The invention relates to a method for synthesizing fluoroalkyl substituted 4, 4apos; novel method for preparing-diaminodiphenylmethane compound

Abstract

The invention provides a novel method for synthesizing a fluoroalkyl substituted 4, 4 '-diaminodiphenylmethane compound, which comprises the following steps: under the action of a catalyst, reacting an amine compound with a fluorine-containing aldehyde compound in an organic solvent, and after the reaction is finished, carrying out post-treatment to obtain the fluoroalkyl substituted 4, 4'-diaminodiphenylmethane compound. The method has the advantages of mild reaction conditions, simple operation, high reaction efficiency, cheap and easily available raw materials, good atom economy, no generation of wastes, and large-scale application prospects. In addition, the fluoroalcohol solvent is recycled through simple distillation operation, the cost of a large amount of solvent is effectively saved, the process safety is improved, and efficient and green industrial production is facilitated.

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and specifically relates to a new method for synthesizing fluoroalkyl substituted 4,4'-diaminodiphenylmethane compounds. Background Art

[0002] Polyimide is a high-performance engineering material. Its rigid imide structure gives it good high temperature resistance, chemical stability, mechanical properties, electrical properties, radiation resistance and self-lubrication. It is widely used in aerospace, machinery, nanotechnology, separation membranes, electrical engineering and microelectronics. However, polyimide has a high melting point, poor solubility, is difficult to form and process, and has high production costs. Its highly conjugated aromatic structure and intermolecular charge transfer complexes lead to its strong coloring, reduced optical transparency and high dielectric constant, which limits its application in technical fields such as flexible electronic products and flexible circuit boards.

[0003] Introducing 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, while improving solubility, transparency and thermal stability, giving it unique advantages and broad development prospects in optoelectronics, aerospace and other fields. Trifluoromethyl-substituted 4,4′-diaminodiphenylmethane is an important fluorine-containing polyimide monomer. In the patent application “1,1,1-trifluoro-2,2-diarylethane production method and 1,1,1-trifluoro-2,2-diarylethane” with publication number CN113396137A, aniline and trifluoroacetaldehyde are used as raw materials. Under anhydrous conditions, anhydrous HF gas is introduced as a catalyst, and a large amount of trifluoromethanesulfonic acid is added. At the same time, special equipment such as stainless steel autoclaves are required to react at high temperature and high pressure, which brings great inconvenience to production operations and is dangerous and complicated to operate. After the reaction is completed, 48% potassium hydroxide aqueous solution is required for neutralization, which produces a large amount of waste water. In addition, the catalyst used is HF gas, which is highly corrosive and highly dangerous, difficult to recycle, and causes serious environmental pollution.

[0004] In summary, the current synthesis methods of trifluoromethyl-substituted 4,4′-diaminodiphenylmethane have some problems. It is particularly important to develop a simple, safe, low-cost and green synthesis method to synthesize trifluoromethyl-substituted and other fluoroalkyl-substituted 4,4′-diaminodiphenylmethane. In addition, there are no reports on the synthesis of fluoroalkyl-substituted 4,4′-diaminodiphenylmethane compounds such as difluoromethyl and pentafluoroethyl. Summary of the invention

[0005] The present invention provides a new method for synthesizing fluoroalkyl substituted 4,4'-diaminodiphenylmethane compounds. The method has readily available raw materials, simple operation, mild reaction conditions, high safety, high reaction yield, good atom economy, and has large-scale application prospects.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] A new method for synthesizing fluoroalkyl substituted 4,4'-diaminodiphenylmethane compounds, comprising:

[0008] Under the action of a catalyst, an amine compound and a fluorine-containing aldehyde compound react in an organic solvent, and after the reaction, post-treatment is performed to obtain the fluoroalkyl-substituted 4,4′-diaminodiphenylmethane compound, which has a structure represented by the following general formula [1]:

[0009]

[0010] In the general formula [1], n1 and n2 are each independently an integer of 0 to 4, and R 1 When there are multiple substituents, they each independently represent a substituent;

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

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

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

[0014] Preferably, the amine compounds include monosubstituted, polysubstituted or unsubstituted aromatic amine compounds and diphenylamine compounds.

[0015] As further preferred, in the monosubstituted, polysubstituted or unsubstituted aromatic amine compounds, each substituent is independently selected from hydrogen, methyl, ethyl, tert-butyl, isopropyl, alkoxy, cycloalkyl, phenyl, propenyl, halogen, hydroxyl, benzyl, sulfanyl, ester, trifluoromethoxy; and the diphenylamine compound is diaminodiphenylmethane, oxydiphenylamine, and sulfodiphenylamine.

[0016] Preferably, the fluorine-containing aldehyde compound includes difluoroacetaldehyde hydrate, difluoroacetaldehyde hemiacetal, trifluoroacetaldehyde hydrate, trifluoroacetaldehyde hemiacetal, trifluoroacetaldehyde hemiacetal, 3,3,3-trifluoropropanal, 2,2,3,3-tetrafluoropropanal hydrate, pentafluoropropanal hydrate, heptafluorobutyraldehyde hydrate or nonafluoropentanal hydrate.

[0017] Preferably, the catalyst is Lewis acid or acid.

[0018] As further preferred, the Lewis acid is selected from phenylboronic acid, boric acid, trimethyl borate, triethyl borate, triisopropyl borate, tributyl borate, triphenyl borate, boron trifluoride ethyl ether, 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-( borane, tris(2,4-bis(trifluoromethyl)phenyl)borane, trimethylsilyl trifluoromethanesulfonate, tert-butyldimethylsilyl trifluoromethanesulfonate, trimethylsilyl acetate, trimethylsilyl methanesulfonate, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, (pentafluorophenyl)bis(trifluoromethanesulfonyl)trimethylsilane, di-tert-butylisobutylsilane trifluoromethanesulfonate, tert-butyldiphenyl trifluoromethanesulfonate Silane esters, tert-butyldimethylsilyl trifluoromethanesulfonate, 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, triisopropylsilyl trifluoromethanesulfonate, diisopropylsilylbis(trifluoromethanesulfonate), diethylisopropylsilyl trifluoromethanesulfonate, di-tert-butylsilylbis(trifluoromethanesulfonic acid), 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-trioxatriborane, trityltetrakis(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-perfluoronaphthalene)borane;

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

[0020] Preferably, the organic solvent is 2,2-difluoroethanol, hexafluoroisopropanol, hexafluoro-2-methylisopropanol, hexafluoro-2-phenylisopropanol, trifluoroethanol, perfluoroalkylethanol, perfluorotert-butyl alcohol, ethylene glycol, tetrafluoropropanol, tetrafluorobutanediol, hexafluorobutanol or octafluoropentanol.

[0021] Preferably, the reaction temperature is room temperature to 130°C, and the reaction time is 12 to 24 hours, more preferably 45 to 90°C for 12 to 20 hours.

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

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

[0024] Preferably, the post-treatment comprises: after the reaction is completed, removing the solvent under reduced pressure, and recrystallizing the crude reaction product to obtain a fluoroalkyl-substituted 4,4′-diaminodiphenylmethane compound.

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

[0026] As a further preference, the fluoroalcohol solvent can be recovered by a simple distillation operation after the reaction is completed.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention provides a new method for synthesizing fluoroalkyl substituted 4,4'-diaminodiphenylmethane compounds, which effectively solves the problems of the traditional method, such as the need for reaction under anhydrous conditions, hydrogen fluoride as a catalyst, high temperature and high pressure, high operating risk, and complex post-processing. Acid as a catalyst does not need to react under anhydrous conditions. The reaction conditions are mild, the operation is simple, the reaction efficiency is high, the raw materials are cheap and easy to obtain, the atom economy is good, no waste is generated, and it has the prospect of large-scale application. In addition, fluoroalcohol solvents can be recycled through simple distillation operations, which effectively saves a lot of solvent costs, improves process safety, and is conducive to efficient and green industrial production. DETAILED DESCRIPTION

[0029] The present invention is described in detail below in conjunction with specific implementation methods. The following specific embodiments are helpful for those skilled in the art to further understand the present invention, but do not limit the present invention in any form.

[0030] Example 1

[0031]

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

[0033] 1H NMR (400MHz, CDCl3) δ7.13 (d, J = 8.2Hz, 4H), 6.64 (d, J = 8.4Hz, 4H), 4.46 (q, J = 10.1Hz, 1H), 3.65 (s, 4H); 19 F NMR (376MHz, CDCl3) δ-66.41 (d, J = 9.9Hz, 3F); 13 C NMR (100MHz, CDCl3) δ145.8,129.9,126.6(d, 1 J C-F =281.8Hz),125.8,115.1,53.9(q, 2 J C-F =27.3Hz); HRMS(ESI)m / z:[M+H] + Calculated value C 14 H 14 F3N2 267.1104; measured value: 267.1108.

[0034] Example 2

[0035]

[0036] 2-Methylaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hemimethyl acetal (49.4 g, 0.38 mol), trifluoroethanol (640 mL), tri[3,5-bis(trifluoromethyl)phenyl]borane (0.038 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 80°C. The reaction was monitored by TLC spot plate, and the reaction was completed in 12 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 107.2 g of the product shown in the above formula (4,4′-(2,2,2-trifluoroethane-1,1-diyl)bis(2-methylaniline)), with a yield of 96%.

[0037] 1 H NMR (400MHz, CDCl3) δ7.04 (d, J = 8.3Hz, 4H), 6.63 (d, J = 7.8Hz, 2H), 4.42 (q, J = 10.3Hz, 1H), 3.58 (s, 4H), 2.14 (s, 6H); 19 F NMR (376MHz, CDCl3) δ-66.24 (d, J = 10.2Hz, 3F); 13 C NMR (100MHz, CDCl3) δ144.0,131.1,127.4,126.6(d, 1 J C-F=281.5Hz),126.0,122.3,114.9,54.1(q, 2 J C-F =27.2Hz),17.4; HRMS(ESI)m / z:[M+H] + Calculated value C 16 H 18 F3N2295.1417; measured value: 295.1413.

[0038] Example 3

[0039]

[0040] 3-Methylaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hemiethanol (54.7 g, 0.38 mol), hexafluoroisopropanol (640 mL), tris(2,4-bis(trifluoromethyl)phenyl)borane (0.019 mol) were added to a 1000 mL reaction bottle 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 14 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethyl acetate to obtain 72.6 g of the product (4,4′-(2,2,2-trifluoroethane-1,1-diyl)bis(3-methylaniline)) shown in the above formula, with a yield of 65%.

[0041] 1 H NMR (400MHz, CDCl3) δ7.17(d,J=8.3Hz,2H),6.53–6.46(m,4H),4.82(q,J=9.7Hz,1H),3.59(s,4H),2.21(s,6H); 19 F NMR (376MHz, CDCl3) δ-65.10 (d, J = 9.8Hz, 3F); 13 CNMR(100MHz,CDCl3)δ145.5,137.8,129.6,127.2(d, 1 J C-F =282.2Hz),124.3,117.2,112.8,45.9(q, 2 J C-F =26.8Hz),19.7; HRMS(ESI)m / z:[M+H] + Calculated value C 16 H 18 F3N2 295.1417; measured value: 295.1416.

[0042] Example 4

[0043]

[0044] 2-Methoxyaniline (0.84 mol, 2.2 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), perfluorotert-butyl alcohol (640 mL), trimethyl borate (0.038 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 50°C. The reaction was monitored by TLC spot plate, and the reaction was completed after 12 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized with methanol to obtain 107.8 g of the product shown in the above formula, with a yield of 87%.

[0045] Example 5

[0046]

[0047] 2-Methylthioaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hemiethanol (54.7 g, 0.38 mol), hexafluoroisopropanol (640 mL), triethyl borate (0.038 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 90°C. The reaction was monitored by TLC spot plate, and the reaction was completed after 12 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 83.3 g of the product shown in the above formula, with a yield of 61%.

[0048] Example 6

[0049]

[0050] 2-aminobiphenyl (0.76 mol, 2 equiv), trifluoroacetaldehyde hemimethyl acetal (49.4 g, 0.38 mol), 2,2-difluoroethanol (640 mL), tris(2,2,2-trifluoroethyl) borate (0.038 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 80°C. The reaction was monitored by TLC spot plate, and the reaction was completed after 15 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized with chloroform to obtain 150.9 g of the product shown in the above formula, with a yield of 95%.

[0051] Example 7

[0052]

[0053] 2-Bromoaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hemimethyl acetal (49.4 g, 0.38 mol), hexafluoro-2-methyl isopropanol (640 mL), tris(hexafluoroisopropyl) borate (0.076 mol) were added to a 1000 mL reaction bottle 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 12 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 82.5 g of the product shown in the above formula, with a yield of 51%.

[0054] Example 8

[0055]

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

[0057] 1 H NMR (400MHz, CDCl3) δ6.95 (s, 4H), 4.38 (q, J = 10.4Hz, 1H), 3.59 (s, 4H), 2.17 (s, 12H); 19 F NMR (376MHz, CDCl3) δ-66.09 (d, J = 10.3Hz, 3F); 13 C NMR (100MHz, CDCl3) δ142.1,128.8,126.7(d, 1 J C-F =281.1Hz),125.4,121.7,54.2(q, 2 J C-F =27.0Hz),17.7; HRMS(ESI)m / z:[M+H] + Calculated value C 18 H 22 F3N2 323.1730; measured value: 323.1731.

[0058] Example 9

[0059]

[0060] 2-Chloro-6-methylaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), perfluoroalkylethanol (640 mL), triisopropylsilyl trifluoromethanesulfonate (0.038 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 65°C. The reaction was monitored by TLC spot plate, and the reaction was completed after 18 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from 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, yield 96%.

[0062] 1 H NMR (400MHz, CDCl3) δ7.12 (s, 2H), 6.92 (s, 2H), 4.35 (q, J = 9.9Hz, 1H), 4.00 (s, 4H), 2.18 (s, 6H); 19 F NMR (376MHz, CDCl3) δ-66.29 (d, J = 9.8Hz, 3F); 13 C NMR (100MHz, CDCl3) δ140.8,129.3,127.3,126.1(d, 1 J C-F =281.8Hz),125.3,123.6,119.0,53.5(q, 2 J C-F =27.6Hz),18.1; HRMS(ESI)m / z:[M+H] + Calculated value C 16 H 16 F3N2Cl2 363.0637; measured value: 363.0640.

[0063] Example 10

[0064]

[0065] 2-Methyl-3-fluoroaniline (0.76 mol, 2 equiv), trifluoroacetaldehyde hemiethanol (54.7 g, 0.38 mol), hexafluoroisopropanol (640 mL), and bis(perfluorophenyl)borane (0.019 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 45°C. The reaction was monitored by TLC spot plate, and the reaction was completed after 12 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 95.3 g of the product shown in the above formula, with a yield of 76%.

[0066] Embodiment 11

[0067]

[0068] o-Benzylaniline (0.8 mol, 2.1 equiv), trifluoroacetaldehyde hemiethyl acetal (54.7 g, 0.38 mol), tetrafluoropropanol (640 mL), tert-butyldimethylsilyl trifluoromethanesulfonate (0.038 mol) were added to a 1000 mL reaction bottle 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 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 155.9 g of the product shown in the above formula (4,4′-(2,2,2-trifluoroethane-1,1-diyl)bis(2-benzylaniline)), with a yield of 92%.

[0069] 1 H NMR(400MHz, CDCl3)δ7.30(t,J=7.2Hz,4H),7.26–7.15(m,6H),7.14–7.07(m, 4H), 6.64 (d, J = 8.1Hz, 2H), 4.49 (q, J = 10.2Hz, 1H), 3.90 (s, 4H), 3.37 (s, 4H); 19 F NMR (376MHz, CDCl3) δ-66.24 (d, J = 10.1Hz, 3F); 13 C NMR (100MHz, CDCl3) δ144.2,139.0,131.7,128.7,128.4,128.2,126.4,126.6(d, 1 J C-F =281.9Hz),126.0,124.9,115.9,54.1(q, 2 J C-F =27.2Hz),38.2; HRMS(ESI)m / z:[M+H] + Calculated value C 28 H 26 F3N2 447.2043; measured value: 447.2050.

[0070] Example 12

[0071]

[0072] 3,3′-oxydiphenylamine (0.38 mol, 1 equiv), trifluoroacetaldehyde hydrate (44.1 g, 0.38 mol), tetrafluoropropanol (640 mL), and boric acid (0.038 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 65°C. The reaction was monitored by TLC spot plate, and the reaction was completed after 18 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 54.2 g of the product (9-(trifluoromethyl)-9H-xanthene-3,6-diamine) shown in the above formula, with a yield of 51%.

[0073] 1 H NMR(400MHz, CDCl3)δ7.30(d,J=8.3Hz,1H),7.11(t,J=8.1Hz,1H),6.47–6.40( m,2H),6.32(s,1H),6.13(d,J=1.9Hz,1H),5.28(q,J=7.0Hz,1H),3.73(s,4H). 19 F NMR (376MHz, CDCl3) δ-78.02 (d, J = 6.8Hz, 3F). 13 C NMR (100MHz, CDCl3) δ156.7,148.0,130.5,129.8(d, 1 J C-F =281.5Hz),110.0,105.1,67.9(q, 2 J C-F =27.2Hz),29.7.HRMS(ESI)m / z:[M+H] + Calculated value C 14 H 12 F3N2O 281.0896; measured value: 281.0899.

[0074] Embodiment 13

[0075]

[0076] Aniline (0.8 mol, 2 equiv), difluoroacetaldehyde hemiethanol (50.4 g, 0.4 mol), hexafluoroisopropanol (640 mL), and triphenylborane (0.08 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 50°C. The reaction was monitored by TLC spot plate, and the reaction was completed after 18 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 99.2 g of the product (4,4′-(2,2-difluoroethane-1,1-diyl)dianiline) shown in the above formula, with a yield of 96%. 1H 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;Measurement value;249.1195.

[0077] Embodiment 14

[0078]

[0079] 2-Methylaniline (0.8 mol, 2 equiv), difluoroacetaldehyde hydrate (39.2 g, 0.4 mol), hexafluoroisopropanol (640 mL), tris(pentafluorophenyl)borane (0.04 mol) were added to a 1000 mL reaction bottle 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 12 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethyl acetate to obtain 104.9 g of the product shown in the above formula, with a yield of 95%.

[0080] Embodiment 15

[0081]

[0082] 2-tert-butylaniline (0.8 mol, 2 equiv), difluoroacetaldehyde hydrate (39.2 g, 0.4 mol), hexafluorobutanol (640 mL), trimethylsilyl trifluoromethanesulfonate (0.04 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 90°C. The reaction was monitored by TLC spot plate, and the reaction was completed after 14 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 138.2 g of the product shown in the above formula, with a yield of 96%.

[0083] Example 16

[0084]

[0085] 3-Fluoroaniline (0.8 mol, 2 equiv), difluoroacetaldehyde hemiethanol (50.4 g, 0.4 mol), hexafluoroisopropanol (640 mL), and p-toluenesulfonic acid (0.04 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 50°C. The reaction was monitored by TLC spot plate, and the reaction was completed after 14 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 77.2 g of the product shown in the above formula, with a yield of 68%.

[0086] Embodiment 17

[0087]

[0088] In a 1000 mL reaction bottle, methyl 2-aminobenzoate (0.96 mol, 2.4 equiv), difluoroacetaldehyde hemiethanol (50.4 g, 0.4 mol), trifluoroethanol (640 mL), and N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide (0.04 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 20 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain the product shown in the above formula (Dimethylsilyl)

[0089] 5,5′-(2,2-difluoroethane-1,1-diyl)bis(2-aminobenzoate))75.7g, yield 52%.

[0090] 1 H NMR (400MHz, CDCl3) δ7.79 (d, J=2.2Hz, 2H), 7.17 (dd, J=8.5, 2.2Hz, 2H), 6.63 (d, J=8.5Hz, 2H),6.20(td,J=56.0,4.1Hz,1H),5.70(s,4H),4.17(td,J=16.3,4.0Hz,1H),3.86(s,6H); 19 F NMR (376MHz, CDCl3) δ-118.44 (dd, J=56.1, 16.3Hz, 2F); 13 C NMR (100MHz, CDCl3) δ168.3,149.6,134.6,131.4,124.8(t, 3 J C-F =3.4Hz),117.2,116.9(t, 1 J C-F=245.2Hz),110.6,53.0(t, 2 J C-F =20.7Hz),51.6; HRMS(ESI)m / z:[M+H] + Calculated value C 18 H 19 F2N2O4365.1307; measured value; 365.1305.

[0091] Embodiment 18

[0092]

[0093] 2-Aminophenol (0.8 mol, 2 equiv), difluoroacetaldehyde hemiethanol (50.4 g, 0.4 mol), hexafluoroisopropanol (640 mL), tris(2,6-difluorophenyl)borane (0.04 mol) were added to a 1000 mL reaction bottle 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 15 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized with methanol to obtain 81.8 g of the product shown in the above formula, with a yield of 73%.

[0094] Embodiment 19

[0095]

[0096] 2-isopropenylphenylaniline (0.88 mol, 2.2 equiv), difluoroacetaldehyde hemiethanol (50.4 g, 0.4 mol), tetrafluorobutanediol (640 mL), tris(2,5-bis(trifluoromethyl)phenyl)borane (0.04 mol) were added to a 1000 mL reaction bottle in sequence, and the reaction was carried out at 50°C. The reaction was monitored by TLC spot plate, and the reaction was completed after 18 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 66.9 g of the product shown in the above formula, with a yield of 51%.

[0097] Embodiment 20

[0098]

[0099] Aniline (0.64 mol, 2 equiv), pentafluoropropionaldehyde hydrate (53 g, 0.32 mol), hexafluoroisopropanol (640 mL), tris(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)borane (0.032 mol) were added to a 1000 mL reaction bottle 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 14 hours. After the reaction was completed, the solvent was recovered by rotary evaporation, and the crude product was recrystallized from ethanol to obtain 68.8 g of the product shown in the above formula, with a yield of 68%.

[0100] Obviously, the above embodiments of the present invention are merely examples to more clearly illustrate the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A novel method for synthesizing fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compounds, characterized in that: include: Under the action of a catalyst, an amine compound and a fluorine-containing aldehyde compound react in an organic solvent, and after the reaction, post-treatment is performed to obtain the fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compound, which has a structure represented by the following general formula [1]: In the general formula [1], n1 and n2 are each independently an integer of 0 to 4, and R 1 When there are multiple substituents, they each independently represent a substituent; R 1 independently selected from hydrogen, alkyl, alkoxy, cycloalkyl, aryl, propenyl, halogen, hydroxyl, benzyl, sulfanyl, ester; R f Independently selected from difluoromethyl, trifluoromethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl; X is independently selected from methylene, oxygen or sulfur.

2. A novel method for synthesizing fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compounds according to claim 1, characterized in that: The amine compounds include monosubstituted, polysubstituted or unsubstituted aromatic amine compounds and diphenylamine compounds.

3. A novel method for synthesizing fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compounds according to claim 2, characterized in that: In the monosubstituted, polysubstituted or unsubstituted aromatic amine compounds, each substituent is independently selected from hydrogen, methyl, ethyl, tert-butyl, isopropyl, alkoxy, cycloalkyl, phenyl, propenyl, halogen, hydroxyl, benzyl, sulfanyl, ester, trifluoromethoxy; the diphenylamine compound is diaminodiphenylmethane, oxydiphenylamine, and sulfodiphenylamine.

4. A novel method for synthesizing fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compounds according to claim 1, characterized in that: The fluorine-containing aldehyde compounds include difluoroacetaldehyde hydrate, difluoroacetaldehyde hemiacetal, trifluoroacetaldehyde hydrate, trifluoroacetaldehyde hemiacetal, trifluoroacetaldehyde hemiacetal, 3,3,3-trifluoropropanal, 2,2,3,3-tetrafluoropropanal hydrate, pentafluoropropanal hydrate, heptafluorobutyraldehyde hydrate or nonafluorovaleraldehyde hydrate.

5. A novel method for synthesizing fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compounds according to claim 1, characterized in that: The catalyst is Lewis acid or acid.

6. A novel method for synthesizing fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compounds according to claim 5, characterized in that: The Lewis acid is selected from phenylboronic acid, boric acid, trimethyl borate, triethyl borate, triisopropyl borate, tributyl borate, triphenyl borate, boron trifluoride ethyl ether, 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, tert-butyldimethylsilyl trifluoromethanesulfonate, trimethylsilyl acetate, trimethylsilyl methanesulfonate, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, (pentafluorophenyl)bis(trifluoromethanesulfonyl)trimethylsilane, di-tert-butylisobutylsilane trifluoromethanesulfonate, tert-butyldiphenylsilyl trifluoromethanesulfonate, tert-Butyldimethylsilyl trifluoromethanesulfonate, 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, triisopropylsilyl trifluoromethanesulfonate, diisopropylsilylbis(trifluoromethanesulfonate), diethylisopropylsilyl trifluoromethanesulfonate, di-tert-butylsilylbis(trifluoromethanesulfonic acid), 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-trioxatriborane, trityltetrakis(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-perfluoronaphthalene)borane; The The acid is selected from acetic acid, benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, camphorsulfonic acid, Amberlyst 15 ion exchange resin, diphenyl phosphate, binaphthol phosphate, trifluoroacetic acid, trifluoromethanesulfonic acid, lactic acid, oxalic acid, sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid or polyphosphoric acid.

7. A novel method for synthesizing fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compounds according to claim 1, characterized in that: The organic solvent is 2,2-difluoroethanol, hexafluoroisopropanol, hexafluoro-2-methylisopropanol, hexafluoro-2-phenylisopropanol, trifluoroethanol, perfluoroalkylethanol, perfluorotert-butyl alcohol, ethylene glycol, tetrafluoropropanol, tetrafluorobutanediol, hexafluorobutanol or octafluoropentanol.

8. A novel method for synthesizing fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compounds according to any one of claims 1 to 7, characterized in that: The reaction temperature is from room temperature to 130°C, and the reaction time is 12 to 24 hours.

9. A novel method for synthesizing fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compounds according to claim 1, characterized in that: The molar ratio of the amine compound to the fluorine-containing aldehyde compound is 1-2.4:

1.

10. A novel method for synthesizing fluoroalkyl-substituted 4,4'-diaminodiphenylmethane compounds according to claim 1 or 9, characterized in that: The molar ratio of the fluorine-containing aldehyde compound to the catalyst is 1:0-0.2.

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