A method for synthesizing fluoralkyl-substituted 4,4'-diaminodiphenylmethane compounds

Abstract

The application provides a method for synthesizing fluorine alkyl substituted 4,4'-diamino diphenyl methane compounds, which comprises the following steps: under the action of a catalyst, an amine compound is reacted with a fluorine-containing aldehyde compound in an organic solvent, and after the reaction is completed, post-treatment is performed to obtain the fluorine alkyl substituted 4,4'-diamino diphenyl methane compounds. The method has the advantages of mild reaction condition, simple operation, high reaction efficiency, cheap and easily obtained raw materials, good atomic economy, no waste generation, and large-scale application prospect. In addition, the fluorine alcohol solvent can be recycled through simple distillation operation, the cost of a large amount of solvent is effectively saved, the process safety is improved, and the efficient and green industrial production is facilitated.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic synthesis, and particularly relates to a method for synthesizing fluorine alkyl-substituted 4,4'-diaminodiphenyl methane compounds. BACKGROUND

[0002] Polyimide is a high-performance engineering material. The rigid imide structure makes it have good high-temperature resistance, chemical stability, mechanical properties, electrical properties, radiation resistance and self-lubricity, and is widely used in aerospace, machinery, nanotechnology, separation membrane, electrical and microelectronic industries. However, polyimide has high melting point, poor solubility, is not easy to be formed and processed, and has high production cost. The highly conjugated aromatic structure and intermolecular charge transfer complex result in strong coloring, reduced optical transparency and high dielectric constant, which limits its application range in the technical field of flexible electronic products, flexible circuit board and the like.

[0003] The introduction of fluorine-containing substituents into the molecular structure of polyimide can effectively make up for these deficiencies, reduce optical loss, dielectric constant and moisture absorption rate, and at the same time improve solubility, transparency and thermal stability, so that it has unique advantages and broad development prospects in the fields of optoelectronics, aerospace and the like. As an important fluorine-containing polyimide monomer, 4,4'-diaminodiphenyl methane substituted with a trifluoromethyl group is disclosed in the patent application "Manufacturing method of 1,1,1-trifluoro-2,2-bisaryl ethane, and 1,1,1-trifluoro-2,2-bisaryl ethane" with publication number CN113396137A. In the application, aniline and trifluoroacetaldehyde are used as raw materials, anhydrous HF gas is introduced as a catalyst under anhydrous conditions, a large amount of trifluoromethanesulfonic acid is added, and at the same time, special equipment such as a stainless steel autoclave is needed to carry out the reaction under high temperature and high pressure, which brings great inconvenience to production operation and is dangerous and complicated to operate. After the reaction is completed, 48% potassium hydroxide aqueous solution is needed for neutralization, which produces a large amount of wastewater. In addition, the catalyst used is HF gas, which has strong corrosiveness and high risk, is difficult to recycle, and causes serious environmental pollution.

[0004] In summary, there are some problems in the current synthesis method of 4,4'-diaminodiphenyl methane substituted with a trifluoromethyl group. It is particularly important to develop a simple, safe, low-cost and green synthesis method for synthesizing 4,4'-diaminodiphenyl methane substituted with a trifluoromethyl group and other fluorine alkyl groups. In addition, there is no report on the synthesis of 4,4'-diaminodiphenyl methane compounds substituted with fluorine alkyl groups such as difluoromethyl and pentafluoroethyl. SUMMARY

[0005] The present application provides a method for synthesizing fluorine alkyl-substituted 4,4'-diaminodiphenyl methane compounds. The method has easy-to-obtain raw materials, simple operation, mild reaction conditions, high safety and high reaction yield, good atom economy, and large-scale application prospects.

[0006] To achieve the above object, the technical scheme adopted by the present application is:

[0007] A method for synthesizing fluorine alkyl substituted 4,4'-diamino diphenyl methane compounds, comprising:

[0008] Under the action of a catalyst, an amine compound and a fluorine-containing aldehyde compound are reacted in an organic solvent, and after the reaction is completed, post-treatment is performed to obtain the fluorine alkyl substituted 4,4'-diamino diphenyl methane compound, which has a structure represented by the following general formula [1]:

[0009]

[0010] In the general formula [1], n1 and n2 are independently integers from 0 to 4, R 1 independently represent a substituent group when multiple exist;

[0011] R 1 is independently selected from hydrogen, alkyl, alkoxy, cycloalkyl, aryl, propenyl, halogen, hydroxyl, benzyl, thioalkyl, ester group;

[0012] R f is independently selected from difluoromethyl, trifluoromethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl;

[0013] X is independently selected from methylene, oxygen or sulfur.

[0014] As a preference, the amine compound includes monosubstituted, polysubstituted or unsubstituted arylamine compounds and diphenylamine compounds.

[0015] As a further preference, in the monosubstituted, polysubstituted or unsubstituted arylamine compounds, each substituent group is independently selected from hydrogen, methyl, ethyl, tert-butyl, isopropyl, alkoxy, cycloalkyl, phenyl, propenyl, halogen, hydroxyl, benzyl, thioalkyl, ester group, trifluoromethoxy; and the diphenylamine compound is diamino diphenyl methane, oxydiphenylamine, thiodiphenylamine.

[0016] As a preference, the fluorine-containing aldehyde compound includes difluoroacetaldehyde hydrate, difluoroacetaldehyde hemiethanol, trifluoroacetaldehyde hydrate, trifluoroacetaldehyde hemimethyl alcohol, trifluoroacetaldehyde hemiethanol, 3,3,3-trifluoropropionaldehyde, 2,2,3,3-tetrafluoropropionaldehyde hydrate, pentafluoropropionaldehyde hydrate, heptafluorobutyraldehyde hydrate or nonafluoropentanal hydrate.

[0017] As a preference, the catalyst is a Lewis acid or acid.

[0018] As further preferred, the Lewis acid is selected from the group consisting of benzenboronic acid, boric acid, trimethylborate, triethylborate, triisopropylborate, tributylborate, triphenylborate, boron trifluoride etherate, tris(2,4-bis(trifluoromethyl)phenyl)borane, tris(pentafluorophenyl)borane, tris(2,2,2-trifluoroethyl)borate, triphenylborane, tris(hexafluoroisopropyl)borate, tris(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)borane, tris(2,4-bis(trifluoromethyl)phenyl)borane, trimethylsilyl trifluoromethanesulfonate, t-butyldimethylsilyl trifluoromethanesulfonate, trimethylsilyl acetate, trimethylsilyl methane sulfonate, N-(trimethylsilyl)bis(trifluoromethylsulfonyl)imide, (pentafluorophenyl)bis(trifluoromethylsulfonyl)trimethylsilane, di-t-butylisobutylsilyl trifluoromethanesulfonate, t-butyldiphenylsilyl trifluoromethanesulfonate, t-butyldimethylsilyl trifluoromethanesulfonate, 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, triisopropylsilyl trifluoromethanesulfonate, diisopropylsilyl bis(trifluoromethanesulfonate), diethylisopropylsilyl trifluoromethanesulfonate, di-t-butylsilyl bis(trifluoromethanesulfonate), triethylsilyl trifluoromethanesulfonate, tris(2,6-difluorophenyl)borane, tris(2,5-bis(trifluoromethyl)phenyl)borane, 2,4,6-tris(3-(trifluoromethyl)phenyl)-1,3,5,2,4,6-trioxabenzene, trityl tetra(pentafluorophenyl)borate, bis(perfluorophenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris[3,5-bis(trifluoromethyl)phenyl]borane, tris(2,2',2"-perfluorobiphenyl)borane, bis(pentafluorophenyl)-(2-perfluorobiphenyl)borane, or tris(2-perfluoronaphthyl)borane;

[0019] The The acid is selected from the group consisting of acetic acid, benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid, methylsulfonic acid, camphorsulfonic acid, Amberlyst 15 ion exchange resin, diphenyl phosphate, binaphthyl phosphate, trifluoroacetic acid, trifluoromethanesulfonic acid, lactic acid, oxalic acid, sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, or polyphosphoric acid.

[0020] As preferred, the organic solvent is 2,2-difluoroethanol, hexafluoroisopropanol, hexafluoro-2-methylisopropanol, hexafluoro-2-phenylisopropanol, trifluoroethanol, perfluoroalkylethanol, perfluoro-t-butanol, ethylene glycol, tetrafluoropropanol, tetrafluorobutanediol, hexafluorobutanol, or octafluoropentanol.

[0021] As preferred, the temperature of the reaction is from room temperature to 130 °C and the time of the reaction is from 12 to 24 h. More preferred is a temperature of 45 to 90 °C for 12 to 20 h.

[0022] As preferred, the molar ratio of the amine compound to the fluorine-containing aldehyde compound is from 1 to 2.4:1.

[0023] As preferred, the molar ratio of the fluorine-containing aldehyde compound to the catalyst is 1:0-0.2.

[0024] As preferred, the post-treatment includes: after the reaction is completed, removing the solvent under reduced pressure, recrystallizing the reaction crude product, and obtaining the fluorine alkyl-substituted 4,4'-diaminodiphenyl methane compound.

[0025] As further preferred, the solvent used in the recrystallization includes ethanol, methanol, toluene, ethyl acetate, chloroform.

[0026] As further preferred, the fluorine alcohol solvent can be recovered through simple distillation operation after the reaction is completed.

[0027] Compared with the prior art, the present application has the following advantages:

[0028] The present application provides a method for synthesizing fluorine alkyl-substituted 4,4'-diaminodiphenyl methane compound, effectively solving the problems existing in the traditional method, such as the need for anhydrous reaction, hydrogen fluoride as a catalyst, high temperature and high pressure, high operation risk, and complex post-treatment. The present application uses Lewis acid or acid as a catalyst, does not need anhydrous reaction, has mild reaction conditions, simple operation, high reaction efficiency, cheap and readily available raw materials, good atomic economy, no waste generation, and large-scale application prospects. In addition, the fluorine alcohol solvent is recycled through simple distillation operation, effectively saving a large amount of solvent cost, improving process safety, and being conducive to efficient and green industrial production. DETAILED DESCRIPTION

[0029] The present application will be described in detail below in conjunction with specific embodiments, and the following specific examples are helpful for those skilled in the art to further understand the present application, but do not limit the present application in any form.

[0030] Example 1

[0031]

[0032] In a 1000 mL reaction bottle, aniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), trifluoroethanol (640 mL), and phenylboronic acid (0.038 mol) were sequentially added, and the reaction was carried out at 45°C, and the reaction was monitored by TLC spotting. The reaction was completed after 12 h. After the reaction was completed, the solvent was recovered by rotary evaporation, and the reaction crude product was recrystallized with toluene to obtain the product shown in the formula (4,4'- (2,2,2-trifluoroethane-1,1-diyl)dianiline) 80.8 g, with a yield of 80%.

[0033] 1H NMR (400 MHz, CDC13) δ 7.13 (d, J = 8.2 Hz, 4H), 6.64 (d, J = 8.4 Hz, 4H), 4.46 (q, J = 10.1 Hz, 1H), 3.65 (s, 4H); 19 F NMR (376 MHz, CDC13) δ -66.41 (d, J = 9.9 Hz, 3F); 13 C NMR (100 MHz, CDC13) δ 145.8, 129.9, 126.6 (d, 1 J C-F = 281.8 Hz), 125.8, 115.1, 53.9 (q, 2 J C-F = 27.3 Hz); HRMS (ESI) m / z: [M + H] + Calcd for C 14 H 14 F3N2267.1104; Found: 267.1108.

[0034] Example 2

[0035]

[0036] In a 1000 mL reaction flask, 2-methylaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hemimethylole (49.4 g, 0.38 mol), trifluoroethanol (640 mL), tris[3,5-bis(trifluoromethyl)phenyl]borane (0.038 mol) were added sequentially and the reaction was carried out at 80 °C. The reaction was monitored by TLC spot plate and was complete in 12 h. After completion of the reaction, the solvent was recovered by rotary evaporation and the crude reaction product was recrystallized from ethanol to obtain the product shown above (4,4'-(2,2,2-trifluoroethane-l,l-diyl)bis(2-methylaniline)) 107.2 g in 96% yield.

[0037] 1 H NMR (400 MHz, CDC13) δ 7.04 (d, J = 8.3 Hz, 4H), 6.63 (d, J = 7.8 Hz, 2H), 4.42 (q, J = 10.3 Hz, 1H), 3.58 (s, 4H), 2.14 (s, 6H); 19 F NMR (376 MHz, CDC13) δ -66.24 (d, J = 10.2 Hz, 3F); 13 C NMR (100 MHz, CDC13) δ 144.0, 131.1, 127.4, 126.6 (d, 1 J C-F= 281.5 Hz), 126.0, 122.3, 114.9, 54.1 (q, J = 27.2 Hz), 17.4; HRMS (ESI) m / z: [M+H] calcd for C20H18F6N2: 395.1297; found: 395.1298. 2 J C-F = 27.2 Hz), 17.4; HRMS (ESI) m / z: [M+H] calcd for C20H18F6N2: 395.1297; found: 395.1298. + Calcd for C20H18F6N2: 395.1297; found: 395.1298. 16 H 18 F3N2295.1417; found: 295.1413.

[0038] Example 3

[0039]

[0040] In a 1000 mL reaction flask, 3-methylaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hemiacetal (54.7 g, 0.38 mol), hexafluoroisopropanol (640 mL), tris(2,4-bis(trifluoromethyl)phenyl)borane (0.019 mol) were added in sequence and reacted at 65 °C. The reaction was monitored by TLC spot plate. The reaction was completed in 14 h. After the reaction was completed, the solvent was recovered by rotary evaporation. The crude product was recrystallized with ethyl acetate to obtain the product shown in the above formula (4,4'-(2,2,2-trifluoroethane-1,1-diyl)bis(3-methylaniline)) 72.6 g, yield 65%.

[0041] 1 H NMR (400 MHz, CDC13) δ 7.17 (d, J = 8.3 Hz, 2H), 6.53 - 6.46 (m, 4H), 4.82 (q, J = 9.7 Hz, 1H), 3.59 (s, 4H), 2.21 (s, 6H); 19 F NMR (376 MHz, CDC13) δ -65.10 (d, J = 9.8 Hz, 3F); 13 CNMR (100 MHz, CDC13) δ 145.5, 137.8, 129.6, 127.2 (d, 1 J C-F = 282.2 Hz), 124.3, 117.2, 112.8, 45.9 (q, 2 J C-F = 26.8 Hz), 19.7; HRMS (ESI) m / z: [M+H] calcd for C20H18F6N2: 395.1297; found: 395.1298. + Calcd for C20H18F6N2: 395.1297; found: 395.1298. 16 H 18 F3N2295.1417; found: 295.1416.

[0042] Example 4

[0043]

[0044] In a 1000 mL reaction flask, 2-methoxyaniline (0.84 mol, 2.2 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), perfluoro-tert-butyl alcohol (640 mL), trimethyl borate (0.038 mol) were added sequentially and the reaction was carried out at 50 °C. The reaction was monitored by TLC spot test and was complete in 12 h. After completion of the reaction, the solvent was recovered by rotary evaporation and the crude reaction product was recrystallized from methanol to obtain the product as shown in the above formula 107.8 g in 87% yield.

[0045] Example 5

[0046]

[0047] In a 1000 mL reaction flask, 2-methoxyaniline (0.84 mol, 2.2 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), perfluoro-tert-butyl alcohol (640 mL), trimethyl borate (0.038 mol) were added sequentially and the reaction was carried out at 50 °C. The reaction was monitored by TLC spot test and was complete in 12 h. After completion of the reaction, the solvent was recovered by rotary evaporation and the crude reaction product was recrystallized from methanol to obtain the product as shown in the above formula 107.8 g in 87% yield.

[0048] Example 6

[0049]

[0050] In a 1000 mL reaction flask, 2-methoxyaniline (0.84 mol, 2.2 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), perfluoro-tert-butyl alcohol (640 mL), trimethyl borate (0.038 mol) were added sequentially and the reaction was carried out at 50 °C. The reaction was monitored by TLC spot test and was complete in 12 h. After completion of the reaction, the solvent was recovered by rotary evaporation and the crude reaction product was recrystallized from methanol to obtain the product as shown in the above formula 107.8 g in 87% yield.

[0051] Example 7

[0052]

[0053] In a 1000 mL reaction flask, 2-methoxyaniline (0.84 mol, 2.2 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), perfluoro-tert-butyl alcohol (640 mL), trimethyl borate (0.038 mol) were added sequentially and the reaction was carried out at 50 °C. The reaction was monitored by TLC spot test and was complete in 12 h. After completion of the reaction, the solvent was recovered by rotary evaporation and the crude reaction product was recrystallized from methanol to obtain the product as shown in the above formula 107.8 g in 87% yield.

[0054] Example 8

[0055]

[0056] In a 1000 mL reaction flask, 3,5-dimethylaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), hexafluoroisopropanol (640 mL), boron trifluoride diethyl ether (0.038 mol) were added in sequence, and the reaction was carried out at 50 °C, and the reaction was monitored by TLC dot plate, and the reaction was completed after 15 h. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product of the reaction was recrystallized with ethanol to obtain the product shown in the formula (4,4'-(2,2,2-trifluoroethane-1,1-diyl)bis(2,6-dimethylaniline)) 118.7 g, yield 97%.

[0057] 1 H NMR (400 MHz, CDC13) δ 6.95 (s, 4H), 4.38 (q, J = 10.4 Hz, 1H), 3.59 (s, 4H), 2.17 (s, 12H); 19 F NMR (376 MHz, CDC13) δ -66.09 (d, J = 10.3 Hz, 3F); 13 C NMR (100 MHz, CDC13) δ 142.1, 128.8, 126.7 (d, 1 J C-F = 281.1 Hz), 125.4, 121.7, 54.2 (q, 2 J C-F = 27.0 Hz), 17.7; HRMS (ESI) m / z: [M+H] + Calcd for C 18 H 22 F3N2323.1730; Found: 323.1731.

[0058] Example 9

[0059]

[0060] In a 1000 mL reaction flask, 2-chloro-6-methylaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), perfluoroalkyl ethanol (640 mL), triisopropylsilyl trifluoromethanesulfonate (0.038 mol) were added sequentially and the reaction was carried out at 65 °C, monitoring the reaction by TLC spot plate, and the reaction was completed in 18 h. After completion of the reaction, the solvent was recovered by rotary evaporation, and the crude reaction product was recrystallized using toluene to obtain the product shown in the above formula (4,4'-(2,2,2-trifluoroethane-1,1-diyl)bis(2-chloro-6-methylaniline))

[0061] 132.1 g, 96% yield.

[0062] 1 H NMR (400 MHz, CDC13) δ 7.12 (s, 2H), 6.92 (s, 2H), 4.35 (q, J = 9.9 Hz, 1H), 4.00 (s, 4H), 2.18 (s, 6H); 19 F NMR (376 MHz, CDC13) δ -66.29 (d, J = 9.8 Hz, 3F); 13 C NMR (100 MHz, CDC13) δ 140.8, 129.3, 127.3, 126.1 (d, 1 J C-F = 281.8 Hz), 125.3, 123.6, 119.0, 53.5 (q, 2 J C-F = 27.6 Hz), 18.1; HRMS (ESI) m / z: [M+H] + Calcd for C 16 H 16 F3N2Cl2363.0637; Found: 363.0640.

[0063] Example 10

[0064]

[0065] In a 1000 mL reaction flask, 2-chloro-6-methylaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), perfluoroalkyl ethanol (640 mL), triisopropylsilyl trifluoromethanesulfonate (0.038 mol) were added sequentially and the reaction was carried out at 65 °C, monitoring the reaction by TLC spot plate, and the reaction was completed in 18 h. After completion of the reaction, the solvent was recovered by rotary evaporation, and the crude reaction product was recrystallized using toluene to obtain the product shown in the above formula (4,4'-(2,2,2-trifluoroethane-1,1-diyl)bis(2-chloro-6-methylaniline))

[0066] Example 11

[0067]

[0068] In 1000 mL reaction flask, o-benzyl aniline (0.8 mol, 2.1 equiv), trifluoroacetaldehyde hemiacetal (54.7 g, 0.38 mol), tetrafluoropropanol (640 mL), t-butyldimethylsilyl triflate (0.038 mol) were added in sequence and the reaction was carried out at 65 °C. The reaction was monitored by TLC spot plate and the reaction was completed in 18 h. After completion of the reaction, the solvent was recovered by rotary evaporation and the crude reaction product was recrystallized using ethanol to obtain the product (4,4'-(2,2,2-trifluoroethane-1,1-diyl)bis(2-benzylaniline)) 155.9 g in 92% yield.

[0069] 1 H NMR (400 MHz, CDC13) δ 7.30 (t, J = 7.2 Hz, 4H), 7.26 - 7.15 (m, 6H), 7.14 - 7.07 (m, 4H), 6.64 (d, J = 8.1 Hz, 2H), 4.49 (q, J = 10.2 Hz, 1H), 3.90 (s, 4H), 3.37 (s, 4H); 19 F NMR (376 MHz, CDC13) δ -66.24 (d, J = 10.1 Hz, 3F); 13 C NMR (100 MHz, CDC13) δ 144.2, 139.0, 131.7, 128.7, 128.4, 128.2, 126.4, 126.6 (d, 1 J C-F = 281.9 Hz), 126.0, 124.9, 115.9, 54.1 (q, 2 J C-F = 27.2 Hz), 38.2; HRMS (ESI) m / z: [M+H] + Calcd for C 28 H 26 F3N2447.2043; Found: 447.2050.

[0070] Example 12

[0071]

[0072] In 1000 mL reaction flask, 3,3'-oxydianiline (0.38 mol, 1 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), hexafluoroisopropanol (640 mL), boric acid (0.038 mol) were added in sequence and reacted at 65 °C, TLC spot plate monitoring reaction, 18 h reaction was completed. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product of the reaction was recrystallized with ethanol to obtain the product shown in the formula (9-(trifluoromethyl)-9H-xanthene-3,6-diamine) 54.2 g, yield 51%.

[0073] 1 H NMR (400 MHz, CDC13) δ 7.30 (d, J = 8.3 Hz, 1H), 7.11 (t, J = 8.1 Hz, 1H), 6.47 - 6.40 (m, 2H), 6.32 (s, 1H), 6.13 (d, J = 1.9 Hz, 1H), 5.28 (q, J = 7.0 Hz, 1H), 3.73 (s, 4H). 19 F NMR (376 MHz, CDC13) δ -78.02 (d, J = 6.8 Hz, 3F). 13 C NMR (100 MHz, CDC13) δ 156.7, 148.0, 130.5, 129.8 (d, 1 J C-F = 281.5 Hz), 110.0, 105.1, 67.9 (q, 2 J C-F = 27.2 Hz), 29.7. HRMS (ESI) m / z: [M+H] + Calcd for C 14 H 12 F3N2O 281.0896; Found: 281.0899.

[0074] Example 13

[0075]

[0076] In 1000 mL reaction flask, aniline (0.8 mol, 2 equiv), difluoroacetaldehyde hemiacetal (50.4 g, 0.4 mol), hexafluoroisopropanol (640 mL), triphenylborane (0.08 mol) were added in sequence and reacted at 50 °C, TLC spot plate monitoring reaction, 18 h reaction was completed. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product of the reaction was recrystallized with ethanol to obtain the product shown in the formula (4,4'-(2,2-difluoroethane-1,1-diyl)dianiline) 99.2 g, yield 96%.

[0077] 1 H NMR (400MHz, CDCl3) δ7.07(d,J=8.4Hz,4H),6.67–6.62(m,4H),6.19(td,J=56.3,4.4Hz,1H),4.19(td,J=16.2,4.3Hz,1H),3.63(s,4H); 19 F NMR (376MHz, CDCl3) δ-118.04 (dd, J=56.6, 16.2Hz, 2F); 13 C NMR (100MHz, CDCl3) δ145.5,129.8,127.5(t, 3 J C-F =3.5Hz), 117.3(t, 1 J C-F =244.9Hz), 115.2, 53.4(t, 2 J C-F =20.5Hz); HRMS(ESI)m / z:[M+H] + Calculated value C 14 H 15 F2N2249.1198; Measured value; 249.1195.

[0078] Example 14

[0079]

[0080] 2-Methylaniline (0.8 mol, 2 equiv), difluoroacetaldehyde hydrate (39.2 g, 0.4 mol), hexafluoroisopropanol (640 mL), and tris(pentafluorophenyl)borane (0.04 mol) were added sequentially to a 1000 mL reaction flask. The reaction was carried out at 65 °C, and the reaction was monitored by TLC. The reaction was completed in 12 h. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethyl acetate to give 104.9 g of the product shown in the above formula, with a yield of 95%.

[0081] Example 15

[0082]

[0083] 2-tert-butylaniline (0.8 mol, 2 equiv), difluoroacetaldehyde hydrate (39.2 g, 0.4 mol), hexafluorobutanol (640 mL), and trimethylsilyl trifluoromethanesulfonate (0.04 mol) were added sequentially to a 1000 mL reaction flask. The reaction was carried out at 90 °C, and the reaction was monitored by TLC. The reaction was completed in 14 h. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to give 138.2 g of the product shown in the above formula, with a yield of 96%.

[0084] Example 16

[0085]

[0086] In a 1000 mL reaction flask, 3-fluoroaniline (0.8 mol, 2 equiv), difluoroacetaldehyde hemiacetal (50.4 g, 0.4 mol), hexafluoroisopropanol (640 mL), p-toluenesulfonic acid (0.04 mol) were added sequentially and the reaction was carried out at 50 °C. The reaction was monitored by TLC spot plate and the reaction was complete in 14 h. After completion of the reaction, the solvent was recovered by rotary evaporation and the crude reaction product was recrystallized using ethanol to obtain the product shown above as 77.2 g in 68% yield.

[0087] Example 17

[0088]

[0089] In a 1000 mL reaction flask, methyl 2-aminobenzoate (0.96 mol, 2.4 equiv), difluoroacetaldehyde hemiacetal (50.4 g, 0.4 mol), trifluoroethanol (640 mL), N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide (0.04 mol) were added sequentially and the reaction was carried out at 65 °C. The reaction was monitored by TLC spot plate and the reaction was complete in 20 h. After completion of the reaction, the solvent was recovered by rotary evaporation and the crude reaction product was recrystallized using ethanol to obtain the product shown above as Dimethyl 5,5'-(2,2-difluoroethane-l,l-diyl)bis(2-aminobenzoate)) 75.7 g in 52% yield.

[0090] 5,5'-(2,2-difluoroethane-l,l-diyl)bis(2-aminobenzoate)) 75.7 g in 52% yield. 1 H NMR (400 MHz, CDC13) δ 7.79 (d, J = 2.2 Hz, 2H), 7.17 (dd, J = 8.5, 2.2 Hz, 2H), 6.63 (d, J = 8.5 Hz, 2H), 6.20 (td, J = 56.0, 4.1 Hz, 1H), 5.70 (s, 4H), 4.17 (td, J = 16.3, 4.0 Hz, 1H), 3.86 (s, 6H); 19 F NMR (376 MHz, CDC13) δ -118.44 (dd, J = 56.1, 16.3 Hz, 2F); 13 C NMR (100 MHz, CDC13) δ 168.3, 149.6, 134.6, 131.4, 124.8 (t, 3 J C-F = 3.4 Hz), 117.2, 116.9 (t, 1 J C-F = 245.2 Hz), 110.6, 53.0 (t,2 J C-F = 20.7 Hz), 51.6; HRMS (ESI) m / z: [M+H] + Calcd for C 18 H 19 F2N2O4365.1307; Found; 365.1305.

[0091] Example 18

[0092]

[0093] In 1000 mL reaction flask, 2-aminophenol (0.8 mol, 2 equiv), difluoroacetaldehyde hemiacetal (50.4 g, 0.4 mol), hexafluoroisopropanol (640 mL), tris(2,6-difluorophenyl)borane (0.04 mol) were added sequentially and the reaction was carried out at 65 °C, TLC spot plate was used to monitor the reaction, the reaction was completed in 15 h. After completion of the reaction, the solvent was recovered by rotary evaporation, the crude reaction product was recrystallized using methanol to obtain the product as shown in the above formula 81.8 g, yield 73%.

[0094] Example 19

[0095]

[0096] In 1000 mL reaction flask, 2-aminophenol (0.8 mol, 2 equiv), difluoroacetaldehyde hemiacetal (50.4 g, 0.4 mol), hexafluoroisopropanol (640 mL), tris(2,6-difluorophenyl)borane (0.04 mol) were added sequentially and the reaction was carried out at 65 °C, TLC spot plate was used to monitor the reaction, the reaction was completed in 15 h. After completion of the reaction, the solvent was recovered by rotary evaporation, the crude reaction product was recrystallized using methanol to obtain the product as shown in the above formula 81.8 g, yield 73%.

[0097] Example 20

[0098]

[0099] In 1000 mL reaction flask, 2-aminophenol (0.8 mol, 2 equiv), difluoroacetaldehyde hemiacetal (50.4 g, 0.4 mol), hexafluoroisopropanol (640 mL), tris(2,6-difluorophenyl)borane (0.04 mol) were added sequentially and the reaction was carried out at 65 °C, TLC spot plate was used to monitor the reaction, the reaction was completed in 15 h. After completion of the reaction, the solvent was recovered by rotary evaporation, the crude reaction product was recrystallized using methanol to obtain the product as shown in the above formula 81.8 g, yield 73%.

[0100] Obviously, the above embodiments of the present application are merely exemplary and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art, and all the embodiments cannot be enumerated here. Any obvious changes or variations derived from the technical solutions of the present application are still within the protection scope of the present application.

Claims

1. A method of synthesizing a fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compound, characterized by, Comprising: In the presence of a catalyst, aromatic primary amine compounds are reacted with difluoroacetaldehyde hydrate, trifluoroacetaldehyde hydrate, 2,2,3,3-tetrafluoropropionaldehyde hydrate, pentafluoropropionaldehyde hydrate, heptafluorobutyraldehyde hydrate, or nonafluoropentanal hydrate in an organic solvent, and after the reaction is completed, the fluorine alkyl-substituted 4,4'-diaminodiphenylmethane compounds having the structure shown by the following general formula [1] are obtained after post-treatment: ; In General Formula [1], n1and n2are each independently an integer of 0 to 4, R 1 in the case where a plurality of exists, each independently represents a substituent; R 1 independently selected from hydrogen, alkyl, alkoxy, cycloalkyl, aryl, propenyl, halogen, hydroxy, benzyl, thioalkyl; R f independently selected from difluoromethyl, trifluoromethyl, tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl; X is independently selected from methylene, oxygen or sulfur; The catalyst is a Lewis acid or a Brønsted acid; The organic solvent is 2,2-difluoroethanol, hexafluoroisopropanol, hexafluoro-2-methylisopropanol, hexafluoro-2-phenylisopropanol, trifluoroethanol, perfluoroalkylethanol, perfluoro-t-butanol, tetrafluoropropanol, tetrafluorobutanediol, hexafluorobutanol or octafluoropentanol; The post-treatment comprises: after the reaction is completed, the solvent is removed under reduced pressure, the crude product of the reaction is recrystallized to obtain a fluorine alkyl-substituted 4,4'-diaminodiphenylmethane compound; the fluorine alcohol solvent can be recovered by simple distillation operation after the reaction is completed.

2. The method of synthesizing fluoroalkyl substituted 4,4'-diaminodiphenylmethane compounds according to claim 1, wherein, R 1 independently selected from hydrogen, methyl, ethyl, tert-butyl, isopropyl, alkoxy, cycloalkyl, phenyl, propenyl, halogen, hydroxyl, benzyl, sulfanyl.

3. The method of synthesizing fluoroalkyl substituted 4,4'-diaminodiphenylmethane compounds according to claim 1, wherein, The Lewis acid is selected from phenylboronic acid, boric acid, trimethyl borate, triethyl borate, triisopropyl borate, tributyl borate, triphenyl borate, boron trifluoride etherate, tris(2,4-bis(trifluoromethyl)phenyl)borane, tris(pentafluorophenyl)borane, tris(2,2,2-trifluoroethyl)borate, triphenylborane, tris(hexafluoroisopropyl)borate, tris(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)borane, tris(2,4-bis(trifluoromethyl)phenyl)borane, trimethylsilyl trifluoromethanesulfonate, t-butyldimethylsilyl trifluoromethanesulfonate, trimethylsilyl acetate, trimethylsilyl methane sulfonate, N-(trimethylsilyl)bis(trifluoromethylsulfonyl)imide, (pentafluorophenyl)bis(trifluoromethylsulfonyl)trimethylsilane, di-t-butylisobutylsilyl trifluoromethanesulfonate, t-butyldiphenylsilyl trifluoromethanesulfonate, t-butyldimethylsilyl trifluoromethanesulfonate, 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, triisopropylsilyl trifluoromethanesulfonate, diisopropylsilyl bis(trifluoromethanesulfonate), diethylisopropylsilyl trifluoromethanesulfonate, di-t-butylsilyl bis(trifluoromethanesulfonate), triethylsilyl trifluoromethanesulfonate, tris(2,6-difluorophenyl)borane, tris(2,5-bis(trifluoromethyl)phenyl)borane, 2,4,6-tris(3-(trifluoromethyl)phenyl)-1,3,5,2,4,6-trioxabenzene, trityl tetra(pentafluorophenyl)borate, bis(perfluorophenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris[3,5-bis(trifluoromethyl)phenyl]borane, tris(2,2',2''-perfluorobiphenyl)borane, bis(pentafluorophenyl)-(2-perfluorobiphenyl)borane or tris(2-perfluoronaphthyl)borane; The Brønsted acid is selected from acetic acid, benzoic acid, benzene sulfonic acid, p-toluenesulfonic acid, methyl sulfonic acid, camphor sulfonic acid, Amberlyst 15 ion exchange resin, diphenyl phosphate, binaphthyl phosphate, trifluoroacetic acid, trifluoromethanesulfonic acid, lactic acid, oxalic acid, sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid or polyphosphoric acid.

4. The method for synthesizing fluorine alkyl group substituted 4, 4'-diamino diphenyl methane compound according to any one of claims 1-3, characterized in that, The temperature of the reaction is room temperature to 130 ℃, and the time of the reaction is 12-24 h.

5. The method of synthesizing fluoroalkyl substituted 4,4'-diaminodiphenylmethane compounds as claimed in claim 1, wherein, The molar ratio of the aromatic primary amine compound to the difluoroacetaldehyde hydrate, trifluoroacetaldehyde hydrate, 2,2,3,3-tetrafluoropropionaldehyde hydrate, pentafluoropropionaldehyde hydrate, heptafluorobutyraldehyde hydrate or nonafluoropentanal hydrate is 1-2.4:

1. The molar ratio of the aromatic primary amine compound to the difluoroacetaldehyde hydrate, trifluoroacetaldehyde hydrate, 2,2,3,3-tetrafluoropropionaldehyde hydrate, pentafluoropropionaldehyde hydrate, heptafluorobutyraldehyde hydrate or nonafluoropentanal hydrate is 1-2.4:

1.

6. The method for synthesizing fluorine alkyl group substituted 4, 4'-diamino diphenyl methane compound according to claim 1 or 5, characterized in that, The molar ratio of the difluoroacetaldehyde hydrate, the trifluoroacetaldehyde hydrate, the 2,2,3,3-tetrafluoropropionaldehyde hydrate, the pentafluoropropionaldehyde hydrate, the heptafluorobutyraldehyde hydrate or the nonafluoropentanal hydrate to the catalyst is 1:0~0.

2. The molar ratio of the difluoroacetaldehyde hydrate, the trifluoroacetaldehyde hydrate, the 2,2,3,3-tetrafluoropropionaldehyde hydrate, the pentafluoropropionaldehyde hydrate, the heptafluorobutyraldehyde hydrate or the nonafluoropentanal hydrate to the catalyst is

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