CN110845506B

CN110845506B - Amination reagent and preparation method and application thereof

Info

Publication number: CN110845506B
Application number: CN201911145404.9A
Authority: CN
Inventors: 刘超; 刘钘钘
Original assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Current assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Priority date: 2019-11-21
Filing date: 2019-11-21
Publication date: 2022-03-15
Anticipated expiration: 2039-11-21
Also published as: CN110845506A

Abstract

The invention discloses an amination reagent and a preparation method and application thereof. The amination reagent has a structure shown by the following formula:

wherein X is selected from I, Cl, Br and NO₃、ClO₄Y, Z are independently selected from H or C1-4 alkyl. The method for preparing the amination reagent has the advantages of simple process, easily obtained raw materials, lower cost and stable yield, and the prepared amination reagent has stable properties, can be stored at room temperature for a long time and can be taken at any time; meanwhile, the amination reagent prepared by the invention has high performance, wide applicability of boron substrates and good reaction effect, and greatly expands the limitation of the amination reaction of organic boron compounds on the substrates.

Description

Amination reagent and preparation method and application thereof

Technical Field

The invention belongs to the technical field of fine chemical engineering, and particularly relates to an amination reagent and a preparation method and application thereof.

Background

With the continuous development of organic synthetic chemistry, more and more researchers are aware that it is of great significance to develop organic synthetic substrates with wide sources, economic cost and good transformation performance. In recent years, organoboron compounds have been favored by researchers, and provide new solutions to many of the difficulties in organic synthesis. Amine compounds are always important components in organic synthesis, and have important significance in biological, pharmaceutical and chemical industries. From current research, boronic acid substrates, which resemble boron compound amination reactions, often select more reactive aryl groups, which limits the diversity of synthetic substrates to some extent. At present, amination research on general alkyl borate and aryl borate compounds is less, and if the problem of substrate conversion can be solved, the method has great significance for development of organoboron compounds. Therefore, the invention provides the efficient amination reagent which is convenient to synthesize, economic in source and capable of being stored for a long time, and can well realize amination reaction of the borate substrate.

Disclosure of Invention

The invention mainly aims to provide an amination reagent, a preparation method and application thereof, so as to overcome the defects of the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

embodiments of the present invention provide an amination reagent having a structure as shown in formula (I) or (II):

wherein X is selected from I, Cl, Br and NO₃、ClO₄Y, Z are independently selected from H or C1-4 alkyl.

The embodiment of the invention also provides a preparation method of the amination reagent, which comprises the following steps:

after a first uniform mixing reaction system containing triethylene diamine, hydroxylamine-O-sulfonic acid and a first solvent is reacted, adding alkali into the first uniform mixing reaction system for continuous reaction, and reacting a second uniform mixing reaction system containing a first solid obtained by the reaction, a second solvent and an acid or iodo-alkyl compound to obtain an amination reagent shown in formula (I) or (II), wherein Y is H;

or reacting a third uniformly mixed reaction system containing triethylene diamine, an iodoalkyl compound and a third solvent, reacting a fourth uniformly mixed reaction system containing a second solid obtained by the reaction, hydroxylamine-O-sulfonic acid and a first solvent, adding alkali into the fourth uniformly mixed reaction system, and continuing to react a fifth uniformly mixed reaction system containing the third solid obtained by the reaction, the second solvent, an acid or the iodoalkyl compound to obtain the amination reagent shown in the formula (I), wherein Y is selected from alkyl with 1-4 carbon atoms.

The embodiment of the present invention also provides an amination reaction of an organoboron compound, which includes:

providing an amination reagent as claimed in claim 1;

reacting a uniformly mixed reaction system containing an organic boron compound, the amination reagent, an alkaline substance and a solvent for 1-3 hours at 80-100 ℃ in a protective atmosphere;

and adding trifluoroacetic anhydride into the mixed system obtained by the reaction in an air atmosphere, continuing the reaction for 1-2 h at the temperature of 80-100 ℃, and then adding a quenching agent to quench the reaction to obtain an organic boron amination product.

Compared with the prior art, the invention has the beneficial effects that: the method for preparing the amination reagent has the advantages of simple process, easily obtained raw materials, lower cost and stable yield, and the prepared amination reagent has stable properties, can be stored at room temperature for a long time and can be taken at any time; meanwhile, the amination reagent prepared by the invention has high performance, wide applicability of boron substrates and good reaction effect, and greatly expands the limitation of the amination reaction of organic boron compounds on the substrates.

Detailed Description

In view of the defects of the prior art, the inventor of the present invention has made extensive studies and practice to provide the technical solution of the present invention, which mainly utilizes the migration characteristic of boron substrate to construct a novel migration structure, and uses N as a linking group to construct N-NH₂Or N-NH-R is a novel structure, and a new leaving group which is easy to leave and contains a DABCO structure is constructed, so that the reaction activity of the amination reagent is improved, and meanwhile, the amination reagent can exist stably and can be taken at any time, the experimental operation steps are simplified, and the amination reaction is more efficient and convenient.

The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

One aspect of embodiments of the present invention provides an amination reagent for use in amination reactions, said amination reagent having a structure according to formula (I) or (II):

wherein X is selected from I, Cl, Br and NO₃、ClO₄Y, Z are independently selected from H or C14 alkyl group.

Further, the alkyl group includes any one of methyl, ethyl, propyl, isopropyl, butyl, and tert-butyl, and is not limited thereto.

In another aspect of an embodiment of the present invention, there is provided a method for preparing the foregoing amination reagent, comprising:

In some more specific embodiments, the method of preparing the amination reagent comprises:

s1, respectively dissolving triethylene diamine and hydroxylamine-O-sulfonic acid in a first solvent, mixing to form a first uniformly mixed reaction system, reacting at 80-100 ℃ for 1-2 h, adding alkali into the first uniformly mixed reaction system, continuously reacting at 10-25 ℃ for 10-30 min, and concentrating and washing to obtain a first solid matter;

s2, dissolving the first solid obtained in the step S1 in a second solvent to form a solution, adding an acid or iodoalkyl compound into the solution to form a second uniformly mixed reaction system, and reacting at-20 to-78 ℃ for 1 to 3 hours to obtain the amination reagent shown in the formula (I) or (II), wherein Y is H.

Further, the molar ratio of the triethylene diamine, the hydroxylamine-O-sulfonic acid, the alkali, the acid or the iodo-alkyl compound is 3.0: 1.0: (1.0-2.0): 1.0.

further, the washing treatment in step S1 is tetrahydrofuran washing; preferably, the number of washing is 4 or more.

s1, dissolving triethylene diamine in a third solvent to form a solution, adding an iodoalkyl compound into the solution to form a third uniformly mixed reaction system, reacting at 0-30 ℃ for 10-18 h, and distilling, washing and drying to obtain a second solid matter;

s2, respectively dissolving the second solid matter obtained in the step S1 and hydroxylamine-O-sulfonic acid in a first solvent, mixing to form a fourth uniformly mixed reaction system, reacting at 80-100 ℃ for 1-2 h, adding alkali into the fourth uniformly mixed reaction system, continuing to react at 10-25 ℃ for 10-30 min, and concentrating and washing to obtain a third solid matter;

s3, dissolving the third solid obtained in the step S2 in a second solvent to form a solution, adding an acid or iodoalkyl compound into the solution to form a fifth uniformly mixed reaction system, and reacting at-20 to-78 ℃ for 1 to 3 hours to obtain the amination reagent shown in the formula (I), wherein Y is selected from alkyl with 1 to 4 carbon atoms.

Further, the molar ratio of the triethylene diamine, the iodo-alkyl compound, the hydroxylamine-O-sulfonic acid, the alkali, the acid or the iodo-alkyl compound is 3.0: 3.0: 1.0: (1.0-2.0): 1.0.

further, the third solvent includes any one of n-hexane, petroleum ether, n-pentane, and cyclohexane, and is not limited thereto.

Further, the washing treatment in step S1 is Tetrahydrofuran (THF) washing; preferably, the number of washing is 4 or more.

In some more specific embodiments, the acid comprises HI, HCl, HBr, HNO₃、HClO₄Without being limited thereto。

Further, the first solvent includes any one of water, methanol, and acetonitrile, and is not limited thereto.

Further, the second solvent includes any one of ethanol, methanol, and isopropanol, and is not limited thereto.

Further, the base includes any one of potassium carbonate, potassium bicarbonate, and sodium carbonate, and is not limited thereto.

Further, the iodoalkyl compound includes any one of methyl iodide, ethyl iodide, propyl iodide, isopropyl iodide, butyl iodide, and tert-butyl iodide, but is not limited thereto.

In another aspect of the embodiments of the present invention, there is provided an amination reaction of an organoboron compound, including:

providing the foregoing amination reagent;

and adding trifluoroacetic anhydride (TFAA) into the mixed system obtained by the reaction in an air atmosphere, continuing the reaction for 1-2 h at the temperature of 80-100 ℃, and then adding a quenching agent to quench the reaction to obtain an organic boron amination product.

Further, the production method according to claim 8, characterized in that: the dosage ratio of the organic boron compound, the amination reagent and the organic base is 1: (1-2): (2.4-4.8);

further, the molar ratio of the trifluoroacetic anhydride to the organoboron compound is 2: 1-4: 1; preferred molar ratios are 2:1 and 4: 1.

Further, the organoboron compound includes any one of an alkyl borate, an aryl borate, and an alkyl diboronate, and is not limited thereto.

Further, the alkyl borate includes any one of a primary alkyl borate, a secondary alkyl borate, and a tertiary alkyl borate, and is not limited thereto.

Further, the solvent includes any one of tetrahydrofuran, toluene, and acetonitrile, and is not limited thereto.

Further, the basic substance includes any one of potassium tert-butoxide, sodium hydride, magnesium methoxide, sodium methoxide, and sodium tert-butoxide, without being limited thereto.

Further, the quenching agent includes any one of ethyl acetate, water, and dichloromethane, and is not limited thereto.

The technical solution of the present invention is further described in detail with reference to several preferred embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.

The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.

Example 1

Preparation of aminating reagent a

(1) Weighing 10mmol (1.13g) of hydroxylamine-O-sulfonic acid, 30mmol (3.37g) of triethylene diamine and magneton in a 25mL Hiike reaction tube, adding 5mL of water, sealing a cock, placing the Hiike reaction tube in a heating module at 90 ℃, and stirring for reacting for 1 h; after the reaction is finished, cooling the reaction tube to room temperature, opening a cock, adding 10mmol (1.38g) of potassium carbonate into the system, stirring at room temperature for 10min, carrying out rotary evaporation and concentration on the reaction liquid, adding 10mmol (1.38g) of potassium carbonate into a rotary evaporation round-bottom flask after the first rotary evaporation is finished, fully stirring, and continuously carrying out rotary evaporation until the reaction is dry. Adding about 25mL of tetrahydrofuran into a round-bottom flask, adding magnetophores, fully stirring, standing, sucking out a supernatant, continuously adding tetrahydrofuran into lower-layer solid particles, washing, and repeating the operation for 4 times. Wherein, the reaction in the step (1) is shown as the following formula:

(2) and collecting solid matters in the round-bottom flask, adding 8mL of absolute ethyl alcohol, fully stirring, carrying out suction filtration, and collecting filtrate. Transferring the filtrate to a 25mL sealed tube, putting the Hirak reaction tube into a low-temperature cooling bath at-78 ℃, slowly adding 10mmol (1.4mL) of hydroiodic acid into the Hirak reaction tube, sealing, and stirring for reaction for 1 h. After the reaction is finished, carrying out suction filtration, washing a filter cake with ethanol, collecting the filter cake, and drying to obtain an amination reagent a, wherein the reaction process in the step (2) is shown as the following formula:

the amination reagent a nuclear magnetic data for this example are as follows:¹HNMR(400MHz,D₂O)δ3.98-3.92(m,6H),3.78-3.72(m,6H)ppm；¹³C NMR(101MHz,D₂O)δ56.4,44.9ppm.

example 2

Preparation of aminating reagent a

(1) Weighing 10mmol (1.13g) of hydroxylamine-O-sulfonic acid, 30mmol (3.37g) of triethylene diamine and magneton in a 25mL Hiike reaction tube, adding 5mL of methanol, sealing a cock, placing the Hiike reaction tube in a heating module at 80 ℃, and stirring for reaction for 2 hours; after the reaction is finished, cooling the reaction tube to room temperature, opening the cock, adding 10mmol (1.06g) of sodium carbonate into the system, stirring for 10min at room temperature, and then carrying out rotary evaporation and concentration on the reaction liquid to be dry. Adding 25mL of tetrahydrofuran into a round-bottom flask, adding magnetophores, fully stirring, standing, sucking out a supernatant, continuously adding tetrahydrofuran into lower-layer solid particles, washing, and repeating the operation for 4 times. Wherein, the reaction in the step (1) is shown as the following formula:

(2) the solid material in the round bottom flask was collected, 8mL of isopropanol was added, stirred well, filtered with suction and the filtrate was collected. The filtrate was transferred to a 25mL sealed tube while placing the claick reaction tube in a-20 ℃ low temperature cold bath, 1.4mL (1.0eq.) of hydroiodic acid was slowly added to the claick reaction tube, and after sealing, the reaction was stirred for 3 hours. After the reaction is finished, carrying out suction filtration, washing a filter cake with isopropanol, collecting the filter cake, and drying to obtain an amination reagent a, wherein the reaction process in the step (2) is shown as the following formula:

example 3

Preparation of aminating reagent a

(1) Weighing 10mmol (1.13g) of hydroxylamine-O-sulfonic acid, 30mmol (3.37g) of triethylene diamine and magneton in a 25mL Hiike reaction tube, adding 5mL of acetonitrile, sealing a cock, placing the Hiike reaction tube in a heating module at 100 ℃, and stirring for reaction for 1 h; after the reaction is finished, cooling the reaction tube to room temperature, opening a cock, adding 10mmol (1.00g) of potassium bicarbonate into the system, stirring at room temperature for 30min, and then carrying out rotary evaporation and concentration on the reaction liquid to be dry. Adding 25mL of tetrahydrofuran into a round-bottom flask, adding magnetophores, fully stirring, standing, sucking out a supernatant, continuously adding tetrahydrofuran into lower-layer solid particles, washing, and repeating the operation for 4 times. Wherein, the reaction in the step (1) is shown as the following formula:

(2) the solid material in the round bottom flask was collected, 8mL of methanol was added, stirred well, filtered with suction, and the filtrate was collected. Transferring the filtrate to a 25mL sealed tube, putting the Hirak reaction tube into a low-temperature cooling bath at the temperature of-30 ℃, slowly adding 10mmol (1.4mL) of hydroiodic acid into the Hirak reaction tube, sealing, and stirring for reacting for 2 h. After the reaction is finished, carrying out suction filtration, washing a filter cake with methanol, collecting the filter cake, and drying to obtain an amination reagent a, wherein the reaction process in the step (2) is shown as the following formula:

example 4

Preparation of aminating reagent b

Weighing 10mmol (1.13g) of hydroxylamine-O-sulfonic acid, 30mmol (3.37g) of triethylene diamine and magneton in a 25mL Hiike reaction tube, adding 5mL of water, sealing a cock, placing the Hiike reaction tube in a heating module at 90 ℃, and stirring for reacting for 1 h; after the reaction is finished, cooling the reaction tube to room temperature, opening a cock, adding 10mmol (1.38g) of potassium carbonate into the system, stirring at room temperature for 20min, carrying out rotary evaporation and concentration on the reaction liquid, adding 10mmol (1.38g) of potassium carbonate into a rotary evaporation round-bottom flask after the first rotary evaporation is finished, fully stirring, and continuously carrying out rotary evaporation until the reaction is dry. Adding about 25mL of tetrahydrofuran into a round-bottom flask, adding magnetophores, fully stirring, standing, sucking out a supernatant, continuously adding tetrahydrofuran into lower-layer solid particles, washing, and repeating the operation for 4 times. Wherein, the reaction in the step (1) is shown as the following formula:

(2) and collecting solid matters in the round-bottom flask, adding 8mL of absolute ethyl alcohol, fully stirring, carrying out suction filtration, and collecting filtrate. Transferring the filtrate to a 25mL sealed tube, putting the Hirak reaction tube into a low-temperature cooling bath at-78 ℃, slowly adding 10mmol (0.8mL) of iodoethane into the Hirak reaction tube, sealing, and stirring for reaction for 1 h. After the reaction is finished, carrying out suction filtration, washing a filter cake with ethanol, collecting the filter cake, and drying to obtain an amination reagent b, wherein the reaction process in the step (2) is shown as the following formula:

the amination reagent b nuclear magnetic data for this example are as follows:¹HNMR(400MHz,D₂O)δ3.38-3.30(m,6H),2.90-2.78(m,6H),2.71-2.65(m,2H),1.01(t,J＝7.6Hz,3H)ppm；¹³C NMR(101MHz,D₂O)δ67.0,48.4,36.0,14.0ppm.

example 5

Preparation of aminating reagent c

(1) Weighing 10mmol (1.13g) of hydroxylamine-O-sulfonic acid, 30mmol (3.37g) of triethylene diamine and magneton in a 25mL Hiike reaction tube, adding 5mL of water, sealing a cock, placing the Hiike reaction tube in a heating module at 90 ℃, and stirring for reacting for 1 h; after the reaction is finished, cooling the reaction tube to room temperature, opening a cock, adding 10mmol (1.38g) of potassium carbonate into the system, stirring at room temperature for 10min, carrying out rotary evaporation and concentration on the reaction liquid, adding 10mmol (1.38g) of potassium carbonate into a rotary evaporation round-bottom flask after the first rotary evaporation is finished, fully stirring, and continuously carrying out rotary evaporation until the reaction is dry. Adding 25mL of tetrahydrofuran into a round-bottom flask, adding magnetophores, fully stirring, standing, sucking out a supernatant, continuously adding tetrahydrofuran into lower-layer solid particles, washing, and repeating the operation for 4 times. Wherein, the reaction in the step (1) is shown as the following formula:

(2) and collecting solid matters in the round-bottom flask, adding 8mL of absolute ethyl alcohol, fully stirring, carrying out suction filtration, and collecting filtrate. Transferring the filtrate to a 25mL sealed tube, putting the Hirak reaction tube into a low-temperature cooling bath at-78 ℃, slowly adding 10mmol (1.1mL) of perchloric acid into the Hirak reaction tube, sealing, and stirring for reaction for 1 h. After the reaction is finished, carrying out suction filtration, washing a filter cake with ethanol, collecting the filter cake, and drying to obtain an amination reagent c, wherein the reaction process in the step (2) is shown as the following formula:

the amination reagent c nuclear magnetic data for this example is as follows:¹HNMR(400MHz,D₂O)δ3.89-3.76(m,6H),3.70-3.62(m,6H)ppm；¹³C NMR(101MHz,D₂O)δ56.0,43.9ppm.

example 6

Preparation of aminating reagent d

(1) Taking a round-bottom flask, dissolving 30mmol (3.37g) of triethylene diamine in 10mL of n-hexane, adding 30mmol (4.23g) of methyl iodide into the system, and stirring at 0 ℃ for reacting for 18h, wherein the reaction in the step (1) is shown as the following formula:

(2) after the reaction is finished, the reaction solvent is dried by a rotary evaporator, the solid is washed by n-hexane for 2 times, and the white solid is obtained by drying again. Respectively dissolving the white solid and hydroxylamine-O-sulfonic acid in water, mixing, heating at 90 ℃, and stirring for reaction for 1 h. After the reaction mixture was cooled, 10mmol (1.38g) of potassium carbonate was added thereto, and the reaction mixture was stirred at room temperature for 10 min. And (2) carrying out rotary evaporation and concentration on the reaction liquid to obtain a solid substance, washing with tetrahydrofuran, collecting the solid, dissolving the solid in ethanol, carrying out vacuum filtration, collecting filtrate, adding 10mmol (1.4mL) of hydroiodic acid at-78 ℃, stirring for reacting for 1h to obtain corresponding ammonium salt, collecting solid particles, and drying to obtain an amination reagent d, wherein the reaction in the step (2) is shown as the following formula:

the amination reagent d nuclear magnetic data for this example is as follows:¹HNMR(400MHz,D₂O)δ4.22-4.15(m,6H),4.14-4.08(m,6H),3.40-3.37(s,3H)ppm；¹³C NMR(101MHz,D₂O)δ56.5,54.3,52.3ppm.

example 7

Preparation of aminating reagent d

(1) Taking a round-bottom flask, dissolving 30mmol (3.37g) of triethylene diamine in 10mL of petroleum ether, adding 30mmol (4.23g) of methyl iodide into the system, and stirring at 25 ℃ for reacting for 14h, wherein the reaction in the step (1) is shown as the following formula:

(2) after the reaction is finished, the reaction solvent is dried by a rotary evaporator, the solid is washed by petroleum ether for 2 times, and the white solid is obtained by drying again. Respectively dissolving the white solid and hydroxylamine-O-sulfonic acid in acetonitrile, mixing, heating at 100 ℃, and stirring for reaction for 1 h. After the reaction mixture was cooled, 10mmol (1.00g) of potassium hydrogencarbonate was added thereto and the reaction mixture was stirred at room temperature for 10 min. And (2) carrying out rotary evaporation and concentration on the reaction liquid to obtain a solid substance, washing with tetrahydrofuran, collecting the solid, dissolving the solid in methanol, carrying out vacuum filtration, collecting filtrate, adding 10mmol (1.4mL) of hydroiodic acid at-30 ℃, stirring for reaction for 2h to obtain corresponding ammonium salt, collecting solid particles, and drying to obtain an amination reagent d, wherein the reaction in the step (2) is shown as the following formula:

example 8

Preparation of aminating reagent e

(1) Taking a round-bottom flask, dissolving 30mmol (3.37g) of triethylene diamine in 10mL of cyclohexane, adding 30mmol (4.23g) of methyl iodide into the system, and stirring at 30 ℃ for reaction for 10 hours, wherein the reaction in the step (1) is shown as the following formula:

(2) after the reaction, the reaction solvent was spin-dried with a rotary evaporator, and the solid was washed with cyclohexane 2 times and spin-dried again to obtain a white solid. Respectively dissolving the white solid and hydroxylamine-O-sulfonic acid in methanol, mixing, heating at 80 ℃, and stirring for reaction for 2 hours. After the reaction mixture was cooled, 10mmol (1.06g) of sodium carbonate was added thereto, and the reaction mixture was stirred at room temperature for 10 min. And (2) carrying out rotary evaporation and concentration on the reaction liquid to obtain a solid substance, washing with tetrahydrofuran, collecting the solid, dissolving the solid in methanol, carrying out vacuum filtration, collecting filtrate, adding 10mmol (1.41g) of iodomethane at the temperature of-30 ℃, stirring and reacting for 2 hours to obtain corresponding ammonium salt, collecting solid particles, and drying to obtain an amination reagent e, wherein the reaction in the step (2) is shown as the following formula:

example amination reagent e nuclear magnetic data is as follows:¹HNMR(400MHz,D₂O)δ4.52-4.39(m,6H),4.23-4.19(m,6H),3.35-3.27(s,3H),2.01-1.95(m,3H)ppm；¹³C NMR(101MHz,D₂O)δ53.2,50.3,29.7,14.6ppm.

example 9

Preparation of amination reagent f

(1) Taking a round-bottom flask, dissolving 30mmol (3.37g) of triethylene diamine in 10mL of n-hexane, adding 30mmol (2.91g) of iodopropane into the system, and stirring at 0 ℃ for reacting for 18h, wherein the reaction in the step (1) is shown as the following formula:

(2) after the reaction is finished, the reaction solvent is dried by a rotary evaporator, the solid is washed by n-hexane for 2 times, and the white solid is obtained by drying again. Respectively dissolving the white solid and hydroxylamine-O-sulfonic acid in acetonitrile, mixing, heating at 100 ℃, and stirring for reaction for 1 h. After the reaction mixture was cooled, 10mmol (1.00g) of potassium hydrogencarbonate was added thereto and the reaction mixture was stirred at room temperature for 10 min. And (2) carrying out rotary evaporation and concentration on the reaction liquid to obtain a solid substance, washing with tetrahydrofuran, collecting the solid, dissolving the solid in methanol, carrying out vacuum filtration, collecting filtrate, adding 10mmol (1.41g) of iodomethane at the temperature of-30 ℃, stirring and reacting for 2 hours to obtain corresponding ammonium salt, collecting solid particles, and drying to obtain an amination reagent f, wherein the reaction in the step (2) is shown as the following formula:

example amination reagent f nuclear magnetic data is as follows:¹HNMR(400MHz,D₂O)δ4.12-3.82(m,6H),3.80-3.75(m,6H),3.21(t,J＝4.0Hz,2H),2.45-2.40(m,3H),1.87-1.70(m,2H),0.94(t,J＝8.0Hz,3H)ppm；¹³C NMR(101MHz,D₂O)δ66.3,62.5,50.3,32.1,15.0,10.6ppm.

examples 10 to 15

The amination reagent a synthesized in examples 1, 2 and 3 was used for amination of primary and secondary alkyl borate esters: weighing 0.25mmol of boron substrate, 0.25mmol of amination reagent a and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 0.6mmol of potassium tert-butoxide and 3mL of tetrahydrofuran in the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring the Hiike reaction tube out of the glove box, placing the Hiike reaction tube in a heating module at 80 ℃, and reacting for 1 h. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 2.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 80 ℃, and continuing to react for 2 hours. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of water to quench the reaction, and detecting by GC/GC-MS.

Example 16

The amination reagent a synthesized in examples 1, 2 and 3 was used for amination of primary and secondary alkyl borate esters: weighing 0.25mmol of boron substrate, 0.25mmol of amination reagent a and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 0.6mmol of sodium tert-butoxide and 3mL of methylbenzene into the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring out of the glove box, placing the Hiike reaction tube in a heating module at 80 ℃, and reacting for 2 hours. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 2.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 80 ℃, and continuing to react for 1 hour. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of dichloromethane to quench the reaction, and detecting by GC/GC-MS.

Examples 17 to 19

The amination reagent a synthesized in examples 1, 2 and 3 was used for amination of primary and secondary alkyl borate esters: weighing 0.25mmol of boron substrate, 0.25mmol of amination reagent a and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 0.6mmol of magnesium methoxide and 3mL of acetonitrile into the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring the Hiike reaction tube out of the glove box, placing the Hiike reaction tube in a heating module at 80 ℃ and reacting for 2 hours. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 2.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 80 ℃, and continuing to react for 2 hours. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of ethyl acetate to quench the reaction, and detecting by GC/GC-MS.

Example 20

The aminating reagent b synthesized in example 4 was used for the amination of primary and secondary alkyl borates: weighing 0.25mmol of boron substrate, 0.25mmol of amination reagent b and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 0.6mmol of sodium methoxide and 3mL of tetrahydrofuran in the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring the Hiike reaction tube out of the glove box, placing the Hiike reaction tube in a heating module at 80 ℃ and reacting for 1 h. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 2.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 80 ℃, and continuing to react for 2 hours. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of ethyl acetate to quench the reaction, and detecting by GC/GC-MS.

Examples 21 to 25

The aminating reagent c synthesized in example 5 was used for the amination of primary and secondary alkyl borates: weighing 0.25mmol of boron substrate, 0.25mmol of amination reagent c and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 0.6mmol of potassium tert-butoxide and 3mL of tetrahydrofuran in the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring the Hiike reaction tube out of the glove box, placing the Hiike reaction tube in a heating module at 80 ℃, and reacting for 1 h. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 2.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 80 ℃, and continuing to react for 2 hours. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of ethyl acetate to quench the reaction, and detecting by GC/GC-MS.

Example 26

The amination reagent d synthesized in examples 6 and 7 was used for amination reaction of tertiary alkyl borate: weighing 0.25mmol of boron substrate, 0.25mmol of amination reagent d and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 0.88mmol of potassium tert-butoxide and 3mL of tetrahydrofuran in the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring the Hiike reaction tube out of the glove box, placing the Hiike reaction tube in a heating module at 100 ℃ and reacting for 3 hours. After the reaction, taking out the Hirak reaction tube, cooling to room temperature, adding 2.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 100 ℃, and continuing to react for 1 hour. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of ethyl acetate to quench the reaction, and detecting by GC/GC-MS.

Example 27

The amination reagent e synthesized in example 8 was used in the amination reaction of a tertiary alkyl borate: weighing 0.25mmol of boron substrate, 0.25mmol of amination reagent e and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 0.88mmol of sodium hydride and 3mL of toluene in the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring the Hiike reaction tube out of the glove box, placing the Hiike reaction tube in a heating module at 100 ℃ and reacting for 3 hours. After the reaction, taking out the Hirak reaction tube, cooling to room temperature, adding 2.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 100 ℃, and continuing to react for 1 hour. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of ethyl acetate to quench the reaction, and detecting by GC/GC-MS.

Examples 28 to 30

The amination reagent f synthesized in example 9 was used in the amination reaction of a tertiary alkyl borate: weighing 0.25mmol of boron substrate, 0.25mmol of amination reagent f and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 0.88mmol of sodium methoxide and 3mL of acetonitrile into the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring the Hiike reaction tube out of the glove box, placing the Hiike reaction tube in a heating module at 90 ℃ and reacting for 3 hours. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 2.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 90 ℃, and continuing to react for 1 hour. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of ethyl acetate to quench the reaction, and detecting by GC/GC-MS.

Examples 31 to 32

The amination reagent a synthesized in examples 1, 2 and 3 was used for amination of arylboronic acid esters: weighing 0.25mmol of boron substrate, 0.25mmol of amination reagent a and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 0.6mmol of potassium tert-butoxide and 3mL of tetrahydrofuran in the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring out of the glove box, placing in a heating module at 100 ℃, and reacting for 3 hours. After the reaction, taking out the Hirak reaction tube, cooling to room temperature, adding 2.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 100 ℃, and continuing to react for 1 hour. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of ethyl acetate to quench the reaction, and detecting by GC/GC-MS.

Examples 33 to 39

The amination reagent c synthesized in example 5 was used for the amination of arylboronic acid esters: weighing 0.25mmol of boron substrate, 0.25mmol of amination reagent c and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 0.6mmol of magnesium methoxide and 3mL of acetonitrile into the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring the Hiike reaction tube out of the glove box, placing the Hiike reaction tube in a heating module at 90 ℃ and reacting for 3 hours. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 2.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 90 ℃, and continuing to react for 1 hour. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of ethyl acetate to quench the reaction, and detecting by GC/GC-MS.

Examples 40 to 42

The amination reagent a synthesized in examples 1, 2 and 3 was used in the amination reaction of alkyl diboronate: weighing 0.25mmol of boron substrate, 0.5mmol of amination reagent a and magnetons in 25mL of dried Hiike reaction tube, transferring the Hiike reaction tube into a glove box, adding 1.2mmol of potassium tert-butoxide and 3mL of tetrahydrofuran in the Hiike reaction tube under protective gas, sealing the Hiike reaction tube, transferring out of the glove box, placing in a heating module at 100 ℃, and reacting for 3 hours. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 4.0eq.TFAA in the air atmosphere, sealing the Hirak reaction tube, putting the Hirak reaction tube back into the heating module at 100 ℃, and continuing to react for 1 hour. After the reaction is finished, taking out the Hirak reaction tube, cooling to room temperature, adding 3mL of ethyl acetate to quench the reaction, and detecting by GC/GC-MS.

TABLE 1 structures and yields of organoboron compound substrates and amination products used in examples 10-42

All of the products obtained in examples 10 to 42 above were obtained by¹H-NMR，¹³C-NMR characterization was confirmed and all unknown samples were confirmed by High Resolution Mass Spectrometry (HRMS). The specific results are as follows:

the nuclear magnetic data of the product obtained in example 10 are as follows:¹HNMR(400MHz,CDCl₃)δ7.38-7.30(m,2H),7.29-7.23(m,1H),7.22-7.16(m,2H),6.42(br,1H),3.65-3.58(m,2H),2.89(t,J＝6.8Hz,2H)ppm；¹³CNMR(101MHz,CDCl₃)δ157.2(q,J＝37.4Hz),137.6,128.8,128.6,126.9,115.8(q,J＝288.9Hz),41.0,34.9ppm.

the nuclear magnetic data of the product obtained in example 11 are as follows:¹HNMR(400MHz,CDCl₃)δ7.33-7.14(m,5H),6.39(br,1H),3.42-3.34(m,2H),2.68(t,J＝7.2Hz,2H),1.97-1.88(m,2H)ppm；¹³C NMR(101MHz,CDCl₃)δ157.2(q,J＝37.4Hz),140.6,128.6,128.2,126.3,115.8(q,J＝288.9Hz),39.6,33.0,30.3ppm.

the nuclear magnetic data of the product obtained in example 12 are as follows:¹H NMR(400MHz,CDCl₃)δ6.87(br,1H),3.44-3.38(m,2H),2.45-3.40(m,2H),1.81-1.69(m,4H)ppm；¹³C NMR(101MHz,CDCl₃):δ157.5(q,J＝37.4Hz),119.1,115.8(q,J＝288.9Hz),38.8,27.9,22.5,16.7ppm.HRMS(ESI)calcd forC₇H₉F₃N₂O[M+Na]⁺:217.0565；found:217.0568.

the nuclear magnetic data of the product obtained in example 13 are as follows:¹HNMR(400MHz,CDCl₃)δ6.36(br,1H),3.42-3.32(m,2H),1.70-1.52(m,3H),1.37-1.27(m,6H),0.94-0.86(m,3H)ppm；¹³C NMR(101MHz,CDCl₃)δ157.3(q,J＝37.4Hz),115.9(q,J＝288.9Hz),40.0,31.3,28.8,26.3,22.4,13.8ppm.

the nuclear magnetic data of the product obtained in example 14 are as follows:¹HNMR(400MHz,CDCl₃)δ7.32-7.26(m,2H),7.14-7.09(m,2H),6.63(br,1H),3.61-3.53(m,2H),2.86(t,J＝7.2Hz,2H)ppm；¹³C NMR(101MHz,CDCl₃)δ157.3(q,J＝37.1Hz),136.0,132.8,130.0,128.9,115.7(q,J＝288.9Hz),40.9,34.3ppm.

the nuclear magnetic data of the product obtained in example 15 are as follows:¹HNMR(400MHz,CDCl₃)δ6.51(br,1H),3.41-3.34(m,2H),1.77-1.67(m,5H),1.52-1.44(m,2H),1.30-1.11(m,4H),1.00-0.88(m,2H)ppm；¹³CNMR(101MHz,CDCl₃)δ157.2(q,J＝37.4Hz),115.9(q,J＝288.9Hz),37.9,36.3,35.2,33.0,26.4,26.1ppm.HRMS(ESI)calcd for C₁₀H₁₆F₃NO[M+Na]⁺:246.1082；found:246.1077.

the nuclear magnetic data of the product obtained in example 16 are as follows:¹H NMR(400MHz,CDCl₃):δ7.42(br,1H),4.77-4.69(m,1H),4.18-4.08(m,2H),3.84-3.73(m,2H),3.56-3.47(m,2H),2.16-2.02(m,1H),1.91-1.83(m,2H),1.42-1.35(m,1H)ppm；¹³C NMR(101MHz,CDCl₃):δ156.8(q,J＝36.4Hz),115.9(q,J＝288.9Hz),101.1,66.9,35.2,32.8,25.5ppm.HRMS(ESI)calcd for C₈H₁₂F₃NO₃[M+Na]⁺:250.0667；found:250.0663.

the nuclear magnetic data of the product obtained in example 17 are as follows:¹H NMR(400MHz,CDCl₃)δ6.47(br,1H),4.24-4.04(m,1H),3.19-3.14(m,3H),1.60-1.23(m,9H),1.21(t,J＝6.0Hz,3H),1.13(s,6H),0.94-0.90(m,3H)ppm；¹³C NMR(101MHz,CDCl₃)δ157.1,156.9,156.7,156.5,156.4,156.2,156.0,155.8,120.2,117.3,114.5,114.4,111.6,74.6,74.5,48.9,44.6,44.4,43.7,43.6,40.0,39.8,37.4,37.2,29.8,29.6,24.9,24.8,24.7,21.1,20.9(2),20.8(8),20.2,19.4,19.3ppm.HRMS(ESI)calcd forC₁₄H₂₆F₃NO₂[M+Na]⁺:320.1813；found:320.1810.

the nuclear magnetic data of the product obtained in example 18 are as follows:¹HNMR(400MHz,CDCl₃)δ6.27(br,1H),3.93-3.82(m,1H),1.81-1.66(m,5H),1.46-1.34(m,1H),1.31-1.14(m,6H),1.06-0.92(m,2H)ppm；¹³CNMR(101MHz,CDCl₃)δ156.6(q,J＝36.4Hz),116.0(q,J＝289.9Hz),50.7,42.7,29.0,28.9,26.2,25.9,17.4ppm.

nuclei of product obtained in example 19The magnetic data are as follows:¹H NMR(400MHz,CDCl₃)δ7.30-7.13(m,5H),6.38(br,1H),4.12-3.99(m,1H),2.65(t,J＝8.0Hz,2H),1.91-1.79(m,2H),1.24(d,J＝6.8Hz,3H)ppm；¹³C NMR(101MHz,CDCl₃)δ156.6(q,J＝36.9Hz),140.8,128.5,128.2,126.2,115.9(q,J＝288.9Hz),41.3,37.6,32.2,20.2ppm.

the nuclear magnetic data of the product obtained in example 20 are as follows:¹H NMR(400MHz,CDCl₃)δ6.34-6.14(m,1H),5.11-5.02(m,1H),4.22-4.04(m,1H),2.05-1.91(m,2H),1.68(s,3H),1.60(s,3H),1.56-1.26(m,5H),1.24-1.19(m,3H),0.95-0.89(m,3H)ppm；¹³C NMR(101MHz,CDCl₃)δ156.7,156.5,156.4,156.2,131.5(1),131.4(8),124.3,115.9(q,J＝290.9Hz),44.7,44.5,43.9,43.7,37.0,36.7,29.4,29.0,25.6,25.2(2),25.2(0),21.1,20.3,19.4,17.6ppm.HRMS(ESI)calcd for C₁₃H₂₂F₃NO[M+Na]+:288.1551；found:288.1548.

the nuclear magnetic data of the product obtained in example 21 are as follows:¹HNMR(400MHz,CDCl₃)δ6.21(br,1H),4.07-3.96(m,1H),1.57-1.46(m,2H),1.35-1.26(m,6H),1.21(d,J＝6.4Hz,3H),0.93-0.84(m,3H)ppm；¹³C NMR(101MHz,CDCl₃)δ156.5(q,J＝36.4Hz),115.9(q,J＝288.9Hz),46.6,36.3,31.4,25.5,22.4,20.3,13.9ppm.

the nuclear magnetic data of the product obtained in example 22 are as follows:¹H NMR(400MHz,CDCl₃)δ6.28(br,1H),3.98-3.74(m,1H),2.03-1.93(m,2H),1.81-1.72(m,2H),1.70-1.61(m,1H),1.44-1.32(m,2H),1.30-1.19(m,3H)ppm；¹³C NMR(101MHz,CDCl₃)δ156.3(q,J＝36.4Hz),115.9(q,J＝289.9Hz),49.3,32.4,25.2,24.6ppm.

the nuclear magnetic data of the product obtained in example 23 are as follows:¹HNMR(400MHz,CDCl₃)δ7.30-7.10(m,5H),7.07-7.02(m,2H),6.86-6.80(m,2H),6.16-6.09(m,1H),4.24-4.13(m,1H),3.77(s,3H),2.88-2.75(m,2H),2.73-2.58(m,2H),1.99-1.86(m,1H),1.85-1.71(m,1H)ppm；¹³C NMR(101MHz,CDCl₃)δ158.6,156.7(q,J＝36.4Hz),140.8,130.3,128.6,128.4,128.2,126.2,115.8(q,J＝289.9Hz),114.1,55.2,51.3,39.4,35.0,32.3ppm.HRMS(ESI)calcd for C₁₉H₂₀F₃NO₂[M+Na]⁺:374.1344；found:374.1339.

the nuclear magnetic data of the product obtained in example 24 are as follows:¹HNMR(400MHz,CDCl₃)δ7.38-7.13(m,5H),6.40-6.06(m,1H),4.32-4.15(m,1H),2.99-2.81(m,1H),1.32(d,J＝6.8Hz,3H),1.20(d,J＝6.8Hz,0.63H),1.04(d,J＝6.8Hz,2.27H)ppm；¹³C NMR(101MHz,CDCl₃)δ157.1,156.7,156.6,156.4,156.3,156.0,142.0,141.6,128.6,127.9,127.7,127.1(1),127.0(5),115.9(q,J＝288.9Hz),51.0,50.8,44.8,44.4,18.2,18.1,17.3ppm.HRMS(ESI)calcd for C₁₂H₁₄F₃NO[M+Na]⁺:268.0925；found:268.0921.

the nuclear magnetic data of the product obtained in example 25 are as follows:¹H NMR(400MHz,CDCl₃)δ7.49-7.35(m,5H),7.27-7.06(m,5H),6.01-5.89(m,1H),3.82-3.70(m,1H),2.70-2.61(m,1H),2.61-2.45(m,1H),2.00-1.84(m,1H),1.76-1.63(m,1H),0.38-0.34(m,6H)ppm；¹³C NMR(101MHz,CDCl₃)δ156.9(q,J＝36.4Hz),141.0,134.5,133.9,130.0,128.5,128.3,128.2,126.1,116.0(q,J＝288.9Hz),41.1,33.7,32.3,-5.0,-5.5ppm.HRMS(ESI)calcd for C₁₉H₂₂F₃NOSi[M+Na]⁺:388.1321；found:388.1316.

the nuclear magnetic data of the product obtained in example 26 are as follows:¹H NMR(400MHz,CDCl₃)δ7.11-7.06(m,2H),6.85-6.60(m,2H),6.02(br,1H),3.77(s,3H),2.58-2.51(m,2H),2.08-1.99(m,2H),1.43(s,6H)ppm；¹³C NMR(101MHz,CDCl₃)δ158.0,156.0(q,J＝36.4Hz),133.3,129.2,115.6(q,J＝290.9Hz),114.0,55.3,55.2,41.7,29.6,26.4ppm.HRMS(ESI)calcd for C₁₄H₁₈F₃NO₂[M+Na]⁺:312.1188；found:312.1180.

the nuclear magnetic data of the product obtained in example 27 are as follows:¹HNMR(400MHz,CDCl₃)δ7.31-7.14(m,5H),6.02(br,1H),2.64-2.56(m,2H),2.13-2.03(m,2H),1.44(s,6H)ppm；¹³C NMR(101MHz,CDCl₃)δ156.1(q,J＝36.4Hz),141.3,128.5,128.3,126.1,115.6(q,J＝290.9Hz),55.4,41.4,30.5,26.5ppm.HRMS(ESI)calcd for C₁₃H₁₆F₃NO[M+Na]⁺:282.1082；found:282.1086.

the nuclear magnetic data of the product obtained in example 28 are as follows:¹HNMR(400MHz,CDCl₃)δ7.34-7.10(m,10H),5.70-5.57(br,1H),3.59-3.48(m,2H),2.93-2.86(m,2H),1.18(s,3H)ppm；¹³C NMR(101MHz,CDCl₃)δ156.7(q,J＝36.4Hz),136.2,130.5,128.3,126.9,115.5(q,J＝290.9Hz),58.3,43.5,24.0ppm.HRMS(ESI)calcd for C₁₈H₁₈F₃NO[M+Na]⁺:344.1238；found:344.1233.

the nuclear magnetic data of the product obtained in example 29 are as follows:¹HNMR(400MHz,CDCl₃)δ5.89(br,1H),2.15-2.11(m,3H),2.05-2.02(m,6H),1.73-1.68(m,6H)ppm；¹³C NMR(101MHz,CDCl₃)δ155.7(q,J＝36.4Hz),115.6(q,J＝290.9Hz),53.4,41.0,36.0,29.3ppm.

the nuclear magnetic data of the product obtained in example 30 are as follows:¹HNMR(400MHz,CDCl₃)δ7.30-7.14(m,5H),6.46(br,1H),2.77-2.68(m,2H),2.00-1.91(m,2H),0.89-0.74(m,4H)ppm；¹³C NMR(101MHz,CDCl₃)δ157.3(q,J＝36.4Hz),141.2,128.6,128.2,126.1,115.6(q,J＝289.9Hz),37.3,33.6,32.8,13.4ppm.HRMS(ESI)calcd for C₁₃H₁₄F₃NO[M+Na]⁺:280.0925；found:280.0920.

the nuclear magnetic data of the product obtained in example 31 are as follows:¹H NMR(400MHz,CDCl₃)δ8.27(br,1H),7.59-7.51(m,2H),7.41-7.32(m,2H),7.27-7.18(m,1H)ppm；¹³C NMR(101MHz,CDCl₃)δ155.0(q,J＝37.4Hz),135.1,129.3,126.4,120.7,115.7(q,J＝289.9Hz)ppm.

the nuclear magnetic data of the product obtained in example 32 are as follows:¹H NMR(400MHz,CDCl₃)δ8.12(br,1H),7.58-7.49(m,2H),7.13-7.03(m,2H)ppm；¹³C NMR(101MHz,CDCl₃)δ161.8,159.3,155.0(q,J＝37.4Hz),131.1,131.0,122.7,122.6,116.3,116.0,115.7(q,J＝289.9Hz)ppm.

the nuclear magnetic data of the product obtained in example 33 are as follows:¹H NMR(400MHz,CDCl₃)δ8.21(br,1H),7.20-7.15(m,2H),6.87-6.83(m,1H),2.28(s,6H)ppm；¹³C NMR(101MHz,CDCl₃)δ155.0(q,J＝37.4Hz),139.1,134.9,128.0,118.4,115.8(q,J＝289.9Hz),21.1ppm.

the nuclear magnetic data of the product obtained in example 34 are as follows:¹H NMR(400MHz,CDCl₃)δ8.24(br,1H),7.30-7.20(m,2H),7.10-7.03(m,1H),6.82-6.72(m,1H),3.80(s,3H)ppm；¹³C NMR(101MHz,CDCl₃)δ160.2,155.0(q,J＝37.4Hz),136.2,130.0,115.7(q,J＝289.9Hz),112.8,112.1,106.5,55.3ppm.

the nuclear magnetic data of the product obtained in example 35 are as follows:¹H NMR(400MHz,CDCl₃)δ8.34(br,1H),7.56-7.44(m,1H),7.32-7.24(m,2H),7.15-7.04(m,1H),2.45(s,3H)ppm；¹³C NMR(101MHz,CDCl₃)δ155.1(q,J＝37.4Hz),140.4,135.6,129.4,124.1,118.1,117.1,115.6(q,J＝289.9Hz),15.3ppm.HRMS(ESI)calcd for C₉H₈F₃NOS[M+Na]⁺:258.0176；found:258.0175.

the nuclear magnetic data of the product obtained in example 36 are as follows:¹H NMR(400MHz,DMSO)δ11.58(br,1H),7.93-7.85(m,2H),7.80-7.73(m,2H)ppm；¹³C NMR(101MHz,DMSO)δ154.9(q,J＝37.4Hz),140.6,133.3,121.1,118.5,115.4(q,J＝289.9Hz),107.7ppm.

the nuclear magnetic data of the product obtained in example 37 are as follows:¹H NMR(400MHz,DMSO)δ11.56(br,1H),7.90(m,2H),7.74(m,2H)ppm；¹³C NMR(101MHz,DMSO)δ154.9(q,J＝38.4Hz),140.0,126.1(q,J＝4.0Hz),125.7(q,J＝32.3Hz),124.0(q,J＝272.2Hz),115.6(q,J＝289.9Hz)ppm.

the nuclear magnetic data of the product obtained in example 38 are as follows:¹H NMR(400MHz,DMSO)δ11.52(br,1H),8.03-7.96(m,2H),7.85-7.78(m,2H),2.56(s,3H)ppm；¹³C NMR(101MHz,DMSO)δ196.7,154.7(q,J＝37.4Hz),140.5,133.7,129.3,120.4,115.6(q,J＝289.9Hz),26.5ppm.

the nuclear magnetic data of the product obtained in example 39 are as follows:¹H NMR(400MHz,CDCl₃)δ7.82-7.74(m,2H),7.46-7.38(m,1H),7.32-7.23(m,2H),6.76-6.71(m,1H),4.07(br,2H)ppm；¹³C NMR(101MHz,CDCl₃)δ142.0,134.3,128.5,126.3,125.8,124.8,123.6,120.7,118.9,109.6ppm.

the nuclear magnetic data of the product obtained in example 40 are as follows:¹HNMR(400MHz,DMSO)δ9.50-9.44(m,1H),9.18-9.10(m,1H),4.04-3.90(m,1H),3.32-3.26(m,2H),1.52-1.45(m,2H),1.32-1.18(m,4H),0.88-0.81(m,3H)ppm；¹³C NMR(101MHz,DMSO)δ156.6(q,J＝36.4Hz),156.4(q,J＝36.4Hz),115.9(1)(q,J＝289.9Hz),115.8(8)(q,J＝288.9Hz),49.3,42.6,30.2,27.5,21.6,13.6ppm.HRMS(ESI)calcd for C₁₀H₁₄F₆N₂O₂[M+Na]⁺:331.0857；found:331.0855.

the nuclear magnetic data of the product obtained in example 41 are as follows:¹HNMR(400MHz,DMSO)δ8.98-8.81(m,2H),4.21-4.01(m,2H),1.81-1.64(m,4H),1.62-1.52(m,2H),1.42-1.31(m,2H)ppm；¹³C NMR(101MHz,DMSO)δ156.3(q,J＝36.4Hz),115.8(q,J＝288.9Hz),49.4,26.6,21.3ppm.

the nuclear magnetic data of the product obtained in example 42 are as follows:¹H NMR(400MHz,DMSO)9.39-9.32(m,1H),9.28-9.20(m,1H),3.93-3.83(m,1H),3.22-3.13(m,2H),1.75-1.68(m,2H),1.13(d,J＝6.4Hz,3H)ppm；¹³C NMR(101MHz,DMSO)δ156.2(q,J＝36.4Hz),155.6(q,J＝36.4Hz),115.9(1)(q,J＝288.9Hz),115.8(9)(q,J＝289.9Hz),43.6,36.4,33.9,19.6ppm.HRMS(ESI)calcd forC₈H₁₀F₆N₂O₂[M+Na]⁺:303.0544；found:303.0541.

in addition, the inventor also refers to the modes of examples 3-35, tests are carried out by using other raw materials listed in the specification, corresponding effects can be achieved, the reaction conditions are relatively mild, the operation is simple, the raw materials are economical and easy to obtain, the reaction is efficient, and the application prospect is wide.

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.

Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.

It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.

While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims

1. An amination reagent, characterized in that said amination reagent has the structure shown in formula (I) or (II):

2. A process for the preparation of an amination reagent as claimed in claim 1, characterized in that it comprises:

or reacting a third uniformly mixed reaction system containing triethylene diamine, an iodoalkyl compound 1 and a third solvent, reacting a fourth uniformly mixed reaction system containing a second solid obtained by the reaction, hydroxylamine-O-sulfonic acid and a first solvent, adding alkali into the fourth uniformly mixed reaction system, and continuing to react a fifth uniformly mixed reaction system containing a third solid obtained by the reaction, a second solvent, an acid or an iodoalkyl compound 2 to obtain the amination reagent shown in the formula (I), wherein Y is selected from alkyl with 1-4 carbon atoms.

3. The method according to claim 2, comprising:

s1, dissolving triethylene diamine and hydroxylamine-O-sulfonic acid in a first solvent respectively, mixing to form a first uniform mixed reaction system, reacting at 80-100 ℃ for 1-2 h, adding alkali into the first uniform mixed reaction system, continuing to react at 10-25 ℃ for 10-30 min, and concentrating and washing to obtain a first solid matter;

s2, dissolving the first solid obtained in the step S1 in a second solvent to form a solution, adding an acid or iodoalkyl compound into the solution to form the second uniformly mixed reaction system, and reacting at-20 to-78 ℃ for 1-3H to obtain the amination reagent shown in the formula (I) or (II), wherein Y is H.

4. The method according to claim 2, comprising:

s1, dissolving triethylene diamine in a third solvent to form a solution, adding iodoalkyl compound 1 into the solution to form a third uniformly mixed reaction system, reacting at 0-30 ℃ for 10-18 h, and distilling, washing and drying to obtain a second solid matter;

s2, respectively dissolving the second solid matter obtained in the step S1 and hydroxylamine-O-sulfonic acid in a first solvent, mixing to form a fourth uniformly mixed reaction system, reacting at 80-100 ℃ for 1-2 hours, adding alkali into the fourth uniformly mixed reaction system, continuing to react at 10-25 ℃ for 10-30 min, and concentrating and washing to obtain a third solid matter;

s3, dissolving the third solid obtained in the step S2 in a second solvent to form a solution, adding an acid or iodoalkyl compound 2 into the solution to form the fifth uniform mixed reaction system, and reacting at-20 to-78 ℃ for 1-3 h to obtain the amination reagent shown in the formula (I), wherein Y is selected from alkyl with 1-4 carbon atoms.

5. The production method according to claim 2 or 3, characterized in that: the molar ratio of the triethylene diamine to the hydroxylamine-O-sulfonic acid to the alkali to the acid to the iodo alkyl compound is 3.0: 1.0: (1.0-2.0): 1.0.

6. the production method according to claim 2 or 4, characterized in that: the molar ratio of the triethylene diamine to the iodo-alkyl compound 1 to the hydroxylamine-O-sulfonic acid to the alkali to the acid to the iodo-alkyl compound 2 is 3.0: 3.0: 1.0: (1.0-2.0): 1.0.

7. the production method according to claim 2 or 4, characterized in that: the third solvent is any one of n-hexane, petroleum ether, n-pentane and cyclohexane.

8. The production method according to any one of claims 2 to 4, characterized in that: the acid is selected from HI, HCl, HBr, HNO₃、HClO₄Any one of them.

9. The production method according to any one of claims 2 or 3, characterized in that: the first solvent is selected from any one of water, methanol and acetonitrile.

10. The production method according to any one of claims 2 or 3, characterized in that: the second solvent is selected from any one of ethanol, methanol and isopropanol.

11. The production method according to any one of claims 2 to 4, characterized in that: the alkali is selected from any one of potassium carbonate, potassium bicarbonate and sodium carbonate.

12. The production method according to any one of claims 2 or 3, characterized in that: the iodoalkyl compound is selected from any one of methyl iodide, ethyl iodide, propyl iodide, isopropyl iodide, butyl iodide and tert-butyl iodide.

13. An amination reaction of an organoboron compound, characterized by comprising:

providing an amination reagent as claimed in claim 1;

and adding trifluoroacetic anhydride into the mixed system obtained by the reaction in an air atmosphere, and performing reaction at 80-100 DEG C^oAnd C, continuously reacting for 1-2 h, and then adding a quenching agent to quench the reaction to obtain an organic boron amination product.

14. The amination reaction according to claim 13, characterized in that: the dosage ratio of the organic boron compound, the amination reagent and the alkaline substance is 1: (1-2): (2.4-4.8).

15. The amination reaction according to claim 13, characterized in that: the molar ratio of the trifluoroacetic anhydride to the organoboron compound is 2: 1-4: 1.

16. The amination reaction according to claim 13, characterized in that: the organoboron compound is selected from any one of alkyl borate, aryl borate and alkyl diboronate.

17. The amination reaction according to claim 16, characterized in that: the alkyl borate is selected from any one of primary alkyl borate, secondary alkyl borate and tertiary alkyl borate.

18. The amination reaction according to claim 13, characterized in that: the solvent is selected from any one of tetrahydrofuran, toluene and acetonitrile.

19. The amination reaction according to claim 13, characterized in that: the alkaline substance is selected from any one of potassium tert-butoxide, sodium hydride, magnesium methoxide, sodium methoxide and sodium tert-butoxide.

20. The amination reaction according to claim 13, characterized in that: the quenching agent is selected from any one of ethyl acetate, water and dichloromethane.