²⁸, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).

Preferably, in Z, R ²⁶、R²⁷ or R ²⁸, the C6-C10 aryl, the R ^N substituted C6-C10 aryl and the C6-C10 aryl of the R ^M substituted C6-C10 aryl are independently phenyl.

Preferably, Z, R ^M or R ^N, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.

Preferably, in R ^M or R ^N, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in R ^M or R ^N, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy.

Preferably, in R ²⁶、R²⁷ or R ²⁸, the number of the substitutions of R ^M in the C6-C10 aryl substituted by R ^M is 1-3 (for example, 1), and each R ^M is the same or different.

Preferably, in R ²⁹、R³⁰ or R ³¹, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in Z, the number of R ^N substituted in the C6-C10 aryl substituted by R ^N is 1-3 (for example 1), and each R ^N is the same or different.

Preferably, R ²⁶、R²⁷ and R ²⁸ are independentlyR ²⁹、R³⁰ and R ³¹ are independently C1-C3 alkyl (e.g., methyl, ethyl, n-propyl or isopropyl).

Preferably, Z is H or halogen, more preferably Z is H.

Preferably, the compound represented by the formula (XII-A) is

In the method for preparing the silicon difluorosulfinate represented by the formula (XII), the ratio of the compound represented by the formula (XII-A) to the amount of the difluorosulfimide may be a ratio commonly used in the art for such reactions, for example, the molar ratio of the compound represented by the formula (XII-A) to the amount of the difluorosulfimide is (1-10): 1, e.g., 1:1.

In the preparation method of the silicon bisfluorosulfonyl imide shown in the formula (XII), the reaction can be carried out in a solvent or in a solvent, wherein the solvent can be one or more solvents commonly used in the field of such reactions, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., for example, acetonitrile or methylene chloride. Preferably, the reaction is carried out in the absence of a solvent.

In the method for preparing the silicon bisfluorosulfonyl imide represented by the formula (XII), the temperature of the reaction may be a temperature commonly used in the art for such a reaction, for example, 0℃to room temperature, for example, room temperature.

In the preparation method of the silicon bisfluorosulfonyl imide shown in the formula (XII), the progress of the reaction can be generally monitored by a detection method conventional in the art (such as TLC, HPLC or GC or NMR), and the endpoint of the reaction is generally the point when bisfluorosulfonyl imide disappears. The reaction time is preferably 30 minutes to 2 hours, for example 1 hour.

The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (XIII) as a catalyst, which comprises the following steps:

under the action of bisfluorosulfonyl imide, a compound shown in a formula (XIII-A), a compound shown in a formula (XIII-B) and a compound shown in a formula (XIII-C) react to obtain a compound shown in a formula (XIII);

Wherein Q is CH or N;

r ³² is halogen, C1-C16 alkyl, C6-C10 aryl or R ^O substituted C6-C10 aryl;

m ₃ is 0, 1, 2,3 or 4;

R ³³ is C1-C16 alkyl, C6-C10 aryl or R ^P substituted C6-C10 aryl;

R ^O and R ^P are independently halogen, C1-C6 alkyl or C1-C6 alkoxy.

Preferably, m ₃ is 0 or 1 (e.g., m ₃ is 0).

Preferably, Q is N.

Preferably, in R ³², the halogen is fluorine, chlorine, bromine or iodine, such as chlorine.

Preferably, in R ³² or R ³³, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).

Preferably, in R ³² or R ³³, the C6-C10 aryl, the R ^O substituted C6-C10 aryl, and the C6-C10 aryl in the R ^P substituted C6-C10 aryl are independently phenyl.

Preferably, in R ^O or R ^P, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.

Preferably, in R ^O or R ^P, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.

Preferably, in R ^O or R ^P, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy.

Preferably, in R ³², the number of substitution of R ^O in the C6-C10 aryl substituted by R ^O is 1-3 (for example, 1), and each R ^O is the same or different.

Preferably, in R ³³, the number of substitution of R ^P in the C6-C10 aryl substituted by R ^P is 1-3 (for example, 1), and each R ^P is the same or different.

Preferably, R ³³ is C1-C6 alkyl, such as C1-C3 alkyl, further such as methyl, ethyl, n-propyl or isopropyl.

In the preparation of the compound of formula (XIII), the amount of the bis-fluorosulfonyl imide is preferably 5% to 20%, for example 10%, of the molar amount of the compound of formula (XIII-B).

In the preparation of the compound represented by the formula (XIII), the ratio of the compound represented by the formula (XIII-A) to the compound represented by the formula (XIII-B) may be a ratio of the amounts commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (XIII-A) to the compound represented by the formula (XIII-B) is (1-2): 1, for example, 1:5.1.

In the preparation of the compound represented by the formula (XIII), the ratio of the compound represented by the formula (XIII-C) to the compound represented by the formula (XIII-B) may be a ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (XIII-C) to the compound represented by the formula (XIII-B) is (1-200): 1, for example, 192.5:1.

In the preparation of the compound shown in the formula (XIII), the reaction can be carried out in a solvent-free state or in a solvent, and the solvent can be one or more solvents commonly used in the field of such reactions, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., for example, acetonitrile or methylene chloride. Preferably, the reaction is carried out in the absence of a solvent.

In the preparation of the compound of formula (XIII), the temperature of the reaction may be a temperature commonly used in such reactions in the art, for example 50℃to 120℃and still more for example 60 ℃.

In the preparation of the compound of formula (XIII), the progress of the reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC or NMR), and the endpoint of the reaction is generally taken as the disappearance of the compound of formula (XIII-B). The reaction time is preferably 1 to 5 hours, for example 3.5 hours.

In the present invention, room temperature means 20℃to 30 ℃.

Unless otherwise indicated, the terms used in the present invention have the following meanings:

The term "alkyl" refers to a straight or branched chain alkyl group having the indicated number of carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like.

Examples of the term "sulfoxide solvents" include, but are not limited to, dimethyl sulfoxide.

Examples of the term "ketone solvent" include, but are not limited to, acetone or N-methylpyrrolidone, etc.

Examples of the term "alcoholic solvent" include, but are not limited to, methanol, ethanol, glycerol, t-butanol, and the like.

Examples of the term "ethereal solvent" include, but are not limited to, diethyl ether, tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether, 1, 4-dioxane, and the like.

Examples of the term "ester solvent" include, but are not limited to, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, ethyl butyrate, and the like.

Examples of the term "nitrile solvent" include, but are not limited to, acetonitrile and the like.

Examples of the term "aromatic solvent" include, but are not limited to, benzene, toluene, xylene, benzotrifluoride, fluorobenzene, and the like.

Examples of the term "amide-based solvent" include, but are not limited to, N-dimethylformamide or N, N-dimethylacetamide and the like.

Examples of the term "halogenated hydrocarbon solvent" include, but are not limited to, methylene chloride, chloroform, 1, 2-dichloroethane, and the like.

Examples of the term "alkane solvent" include, but are not limited to, petroleum ether or n-hexane, and the like.

The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.

The reagents and materials used in the present invention are commercially available.

The invention has the positive progress effects that: the invention creatively applies the difluoro sulfimide to the organic synthesis reaction, can efficiently catalyze various types of reactions, such as Friedel-Crafts reaction, esterification reaction, lactone ring-opening polymerization reaction, silyl ether polymerization reaction, carbonyl compound reduction etherification, alkynyl hydrolysis and the like, and has mild reaction conditions, strong substrate adaptability and high atom economy.

Detailed Description

The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.

Preparation example 1

10G of potassium difluorosulfimide (45.6 mmol) and 10g of 98% concentrated sulfuric acid (100 mmol) were charged into an autoclave, 60 g of sulfur dioxide was introduced at-70℃and slowly warmed to room temperature, a white solid was formed after the reaction for half an hour, then sulfur dioxide gas was slowly released, 50ml of methylene chloride was added, filtration was carried out, the solid was washed with 50ml of methylene chloride, the filtrate was dried by spinning, distillation under reduced pressure was carried out, and 85℃20mm Hg fractions were collected to give 7.7g (42.5 mmol) of difluorosulfimide as a colorless liquid in 93% yield.

¹⁹ F NMR (dichloromethane as solvent, monofluorotrichloromethane as internal standard): 57.3.

Preparation example 2

10G of sodium difluorosulfimide (49.26 mmol) and 10g of 98% concentrated sulfuric acid (100 mmol) were charged into an autoclave, 60 g of sulfur dioxide was introduced at-70℃and slowly warmed to room temperature, a white solid was formed after the reaction for half an hour, then sulfur dioxide gas was slowly released, 50ml of methylene chloride was added, filtration was carried out, the solid was washed with 50ml of methylene chloride, the filtrate was dried by spinning, distillation under reduced pressure was carried out, and 85℃20mm Hg fractions were collected to give 8.1g (44.75 mmol) of difluorosulfimide as a colorless liquid in a yield of 91%.

Example 1

1.9998G (17.54 mmol,1 eq) of caprolactone, 5ml of methylene chloride, 175ul of a 1mol/L solution of phenylpropanol methylene chloride (1% eq) were charged into a 25ml three-necked flask, 35ul of a 0.5mol/L solution of difluoro sulfinamide acid methylene chloride (0.1% eq) was added under nitrogen protection, the reaction was allowed to react overnight at room temperature, the reaction solution was poured into 50ml of cold n-hexane, the solid was precipitated, filtered and dried to give 1.86g (yield 93%) of white polycaprolactone solid, which was checked by GPC, mn ^PS =25267, pdi=1.03.

Example 2

5.01G (16.92 mmol) of octamethyl cyclotetrasiloxane, 0.0687g (0.424 mmol) of hexamethyl silyl ether, and 0.12g of bis-fluorosulfonyl imide (0.66 mmol,4 mol% relative to octamethyl cyclotetrasiloxane) were charged into a 25ml single-neck flask, stirred magnetically, and reacted overnight at room temperature to give a colorless viscous liquid as simethicone. Mn ^PS =9820, pdi=1.0 as measured by GPC.

Example 3

To a 20ml single port flask was added 3-ethynylaniline (0.1068 g,0.912 mmol), sodium azide (0.065 g,1 mmol), triethyl orthoformate (0.162 g,1.1 mmol), glycerol (4 ml), bis-fluorosulfonyl imide (91ul,0.5M in DCM,5 mol% relative to 3-ethynylaniline) were added, the reaction was carried out overnight at room temperature, and after completion of the reaction of the starting material (3-ethynylaniline) for TLC (petroleum ether: ethyl acetate=10:1), 15ml of water was added, and a solid was precipitated, filtered, washed with water, and dried to give 0.13g (0.76 mmol) of a pale yellow solid in 84% yield. Melting point 98.6-100 deg.c.

¹H NMR(400MHz,CD₃CN):3.38(s，1H),7.17-7.32(m,4H),8.10(s,1H).

Example 4

To a 20ml single flask was added 3-bromoaniline (0.1 g,0.58 mmol), sodium azide (0.038 g,0.58 mmol), triethyl orthoformate (0.104 g,0.7 mmol), glycerol (4 ml), bis-fluorosulfonyl imide (58ul,0.5M in DCM,5% mol relative to 3-bromoaniline) and reacted overnight at room temperature, and TLC (petroleum ether: ethyl acetate=10:1) was used to detect the completion of the reaction of the starting material (3-bromoaniline), 15ml of water was added, and solids were precipitated, filtered, washed with water and dried to give 0.113g (0.5 mmol) of a pale yellow solid in 86% yield. Melting point 184-186 ℃.

¹H NMR(400MHz,CDCl₃):6.91-6.93(d，2H),7.4-7.42(d,2H),8.08(s,1H)。

Example 5

To a 20ml single vial was added 4-hexen-3-one (0.3095 g,3.15 mmol), benzyl carbamate (0.476 g,3.15 mmol), acetonitrile (6 ml), bis-fluorosulfonyl imide (315 ul,0.5m in CH ₃ CN,5% mole relative to 4-hexen-3-one), and the reaction was continued for half an hour at room temperature, TLC (petroleum ether: ethyl acetate=10:3), rf=0.4, disappearance of the detection starting material (4-hexen-3-one), purification by column chromatography gave 0.74g of white solid in 95% yield.

¹H NMR(400MHz,CDCl₃):0.94-1.26(m,6H),2.28-2.68(m,4H),3.91-4.17(m,1H),5.08(m,3H),7.3-7.34(m,5H)

LC-MS：272(M+Na)。

Example 6

To a 20ml single flask was added benzyl p-methoxyacetate (0.792 g,4.4 mmol), methoxybenzene (0.476 g,4.4 mmol), methylene chloride (6 ml), bis-fluorosulfonyl imide (440 ul,0.5m in CH ₃ CN,5% mol relative to benzyl p-methoxyacetate), and reacted at room temperature for half an hour, TLC (petroleum ether: ethyl acetate=10:3), rf=0.4, disappearance of the starting material (benzyl p-methoxyacetate) was detected, and spin-drying gave 0.95g (4.17 mmol) as a yellow oil in 95% yield.

¹H NMR(400MHz,CDCl₃):3.80(s,6H),3.89(s,2H),6.83-7.13(m,8H)。

Example 7

In a 20ml single vial was added p-aminophenylacetylene (0.2265 g,1.935 mmol), water (0.1 g,5.56 mmol), 1, 4-dioxane (2.5 ml), bis-fluorosulfonimide (35 mg,0.193mmol,10% mol relative to p-aminophenylacetylene), reacted at 100℃for 8 hours, TLC (petroleum ether: ethyl acetate=5:2, rf=0.3), the disappearance of the starting material (p-aminophenylacetylene) was detected, extraction with ethyl acetate (20 ml) was added, washing with water (20 ml. Times.3), washing with saturated sodium chloride, drying with anhydrous sodium sulfate, and spin-drying to give 0.23g (1.7 mmol) of a yellow solid in 88% yield.

LC-MS：136(M+1)。

¹H NMR(400MHz,CD₃CN):2.42(s,3H),4.79(s,2H),6.58-6.69(d,2H),7.68-7.79(d,2H)。

Example 8

In a20 ml single vial was added 4' -methoxychalcone (0.1157 g, 0.481 mmol), dichloromethane (3 ml), allyltrimethylsilane (66.4 mg,0.58mmol,1.2 eq), bis-fluorosulfonimide (9 mg,0.0497mmol,10% mol relative to 4' -methoxychalcone) was added under ice bath conditions, the reaction was slowly restored to room temperature for two hours, TLC (petroleum ether: ethyl acetate=10:1), the starting material (4 ' -methoxychalcone) was detected to disappear, washed with water (20 ml×3), washed with saturated sodium chloride, dried over anhydrous sodium sulfate, and purified by column chromatography (petroleum ether: ethyl acetate=10:1, rf=0.4) to give 0.11g (0.393 mmol) as a pale yellow solid in 81% yield.

¹H NMR(400MHz,CDCl₃):2.4-2.48(m,2H),3.21-3.23(m,2H),3.41-3.48(m,1H),3.83(s,3H),4.92-5.00(m,2H),5.62-5.72(m,1H),6.86-6.89(m,2H),7.14-7.28(m,5H),7.85-7.88(m,2H).

Example 9

To a 20ml single flask was added aniline (213 mg,2.29 mmol), benzaldehyde (192 mg,1.81 mmol) and bis-fluorosulfonyl imide (98 mg,0.54mmol,30% mole relative to benzaldehyde) and stirred for 5 minutes, then acetophenone (360 mg,3 mmol) was added and stirred overnight at room temperature. Column chromatography purification (n-hexane: ethyl acetate=10:1, rf=0.4) afforded 210mg (0.69 mmol) of the product as a white solid in 38% yield.

¹H NMR(400HMz,CDCl₃):3.39-3.53(m,2H),4.56(s,1H),4.99-5.02(q,1H),6.55-6.57(d,2H),6.64-6.68(t,2H),7.07-7.09(t,2H),7.21-7.26(m,2H),7.30-7.34(t,2H),7.43-7.46(m,3H),7.54-7.58(t,1H),7.90-7.92(d,2H).

Example 10

To a 20ml single flask was added aniline (106 mg,1.14 mmol), p-chlorobenzaldehyde (140 mg,1 mmol) and acetophenone (240 mg,2 mmol), stirred well and bis-fluorosulfonyl imide (54 mg,0.298mmol,30% mol relative to p-chlorobenzaldehyde) was added and reacted overnight at room temperature. TLC (n-hexane: ethyl acetate=10:1) checked for aniline and formaldehyde disappearance and column chromatography purification (n-hexane: ethyl acetate=10:1, rf=0.4) gave 100mg (0.298 mmol) of the product as a white solid in 30% yield.

¹H NMR(400MHz,CDCl3):3.37-3.49(m,2H),4.44(brs,1H),4.94-4.97(t,1H),6.51-6.52(d,2H),6.66-6.68(t,1H),7.06-7.10(t,2H),7.24-7.28(t,2H),7.36-7.38(d,2H),7.42-7.46(t,2H),7.78-7.79(d,2H).

Example 11

Phenyl acetate (220 mg,1.62 mmol) and bis-fluorosulfonyl imide (360 mg,1.99 mmol) were added to a 10ml single-port flask, the reaction was stirred at room temperature overnight, the disappearance of phenyl acetate was detected by TLC (petroleum ether: ethyl acetate=3:1), and purification by column chromatography (petroleum ether: ethyl acetate=3:1, rf=0.3) afforded 50mg (0.367 mmol) as a yellow solid in 23% yield.

¹H NMR(400MHz,d-DMSO):2.43(s,3H),6.79-6.81(d,2H),7.78-7.80(d,2H),

10.30(s,1H)。

Example 12

Phenyl acetate (330 mg,2.4 mmol) and bis-fluorosulfonyl imide (540 mg,2.98 mmol) were added to a 10ml single-port flask, stirred at 60℃for 3h, disappearance of phenyl acetate was detected by TLC (petroleum ether: ethyl acetate=3:1), and purification by column chromatography (petroleum ether: ethyl acetate=3:1, rf=0.3) gave 100mg (0.735 mmol) as a yellow solid in 30% yield.

¹H NMR(400MHz,d-DMSO):2.43(s,3H),6.79-6.81(d,2H),7.78-7.80(d,2H),10.30(s,1H)。

Example 13

Benzoic acid (0.21 g,1.72 mmol), anhydrous methanol (0.3 g,9.375 mmol) and toluene (1 ml) were added under nitrogen protection to a 25ml three-port flask, bis-fluorosulfonyl imide (31 mg,0.171mol,10% mol relative to benzoic acid) was added and reacted under stirring at 85℃for 12h, disappearance of benzoic acid was detected by TLC (petroleum ether: ethyl acetate=30:1), and purification by column chromatography (petroleum ether: ethyl acetate=30:1, rf=0.4) gave 160mg (1.18 mmol) as a colorless oily liquid in 68.6% yield.

¹H NMR(400MHz,CDCl₃):3.92(s,3H),7.42-7.45(t,2H),7.53-7.55(t,2H),8.03-8.05(d,2H)。

Example 14

To a 25ml single flask was added benzaldehyde (0.2198 g,2.07 mmol), triethylsilane (0.27 g,2.327 mmol) and dichloromethane (1 ml) under nitrogen protection, and bis-fluorosulfonyl imide (42 ul,0.5m dichloromethane solution, 1% mol relative to benzaldehyde) was added and reacted at room temperature with stirring for 30 minutes, and the disappearance of benzaldehyde was detected by TLC (petroleum ether: ethyl acetate=30:1), and the purification by column chromatography (petroleum ether: ethyl acetate=30:1, rf=0.4) gave 160mg (0.808 mmol) of colorless oily liquid in 78% yield.

¹H NMR(400MHz,CDCl₃):4.59(s,4H),7.38-7.40(m,10H)。

Example 15

4-Chlorobenzaldehyde (0.32 g, 2.284 mmol), triethylsilane (0.2927 g,2.52 mmol) and dichloromethane (1 ml) were added to a 25ml single port flask under nitrogen protection, and bis-fluorosulfonyl imide (45 ul,0.5M in dichloromethane, 1% mol relative to 4-chlorobenzaldehyde) was reacted at room temperature with stirring for 30 minutes, and the disappearance of benzaldehyde was detected by TLC (petroleum ether: ethyl acetate=30:1), and column chromatography purification (petroleum ether: ethyl acetate=30:1, rf=0.4) to give 260mg (0.974 mmol) of a white solid in 86% yield.

¹H NMR(400MHz,CDCl₃):4.52(s,4H),7.28-7.35(m,8H)。

Example 16

3-Methylbenzaldehyde (0.1387 g,1.156 mmol) was added to a 25ml single-port flask, triethylsilane (0.151 g,1.3 mmol) and methylene chloride (1 ml) were added under nitrogen protection, and bisfluorosulfonyl imide (23 ul,0.5M methylene chloride solution, 1 mol% relative to 3-methylbenzaldehyde) was added to react for 30 minutes under stirring at room temperature, and the disappearance of benzaldehyde was detected by TLC (petroleum ether: ethyl acetate=30:1), and column chromatography purification (petroleum ether: ethyl acetate=30:1, rf=0.6) to give 130mg (0.575 mmol) of a white solid in 99% yield.

¹H NMR(400MHz,CDCl₃):2.35(s,6H),4.52(s,4H),7.09-7.26(m,8H)。

Example 17

4-Methylbenzaldehyde (0.1507 g,1.256 mmol), triethylsilane (0.16 g,1.38 mmol) and dichloromethane (1 ml) were added to a 25ml single-port flask under nitrogen protection, bis-fluorosulfonyl imide (25 ul,0.5M in dichloromethane, 1% mol relative to 4-methylbenzaldehyde) was added, the reaction was stirred at room temperature for 1 hour, disappearance of benzaldehyde was detected by TLC (petroleum ether: ethyl acetate=30:1), and column chromatography purification (petroleum ether: ethyl acetate=30:1, rf=0.5) gave 131mg (0.58 mmol) as a white solid in 92% yield.

¹H NMR(400MHz,CDCl₃):2.35(s,6H),4.5(s,4H),7.14-7.17(d,4H),7.24-7.26(d,4H)。

Example 19

To a 10ml single port flask was added 250ul of a solution of tris (trimethylsilyl) silane in deuterated acetonitrile (0.5M), followed by a slow addition of 250ul of bis-fluorosulfonyl imide in deuterated acetonitrile (0.5M) in ice bath and a slow return to room temperature followed by a 1 hour reaction. Thus obtaining the target product solution.

¹⁹ F NMR (deuterated acetonitrile as solvent, fluorotrichloromethane as internal standard): +54

¹H NMR(400MHz,d-CD₃CN):0.17(S)。

Example 19

In a 20ml single flask was charged benzotriazole (0.111 g,0.933 mmol), 1- (trifluoromethyl) -3, 3-dimethyl-1, 2-benziodooxavaleric ring (0.2 g,0.6 mmol), acetonitrile (6 ml), bis-fluorosulfonimide (12 mg,0.066mmol,10% mol relative to 1- (trifluoromethyl) -3, 3-dimethyl-1, 2-benziodooxavaleric ring) and reacted at 60℃for 3.5 hours, TLC (petroleum ether: ethyl acetate=5:2), 1- (trifluoromethyl) -3, 3-dimethyl-1, 2-benziodooxavaleric ring was detected to disappear, the quantitative yield of the product via fluorine spectrum was 83% (based on benzotrifluoride as internal standard).

¹⁹ F NMR (acetonitrile as solvent, fluorotrichloromethane as internal standard): -53;

LC-MS：229(M+1)。

Comparative example 1

This comparative example is selected from the document org.

4-Hexen-3-one (0.5 mmol,1.0 eq) with benzyl carbamate (0.75 mmol,1.5 eq), acetonitrile (1 ml), bis (trifluoromethanesulfonyl) imide (0.05 mmol,10% eq) was added and reacted at 20℃for 10min to give 117mg of product in 95% yield. The use amount of the bis (trifluoromethanesulfonyl) imide is large, and the reaction condition is severe, and the bis (trifluoromethanesulfonyl) imide needs to be carried out at the temperature of minus 20 ℃.

Comparative example 2

This comparative example is selected from J.org.chem.1987,52,4314-4319.

In reductive etherification of carbonyl compounds, as described in this document 4318, page experiment method a, trimethylsilyl triflate (TRIMETHYLSILYL TRIFLATE,44.45mg,0.20mmol,10% eq) and triethylsilyl hydrogen (0.460 g,4mmol,2 eq) were dissolved in 4ml dichloromethane, benzaldehyde (0.212 g,2mmol,1 eq) was added under ice bath and reacted at room temperature for 2 hours and purified by column chromatography (petroleum ether: ethyl acetate=30:1, rf=0.4) to give 0.1299g colorless oily liquid in 65.6% yield.

¹H NMR(400MHz,CDCl₃):4.59(s,4H),7.38-7.40(m,10H)。

Claims

1. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (IV), comprising the steps of:

Wherein,

X is NH, S or O;

2. Use according to claim 1, wherein in R ⁷、R⁸ or R ⁹, said C1-C16 alkyl is a C1-C10 alkyl, preferably a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);

And/or, in R ⁷、R⁸ or R ⁹, the C6-C10 aryl and the C6-C10 aryl of the R ^C substituted C6-C10 aryl are independently phenyl;

And/or, in R ⁷、R⁸ or R ⁹, the number of substitutions of R ^C in the benzyl group substituted by R ^C is 1 to 3 (for example, 1), and each R ^C is the same or different;

And/or, in R ^C, the halogen is fluorine, chlorine, bromine or iodine;

And/or, in R ^C, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;

And/or, in R ^C, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;

and/or, X is NH;

And/or, in the preparation of the compound shown in the formulSup>A (IV), the use amount of the bisfluorosulfonyl imide is 1-10% (such as 5%) of the molar amount of the compound shown in the formulSup>A (IV-A);

And/or, in the preparation of the compound shown in the formulSup>A (IV), the molar ratio of the compound shown in the formulSup>A (IV-A) to the compound shown in the formulSup>A (IV-B) is 1 (1-10), for example, 1:1;

And/or in the preparation of the compound shown in the formula (IV), the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, and further such as acetonitrile;

and/or, in the preparation of the compound represented by the formula (IV), the temperature of the addition reaction is 20 ℃ to the reflux temperature of the solvent, for example, room temperature;

and/or, in the preparation of the compound represented by the formula (IV), the time of the addition reaction is 10 minutes to 12 hours, for example, 0.5 hours.

3. Use according to claim 2, wherein R ⁷ and R ⁸ are independently C1-C16 alkyl, such as C1-C10 alkyl, further such as C1-C6 alkyl (such as C1-C3 alkyl, further such as methyl, ethyl, n-propyl or isopropyl); preferably, the compound represented by the formulSup>A (IV-A) is

And/or R ⁹ isPreferably, the compound represented by the formula (IV-B) is

4. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (V), comprising the steps of:

Wherein Y is halogen,

r ¹¹ is C1-C6 alkyl or C1-C6 alkoxy.

5. The use according to claim 4, wherein in Y, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine, bromine or iodine;

And/or, in R ¹⁰, said C1-C16 alkyl is C1-C10 alkyl, for example C1-C6 alkyl (for example C1-C3 alkyl, for example methyl, ethyl, n-propyl or isopropyl);

And/or, in R ¹⁰, the C6-C10 aryl and the C6-C10 aryl of the R ^D substituted C6-C10 aryl are independently phenyl;

and/or, in R ¹⁰, the number of substitutions of R ^D in the C6-C10 aryl substituted by R ^D is 1-3 (for example, 1), and each R ^D is the same or different;

And/or, in R ¹⁰, the number of substitutions of R ^E in the benzyl group substituted by R ^E is 1 to 3 (for example, 1), and each R ^E is the same or different;

and/or, in R ^D or R ^E, the halogen is fluorine, chlorine, bromine or iodine;

And/or, in R ^D、R^E or R ¹¹, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;

and/or, in R ^D、R^E or R ¹¹, said C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;

And/or Y is

And/or, in the preparation of the compound shown in the formula (V), the use amount of the bisfluorosulfonyl imide is 0.1-10% (for example, 5%) of the molar amount of the compound shown in the formula (V-B);

And/or, in the preparation of the compound shown as the formulSup>A (V), the molar ratio of the compound shown as the formulSup>A (V-A) to the compound shown as the formulSup>A (V-B) is (1-10): 1, for example, 1:1;

and/or in the preparation of the compound shown in the formula (V), the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, and further such as dichloromethane;

And/or, in the preparation of the compound represented by formula (V), the temperature of the friedel-crafts reaction is 20 ℃ to the reflux temperature of the solvent, for example, room temperature;

And/or, in the preparation of the compound shown as the formula (V), the Friedel-crafts reaction time is 5 minutes to 12 hours, for example, 0.5 hour.

6. The use according to claim 5, wherein R ^D and R ^E are independently C1-C6 alkoxy; preferably, R ¹⁰ is benzyl, phenyl, R ^D -substituted phenyl, or R ^E -substituted benzyl; more preferably, the compound represented by the formulSup>A (V-A) is

And/or R ¹¹ is C1-C6 alkoxy; preferably, the compound represented by the formula (V-B) is

7. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (VI), comprising the steps of:

8. Use according to claim 7, wherein in R ¹², said C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);

And/or, in R ¹², the C6-C10 aryl and the C6-C10 aryl of the R ^F substituted C6-C10 aryl are independently phenyl;

And/or, in R ¹², the number of substitutions of R ^F in the C6-C10 aryl substituted by R ^F is 1-3 (for example, 1), and each R ^F is the same or different;

And/or, in the preparation of the compound shown in the formula (VI), the use amount of the bisfluorosulfonyl imide is 5-30% (for example, 10%) of the molar amount of the compound shown in the formula (VI-A);

And/or, in the preparation of the compound shown in the formula (VI), the molar ratio of the compound shown in the formula (VI-A) to water is 1 (1-10), such as 1:2.9;

And/or in the preparation of the compound shown in the formula (VI), the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, for example, 1, 4-dioxane;

And/or, in the preparation of the compound represented by formula (VI), the temperature of the hydrolysis reaction is 20 ℃ to the reflux temperature of the solvent, for example 100 ℃;

And/or, in the preparation of the compound represented by the formula (VI), the hydrolysis reaction time is 2 to 12 hours, for example 8 hours.

9. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (VII), comprising the steps of:

10. Use according to claim 9, wherein in R ¹³ or R ¹⁴, said C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);

And/or, in R ¹³ or R ¹⁴, the C6-C10 aryl and the C6-C10 aryl of the R ^G substituted C6-C10 aryl are independently phenyl;

and/or, in R ^G, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine;

And/or, in R ^G, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;

And/or, in R ^G, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;

And/or, in R ¹³ or R ¹⁴, the number of substitutions of R ^G in the C6-C10 aryl substituted by R ^G is 1 to 3 (for example, 1), and each R ^G is the same or different;

and/or, in the preparation of the compound shown in the formula (VII), the use amount of the bisfluorosulfonyl imide is 5-30%, such as 10%, of the molar amount of the compound shown in the formula (VII-A);

And/or, in the preparation of the compound shown as the formula (VII), the molar ratio of the compound shown as the formula (VII-A) to the allyltrimethylsilane is 1 (1-10), such as 1:1.2;

And/or in the preparation of the compound shown in the formula (VII), the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, and further such as dichloromethane;

And/or, in the preparation of the compound represented by the formula (VII), the temperature of the reaction is-20 ℃ to room temperature, for example, room temperature;

and/or, in the preparation of the compound represented by the formula (VII), the reaction time is 2 to 12 hours, for example, 2 hours.

11. The use according to claim 10, wherein R ¹³ and R ¹⁴ are independently phenyl or R ^G substituted phenyl, R ^G is C1-C3 alkoxy; preferably, the compound represented by the formula (VII-A) is

12. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (X), comprising the steps of:

13. Use according to claim 12, wherein in R ²² or R ²³, said C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);

And/or, in R ²² or R ²³, C6-C10 aryl of the C6-C10 aryl, the R ^J substituted C6-C10 aryl, and the R ^K substituted C6-C10 aryl are independently phenyl;

And/or, in R ^J or R ^K, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine;

And/or, in R ^J or R ^K, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;

And/or, in R ^J or R ^K, said C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;

And/or, in R ²², the number of substitutions of R ^J in the C6-C10 aryl substituted by R ^J is 1-3 (for example, 1), and each R ^J is the same or different;

And/or, in R ²³, the number of substitutions of R ^K in the C6-C10 aryl substituted by R ^K is 1-3 (for example, 1), and each R ^K is the same or different;

And/or, in the preparation of the compound shown in the formula (X), the use amount of the bisfluorosulfonyl imide is 0.1% -10%, such as 10%, of the molar amount of the compound shown in the formula (X-A);

and/or, in the preparation of the compound shown as the formula (X), the molar ratio of the compound shown as the formula (X-A) to the compound shown as the formula (X-B) is 1 (1-10), such as 1:5.5;

And/or, in the preparation of the compound represented by the formula (X), the reaction is carried out in a solvent or in a solvent-free state, the solvent being one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a haloalkane solvent and an alkane solvent, for example, one or more of tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide and 1, 4-dioxane, for example, toluene; preferably, the reaction is carried out in the absence of a solvent;

And/or, in the preparation of the compound represented by the formula (X), the temperature of the reaction is room temperature-the reflux temperature of the solvent used, for example, 85 ℃;

and/or, in the preparation of the compound represented by the formula (X), the reaction time is 2 to 12 hours, for example, 12 hours.

14. Use of a bis-fluorosulfonyl imide as a catalyst in the reductive etherification of carbonyl compounds of formula (XI-a), comprising the steps of:

15. Use according to claim 14, wherein in R ²⁴ or R ²⁵, said C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);

And/or, in R ²⁴ or R ²⁵, the C6-C10 aryl and the C6-C10 aryl of the R ^L substituted C6-C10 aryl are independently phenyl;

And/or, in R ^L, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine;

And/or, in R ^L, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;

And/or, in R ^L, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;

And/or, in R ²⁴ or R ²⁵, the number of substitutions of R ^L in the C6-C10 aryl substituted by R ^L is 1 to 3 (for example, 1), and each R ^L is the same or different;

And/or R ^24-1 is methyl, ethyl, n-propyl or isopropyl;

and/or, in the reduction etherification reaction of the carbonyl compound shown in the formula (XI-A), the use amount of the bisfluorosulfonyl imide is 0.1-10%, such as 0.1-5%, and still more such as 1% of the molar amount of the carbonyl compound shown in the formula (XI-A);

And/or, in the reduction etherification reaction of the carbonyl compound shown in the formula (XI-A), the molar ratio of the carbonyl compound shown in the formula (XI-A) to the silane compound shown in the formula (XI-B) is 1 (1-2), for example, 1:1.12 or 1:1.10;

And/or in the reductive etherification reaction of the carbonyl compound shown in the formula (XI-A), the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, such as dichloromethane;

and/or, in the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the temperature of the reductive etherification reaction is 0 ℃ to room temperature, for example, room temperature;

and/or, in the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the time of the reductive etherification reaction is 5 minutes to 12 hours, for example, 0.5 hours or 1 hour.

16. The use according to claim 15, wherein R ²⁴ and R ²⁵ are independently H, phenyl or R ^L substituted phenyl, preferably the carbonyl compound of formula (XI-a)

17. A method for preparing silicon bis-fluorosulfonyl imide represented by the formula (XII), comprising the steps of:

18. The method of claim 17, wherein in Z, R ²⁶、R²⁷ or R ²⁸, the C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g., a C1-C3 alkyl, such as methyl, ethyl, n-propyl, or isopropyl);

And/or, Z, R ²⁶、R²⁷ or R ²⁸, C6-C10 aryl of the C6-C10 aryl, the R ^N substituted C6-C10 aryl, and the R ^M substituted C6-C10 aryl are independently phenyl;

And/or Z, R ^M or R ^N, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine;

and/or, in R ^M or R ^N, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;

And/or, in R ^M or R ^N, said C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;

And/or, in R ²⁶、R²⁷ or R ²⁸, the number of substitutions of R ^M in the C6-C10 aryl substituted by R ^M is 1 to 3 (for example, 1), and each R ^M is the same or different;

And/or, in Z, the number of substitutions of R ^N in the C6-C10 aryl substituted by R ^N is 1-3 (for example, 1), and each R ^N is the same or different;

And/or, in R ²⁹、R³⁰ or R ³¹, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;

And/or, in the preparation method of the silicon bis (fluorosulfonyl) imide represented by the formula (XII), the molar ratio of the compound represented by the formula (XII-A) to the bis (fluorosulfonyl) imide is (1-10): 1, e.g., 1:1;

And/or, in the preparation method of the silicon bisfluorosulfonyl imide shown in the formula (XII), the reaction is carried out in a solvent or in a solvent-free state, wherein the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, further such as acetonitrile or dichloromethane; preferably, the reaction is carried out in the absence of a solvent;

And/or, in the preparation method of the silicon bisfluorosulfonyl imide shown in the formula (XII), the temperature of the reaction is 0-room temperature, such as room temperature;

and/or, in the method for producing silicon bisfluorosulfonyl imide represented by the formula (XII), the reaction time is 30 minutes to 2 hours, for example, 1 hour.

19. The method of claim 18, wherein R ²⁶、R²⁷ and R ²⁸ are independentlyR ²⁹、R³⁰ and R ³¹ are independently C1-C3 alkyl (e.g., methyl, ethyl, n-propyl, or isopropyl);

and/or Z is H or halogen, preferably Z is H.

20. Use of a bis-fluorosulfonyl imide as a catalyst in a rearrangement reaction of a compound of formula (IX), comprising the steps of:

21. Use according to claim 20, wherein in R ²¹, said C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);

And/or, in R ²¹, the C6-C10 aryl and the C6-C10 aryl of the R ^I substituted C6-C10 aryl are independently phenyl;

And/or, in R ^I, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine;

And/or, in R ^I, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;

And/or, in R ^I, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;

And/or, in R ²¹, the number of substitutions of R ^I in the C6-C10 aryl substituted by R ^I is 1-3 (for example, 1), and each R ^I is the same or different;

And/or, in the rearrangement reaction of the compound shown in the formula (IX), the amount of the bisfluorosulfonyl imide is 20% -150%, for example 100% -150%, still more for example 123% or 124% of the molar amount of the compound shown in the formula (IX);

And/or in the rearrangement reaction of the compound shown as the formula (IX), the rearrangement reaction is carried out in a solvent or in a solvent-free state, and the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide, and 1, 4-dioxane; preferably, the rearrangement reaction is carried out in the absence of a solvent;

and/or, in the rearrangement reaction of the compound represented by the formula (IX), the temperature of the rearrangement reaction is 20 ℃ to 150 ℃, for example, room temperature, 60 ℃;

and/or, in the rearrangement reaction of the compound represented by the formula (IX), the time of the rearrangement reaction is 2 to 12 hours, for example, 3 hours.

22. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (XIII), comprising the steps of:

Wherein Q is CH or N;

r ³² is halogen, C1-C16 alkyl, C6-C10 aryl or R ^O substituted C6-C10 aryl;

m ₃ is 0, 1, 2,3 or 4;

R ³³ is C1-C16 alkyl, C6-C10 aryl or R ^P substituted C6-C10 aryl;

R ^O and R ^P are independently halogen, C1-C6 alkyl or C1-C6 alkoxy.

23. The use according to claim 22, wherein in R ³², the halogen is fluorine, chlorine, bromine or iodine, such as chlorine;

and/or R ³² or R ³³, said C1-C16 alkyl is, for example, C1-C10 alkyl, further for example, C1-C6 alkyl (e.g., C1-C3 alkyl, further for example, methyl, ethyl, n-propyl or isopropyl);

And/or, in R ³² or R ³³, C6-C10 aryl of the C6-C10 aryl, the R ^O substituted C6-C10 aryl, and the R ^P substituted C6-C10 aryl are independently phenyl;

And/or, in R ^O or R ^P, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine;

And/or, in R ^O or R ^P, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;

And/or, in R ^O or R ^P, said C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;

and/or, in R ³², the number of substitutions for R ^O in the R ^O substituted C6-C10 aryl group may be 1 to 3 (e.g., 1), each R ^O being the same or different;

And/or, in R ³³, the number of substitutions for R ^P in the R ^P substituted C6-C10 aryl group may be 1 to 3 (e.g., 1), each R ^P being the same or different;

And/or, in the preparation of the compound represented by the formula (XIII), the amount of the bisfluorosulfonyl imide is preferably 5% to 20%, for example 10%, of the molar amount of the compound represented by the formula (XIII-B);

and/or, in the preparation of the compound shown in the formula (XIII), the molar ratio of the compound shown in the formula (XIII-A) to the compound shown in the formula (XIII-B) is (1-2): 1, for example, 1:5.1;

And/or, in the preparation of the compound shown in the formula (XIII), the molar ratio of the compound shown in the formula (XIII-C) to the compound shown in the formula (XIII-B) is (1-200): 1;

and/or in the preparation of the compound shown in the formula (XIII), the reaction is carried out in a solvent or in a solvent-free state, wherein the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, for example, acetonitrile or dichloromethane; preferably, the reaction is carried out in the absence of a solvent;

And/or, in the preparation of the compound represented by formula (XIII), the temperature of the reaction is 50-120 ℃, for example 60 ℃;

And/or, in the preparation of the compound represented by the formula (XIII), the reaction time is 1 to 5 hours, for example, 3.5 hours.

24. Use according to claim 23, wherein m ₃ is 0 or 1, preferably m ₃ is 0;

And/or, Q is N;

and/or R ³³ is C1-C6 alkyl, such as C1-C3 alkyl, further such as methyl, ethyl, n-propyl or isopropyl.