2, 2 '-dihalo-1, 1'-binaphthalene compound as well as preparation method and application thereof

Abstract

The invention discloses a 2, 2 '-dihalo-1, 1'-binaphthalene compound as well as a preparation method and application thereof. The structural formula of the 2, 2 '-dihalo-1, 1'-binaphthalene compound is as follows: # imgabs0, in the formula, R1 is one of hydrogen and tertiary butyl, R2 is one of methyl, isobutyl, phenyl, benzyl, 4-fluorophenyl and 4-chlorphenyl, and X is one of chlorine and bromine. The preparation method of the 2, 2 '-dihalo-1, 1'-binaphthalene compounds has the advantages of easily available raw materials, mild reaction conditions, wide substrate universality, simple operation, easy industrial production and the like, and a series of brand new 2, 2 '-dihalo-1, 1'-binaphthalene compounds are prepared. The compounds have unique advantages in construction of binaphthalene skeleton ligands and binaphthalene skeleton catalysts, and are suitable for large-scale industrial application.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to a 2,2'-dihalo-1,1'-binaphthyl compound, a preparation method and application thereof. Background Art

[0002] The binaphthyl structure is a valuable building block for applications in pesticides, pharmaceuticals, and materials (Chem. Soc. Rev. 2021, 50, 2968; Angew. Chem. Int. Ed. 2023, 62, e202303128; ACS. Catal. 2022, 12, 4918). Site-specific functionalization of halogenated binaphthyl compounds also offers unique advantages in constructing ligands and catalysts (Chem. Rev. 2021, 121, 4805; J. Am. Chem. Soc. 2021, 143, 12335). Polyhalogenated binaphthyl compounds are of great value (Eur. J. Org. Chem. 2024, 27, e202300826), but their synthesis remains a major challenge.

[0003] Currently, the synthesis of dihalogenated binaphthyl compounds still relies on the post-halogenation of binaphthyl compounds, such as the Sandmeyer reaction (Tetrahedron: Asymmetry 2013, 24, 894) and electrophilic halogenation reaction (Synth. Commun. 2003, 33, 2763; Eur. J. Org. Chem. 2010, 2010, 1669). These methods not only require pre-functionalization but also usually require harsh reaction conditions. Studies have shown that ring-opening cleavage of cyclic diaryl halide salts (Angew.Chem.Int.Ed.2015,54,8736; Chem.2018,4,599) is a good method for constructing halogenated biaryl compounds, but this method still has obvious defects. For example, the synthesis steps of cyclic halide salts of binaphthyl precursors are cumbersome and the step economy is not high (Angew.Chem.Int.Ed.2021,60,14852; Chem.Sci.2024,15,1557). In summary, the existing synthesis methods of polyhalogenated binaphthyl compounds generally have obvious defects and are not suitable for large-scale industrial applications.

[0004] Therefore, it is of great significance to develop a method for preparing 2,2′-dihalogen-1,1′-binaphthyl compounds with readily available raw materials, mild reaction conditions, wide substrate applicability, simple operation, and easy industrial production, and to prepare a series of new 2,2′-dihalogen-1,1′-binaphthyl compounds. Summary of the Invention

[0005] The purpose of the present invention is to provide a 2,2'-dihalo-1,1'-binaphthyl compound and a preparation method and application thereof.

[0006] The technical solution adopted by the present invention is:

[0007] A 2,2′-dihalogen-1,1′-binaphthyl compound, the structural formula of which is as follows:

[0008] Where R 1 is one of hydrogen and tert-butyl, R 2 is one of methyl, isobutyl, phenyl, benzyl, 4-fluorophenyl and 4-chlorophenyl, and X is one of chlorine and bromine.

[0009] Preferably, the 2,2′-dihalogen-1,1′-binaphthyl compound is

[0010] One of them.

[0011] A method for preparing the above-mentioned 2,2′-dihalo-1,1′-binaphthyl compound comprises the following steps:

[0012] 1) dispersing an alkyne bromide compound and a palladium catalyst in a solvent to react, wherein the structural formula of the alkyne bromide compound is Then the product is separated to obtain the intermediate product;

[0013] 2) The intermediate product, the halogen source and the catalyst are dispersed in a solvent for reaction, and then the product is separated and purified to obtain a 2,2'-dihalogen-1,1'-binaphthyl compound.

[0014] Preferably, in step 1), the molar ratio of the alkynyl bromide compound to the palladium catalyst is 1:0.01-1.

[0015] Preferably, the alkynyl bromide compound in step 1) is one of 2-benzyl-4-bromo-1-phenylbut-3-yn-2-ol, 4-bromo-1-(4-(tert-butyl)phenyl)-2-methylbut-3-yn-2-ol, 3-benzyl-1-bromo-5-methylhex-1-yn-3-ol, 4-bromo-1,2-diphenylbut-3-yn-2-ol, 4-bromo-2-(4-fluorophenyl)-1-phenylbut-3-yn-2-ol and 4-bromo-2-(4-chlorophenyl)-1-phenylbut-3-yn-2-ol.

[0016] Preferably, the palladium catalyst in step 1) is at least one of palladium bromide, palladium chloride, bis(acetonitrile)palladium dichloride, dibenzonitrilepalladium dichloride, palladium acetate, and palladium trifluoroacetate.

[0017] Preferably, the solvent in step 1) is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-N-ethylformamide, N-ethylformamide, and water.

[0018] Preferably, the reaction in step 1) is carried out at a temperature of 20° C. to 80° C., and the reaction time is 8 h to 36 h.

[0019] Preferably, the molar ratio of the alkynyl bromide compound in step 1), the halogen source in step 2), and the catalyst in step 2) is 1:0.5-5:0.01-1.

[0020] Preferably, the halogen source in step 2) is one of N-bromosuccinimide, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chlorosuccinimide, and N-chlorophthalimide.

[0021] Preferably, the catalyst in step 2) is at least one of R-binaphthol phosphate and S-binaphthol phosphate.

[0022] Preferably, the solvent in step 2) is at least one of acetonitrile, dichloromethane, dichloroethane, and toluene.

[0023] Preferably, the reaction in step 2) is carried out at a temperature of 0°C to 50°C, and the reaction time is 2h to 24h.

[0024] Preferably, the purification method in step 2) is column chromatography purification.

[0025] Preferably, the eluent used in the column chromatography purification is one of petroleum ether and a petroleum ether-ethyl acetate mixture.

[0026] A use of the above-mentioned 2,2'-dihalo-1,1'-binaphthyl compound in the preparation of a binaphthyl skeleton ligand or a binaphthyl skeleton catalyst.

[0027] Preferably, the binaphthyl skeleton ligand is 3,3′-dibenzyl-2,2′-dimethylthio-1,1′-binaphthyl.

[0028] Preferably, the binaphthyl skeleton catalyst is 3,3′-dibenzyl-1,1′-binaphthol phosphate.

[0029] The beneficial effects of the present invention are as follows: the method for preparing 2,2′-dihalogen-1,1′-binaphthyl compounds of the present invention has the advantages of readily available raw materials, mild reaction conditions, wide substrate universality, simple operation, and ease of industrial production, thereby preparing a series of novel 2,2′-dihalogen-1,1′-binaphthyl compounds. These compounds have unique advantages in the construction of binaphthyl skeleton ligands and binaphthyl skeleton catalysts and are suitable for large-scale industrial applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 1.

[0031] Figure 2 This is the carbon nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 1.

[0032] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 8.

[0033] Figure 4 This is the carbon nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 8.

[0034] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 9.

[0035] Figure 6 This is the carbon nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 9.

[0036] Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 10.

[0037] Figure 8 This is the carbon nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 10.

[0038] Figure 9 This is the hydrogen nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 11.

[0039] Figure 10 This is the carbon nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 11.

[0040] Figure 11 This is the hydrogen nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 12.

[0041] Figure 12 This is the carbon nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 12.

[0042] Figure 13 This is the hydrogen nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 13.

[0043] Figure 14 This is the carbon nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound of Example 13.

[0044] Figure 15 This is the hydrogen nuclear magnetic resonance spectrum of the binaphthyl skeleton ligand in Application Example 1.

[0045] Figure 16 This is the carbon NMR spectrum of the binaphthyl skeleton ligand in Application Example 1.

[0046] Figure 17 This is the hydrogen nuclear magnetic resonance spectrum of the binaphthyl skeleton catalyst in Application Example 2.

[0047] Figure 18 This is the carbon nuclear magnetic resonance spectrum of the binaphthyl skeleton catalyst in Application Example 2.

[0048] Figure 19 This is the nuclear magnetic resonance phosphorus spectrum of the binaphthyl skeleton catalyst in Application Example 2. DETAILED DESCRIPTION

[0049] The present invention will be further explained and illustrated below with reference to specific embodiments.

[0050] Example 1:

[0051] A 2,2′-dihalo-1,1′-binaphthyl compound, the preparation method of which is as follows:

[0052] 1) 0.2 mmol of 2-benzyl-4-bromo-1-phenylbut-3-yn-2-ol, 0.02 mmol of palladium bromide, 0.15 mL of water, and 2 mL of N,N-dimethylformamide were added to reaction tube A, and stirred at 35°C for 24 h at a stirring rate of 600 rpm. 20 mL of saturated brine was then added to the reaction solution, and the mixture was extracted with 3 mL of ethyl acetate three times. The organic phases were combined, filtered, and the filtrate was concentrated under reduced pressure to obtain an intermediate product;

[0053] 2) The intermediate product and 1 mL of acetonitrile were added to reaction tube B and stirred to dissolve. 0.15 mmol of N-bromophthalimide and 0.01 mmol of R-binaphthol phosphate were dissolved in 1 mL of acetonitrile and added to the reaction tube. The mixture was stirred at 35 ° C for 4 h at a stirring rate of 600 rpm. 5 mL of saturated brine was added to the reaction solution, and the mixture was extracted with 5 mL of ethyl acetate for 3 times. The organic phases were combined, filtered, and the filtrate was concentrated under reduced pressure. The mixture was then separated and purified by column chromatography. The eluent used for column chromatography purification consisted of petroleum ether and ethyl acetate in a volume ratio of 100:1 to obtain 2,2′-dihalo-1,1′-binaphthyl compounds (yield: 43%).

[0054] The nuclear magnetic resonance hydrogen spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is as follows: Figure 1 As shown, the carbon NMR spectrum is as follows Figure 2 shown.

[0055] Spectrum analysis:

[0056] 1 H NMR (400MHz, CDCl3): δ7.81 (d, J = 8.2Hz, 2H), 7.69 (s, 2H), 7.49-7.43 (m, 2H), 7.39-7 .33(m,4H),7.32-7.27(m,6H),7.26-7.22(m,2H),7.05(d,J=8.4Hz,2H),4.41(s,4H).

[0057] 13 C NMR (100MHz, CDCl3): δ139.5,138.9,138.1,132.5,132.0,129.6,129.2,128.6,127.8,126.8,126.4,126.3,126.3,125.7,42.7.

[0058] The high-resolution mass spectrometry data of the 2,2′-dihalo-1,1′-binaphthyl compound in this example are as follows:

[0059] ESI-HRMS (m / z): [M+H] + C 34 H 24 Br2,593.0297,found:593.0293.

[0060] In summary, the structural formula of the 2,2′-dihalogen-1,1′-binaphthyl compound (3,3′-dibenzyl-2,2′-dibromo-1,1′-binaphthyl) in this embodiment is as follows:

[0061]

[0062] Example 2:

[0063] A method for preparing 2,2′-dihalo-1,1′-binaphthyl compounds is identical to Example 1, except that an equal volume of “N,N-dimethylformamide” in step 1) is replaced with “N-methyl-N-ethylformamide”.

[0064] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound (same as in Example 1) in this example is 35%.

[0065] Example 3:

[0066] A method for preparing 2,2′-dihalo-1,1′-binaphthyl compounds is identical to Example 1 except that an equal molar amount of “palladium bromide” in step 1) is replaced with “palladium acetate”.

[0067] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound (same as in Example 1) in this example is 30%.

[0068] Example 4:

[0069] A method for preparing 2,2′-dihalo-1,1′-binaphthyl compounds is identical to Example 1 except that an equal molar amount of “N-bromophthalimide” in step 2) is replaced with “N-bromosuccinimide”.

[0070] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound (same as in Example 1) in this example is 37%.

[0071] Example 5:

[0072] A method for preparing 2,2′-dihalo-1,1′-binaphthyl compounds is identical to Example 1, except that an equal molar amount of “N-bromophthalimide” in step 2) is replaced with “1,3-dibromo-5,5-dimethylhydantoin”.

[0073] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound (same as in Example 1) in this example is 26%.

[0074] Example 6:

[0075] A method for preparing 2,2′-dihalo-1,1′-binaphthyl compounds is identical to Example 1 except that the reaction temperature in step 1) is adjusted from 35° C. to 50° C.

[0076] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound (same as in Example 1) in this example is 40%.

[0077] Example 7:

[0078] A method for preparing 2,2′-dihalo-1,1′-binaphthyl compounds is identical to Example 1 except that the reaction temperature in step 1) is adjusted from 35° C. to 60° C.

[0079] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound (same as in Example 1) in this example is 39%.

[0080] Example 8:

[0081] A 2,2′-dihalo-1,1′-binaphthyl compound, prepared in the same manner as in Example 1, except that an equal molar amount of “2-benzyl-4-bromo-1-phenylbut-3-yn-2-ol” in step 1) is replaced with “4-bromo-1-(4-(tert-butyl)phenyl)-2-methylbut-3-yn-2-ol”.

[0082] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is 41%.

[0083] The nuclear magnetic resonance hydrogen spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is as follows: Figure 3 As shown, the carbon NMR spectrum is as follows Figure 4 shown.

[0084] Spectrum analysis:

[0085] 1 H NMR (400MHz, CDCl3): δ77.83-7.76(m,4H),7.57-7.52(m,2H),6.92(s,2H),2.67(s,6H),1.09(s,18H).

[0086] 13 C NMR (100MHz, CDCl3): δ148.7,138.3,134.7,131.7,130.7,128.2,127.0,126.3,124.9,121.2,34.7,31.0,24.3.

[0087] The high-resolution mass spectrometry data of the 2,2′-dihalo-1,1′-binaphthyl compound in this example are as follows:

[0088] ESI-HRMS (m / z): [M] + calcd for C 30 H 32 Br2,552.0845,found:552.0845.

[0089] In summary, the structural formula of the 2,2′-dihalo-1,1′-binaphthyl compound (2,2′-dibromo-7,7′-di-tert-butyl-3,3′-dimethyl-1,1′-binaphthyl) in this embodiment is as follows:

[0090]

[0091] Example 9:

[0092] A 2,2′-dihalo-1,1′-binaphthyl compound, prepared in the same manner as in Example 1, except that an equal molar amount of “2-benzyl-4-bromo-1-phenylbut-3-yn-2-ol” in step 1) is replaced with “3-benzyl-1-bromo-5-methylhex-1-yn-3-ol”.

[0093] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is 19%.

[0094] The nuclear magnetic resonance hydrogen spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is as follows: Figure 5 As shown, the carbon NMR spectrum is as follows Figure 6 shown.

[0095] Spectrum analysis:

[0096] 1 H NMR (400MHz, CDCl3): δ7.87(d,J=8.2Hz,2H),7.79(s,2H),7.46(t,J=7.5Hz,2H),7.25-7.1 9(m,2H),6.98(d,J=8.5Hz,2H),2.95-2.84(m,4H),2.22-2.11(m,2H),1.07-0.99(m,12H).

[0097] 13 C NMR (100MHz, CDCl3): δ138.8,138.8,132.4,131.8,129.4,127.6,126.4,126.4,126.3,125.8,46.0,29.0,22.4,22.4.

[0098] The high-resolution mass spectrometry data of the 2,2′-dihalo-1,1′-binaphthyl compound in this example are as follows:

[0099] ESI-HRMS (m / z): [M+H] + calcd for C 28 H 29 Br2,525.0610,found:525.0610.

[0100] In summary, the structural formula of the 2,2′-dihalogen-1,1′-binaphthyl compound (2,2′-dibromo-3,3′-diisobutyl-1,1′-binaphthyl) in this embodiment is as follows:

[0101]

[0102] Example 10:

[0103] A 2,2′-dihalo-1,1′-binaphthyl compound, prepared in the same manner as in Example 1, except that an equal molar amount of “2-benzyl-4-bromo-1-phenylbut-3-yn-2-ol” in step 1) is replaced with “4-bromo-1,2-diphenylbut-3-yn-2-ol”.

[0104] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is 42%.

[0105] The nuclear magnetic resonance hydrogen spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is as follows: Figure 7 As shown, the carbon NMR spectrum is as follows Figure 8 shown.

[0106] Spectrum analysis:

[0107] 1 H NMR (400MHz, CDCl3): δ7.98-7.91(m,4H), 7.62-7.57(m,4H), 7.55-7.41(m,8H), 7.38-7.31(m,2H), 7.18(d,J=8.4Hz,2H).

[0108] 13 C NMR (100MHz, CDCl3): δ141.6,140.7,139.0,132.3,130.0,129.9,128.2,127.9,127.6,127.3,126.7,125.9,123.8.

[0109] The high-resolution mass spectrometry data of the 2,2′-dihalo-1,1′-binaphthyl compound in this example are as follows:

[0110] ESI-HRMS (m / z): [M+H] + calcd for C 32 H 21 Br2,564.9984,found:564.9984.

[0111] In summary, the structural formula of the 2,2′-dihalogen-1,1′-binaphthyl compound (2,2′-dibromo-3,3′-diphenyl-1,1′-binaphthyl) in this embodiment is as follows:

[0112]

[0113] Example 11:

[0114] A 2,2′-dihalo-1,1′-binaphthyl compound, prepared in the same manner as in Example 1, except that an equal molar amount of “2-benzyl-4-bromo-1-phenylbut-3-yn-2-ol” in step 1) is replaced with “4-bromo-2-(4-fluorophenyl)-1-phenylbut-3-yn-2-ol”.

[0115] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is 40%.

[0116] The nuclear magnetic resonance hydrogen spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is as follows: Figure 9 As shown, the carbon NMR spectrum is as follows Figure 10 shown.

[0117] Spectrum analysis:

[0118] 1 H NMR (400MHz, CDCl3): δ7.94 (d, J=8.8Hz, 4H), 7.59-7.51 (m, 6H), 7.38-7.31 (m, 2H), 7.20-7.13 (m, 6H).

[0119] 13 C NMR (100MHz, CDCl3): δ163.6,139.7,139.0,137.5,137.4,132.4,132.3,131.6,131.5,130.1,128.2,127.5,126.9,125.9,123.8,115.0,114.8.

[0120] The high-resolution mass spectrometry data of the 2,2′-dihalo-1,1′-binaphthyl compound in this example are as follows:

[0121] ESI-HRMS (m / z): [MH] - calcd for C 32 H 17 Br2F2,596.9671,found:596.9673.

[0122] In summary, the structural formula of the 2,2′-dihalo-1,1′-binaphthyl compound (2,2′-dibromo-3,3′-bis(4-fluorophenyl)-1,1′-binaphthyl) in this embodiment is as follows:

[0123]

[0124] Example 12:

[0125] A 2,2′-dihalo-1,1′-binaphthyl compound, prepared in the same manner as in Example 1, except that an equal molar amount of “2-benzyl-4-bromo-1-phenylbut-3-yn-2-ol” in step 1) is replaced with “4-bromo-2-(4-chlorophenyl)-1-phenylbut-3-yn-2-ol”.

[0126] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is 33%.

[0127] The nuclear magnetic resonance hydrogen spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is as follows: Figure 11 As shown, the carbon NMR spectrum is as follows Figure 12 shown.

[0128] Spectrum analysis:

[0129] 1 H NMR (400MHz, CDCl3): δ7.94 (t, J = 4.0 Hz, 4H), 7.57-7.50 (m, 6H), 7.47-7.42 (m, 4H), 7.38-7.32 (m, 2H), 7.15 (d, J = 8.4Hz, 2H).

[0130] 13 C NMR (100MHz, CDCl3): δ139.5,139.2,138.7,133.5,132.1,132.0,130.9,129.7,127.9,127.8,127.3,126.6,125.5,123.1.

[0131] The high-resolution mass spectrometry data of the 2,2′-dihalo-1,1′-binaphthyl compound in this example are as follows:

[0132] ESI-HRMS (m / z): [M] + calcd for C 32 H 19 Br2Cl2,632.9205,found:632.9200.

[0133] In summary, the structural formula of the 2,2′-dihalogen-1,1′-binaphthyl compound (2,2′-dibromo-3,3′-bis(4-chlorophenyl)-1,1′-binaphthyl) in this embodiment is as follows:

[0134]

[0135] Example 13:

[0136] A 2,2′-dihalo-1,1′-binaphthyl compound is prepared in the same manner as in Example 1, except that an equal molar amount of “N-bromophthalimide” in step 2) is replaced with “N-chlorophthalimide” and the reaction time in step 2) is adjusted from “4 h” to “12 h”.

[0137] According to the test, the yield of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is 18%.

[0138] The nuclear magnetic resonance hydrogen spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in this embodiment is as follows: Figure 13 As shown, the carbon NMR spectrum is as follows Figure 14 shown.

[0139] Spectrum analysis:

[0140] 1 H NMR (400MHz, CDCl3): δ7.83-7.78(m,2H),7.72-7.66(m,2H),7.47-7.41(m,2H),7.39-7.32 (m,4H),7.32-7.26(m,6H),7.26-7.21(m,2H),7.04(d,J=8.5Hz,2H),4.39(d,J=8.8Hz,4H).

[0141] 13 C NMR (100MHz, CDCl3): δ139.5,139.5,138.1,136.9,136.8,136.3,133.1,132.5,132.1,132.0,131.8,129.8,129.7,1 29.2,129.2,129.1,128.6,128.5,127.9,127.8,126.7,126.7,126.4,126.3,126.3,126.2,125.7,125.4,42.7,40.0.

[0142] The high-resolution mass spectrometry data of the 2,2′-dihalo-1,1′-binaphthyl compound in this example are as follows:

[0143] ESI-HRMS (m / z): [MH] - calcd for C 34 H 23 ClBr,545.0677,found:545.0674.

[0144] In summary, the structural formula of the 2,2′-dihalogen-1,1′-binaphthyl compound (3,3′-dibenzyl-2-bromo-2′-chloro-1,1′-binaphthyl) in this embodiment is as follows:

[0145]

[0146] Application Example 1:

[0147] A binaphthyl skeleton ligand, the preparation method of which is as follows:

[0148] 0.075 mmol of the 2,2′-dihalogen-1,1′-binaphthyl compound (3,3′-dibenzyl-2,2′-dibromo-1,1′-binaphthyl) in Example 1 and 1 mL of tetrahydrofuran were added to a reaction tube, and the atmosphere in the reaction tube was replaced with nitrogen three times. After cooling to -78°C, 0.225 mmol of n-butyl lithium was added, and the mixture was stirred at -78°C for 1 hour at a stirring rate of 600 rpm. 0.75 mmol of dimethyl disulfide was dissolved in 0.5 mL of tetrahydrofuran and added to the reaction tube. The low-temperature device was removed and stirring was continued for 3 hours. 5 mL of saturated ammonium chloride solution was added to the reaction solution, and the mixture was extracted with 5 mL of ethyl acetate three times. The organic phases were combined, filtered, and the filtrate was concentrated under reduced pressure. The mixture was then separated and purified by column chromatography. The eluent used for column chromatography separation and purification consisted of petroleum ether and ethyl acetate in a volume ratio of 100:1 to obtain a binaphthyl skeleton ligand (yield: 46%).

[0149] The H NMR spectrum of the binaphthyl skeleton ligand in this application example is as follows Figure 15 As shown, the carbon NMR spectrum is as follows Figure 16 shown.

[0150] Spectrum analysis:

[0151] 1 H NMR (400MHz, CDCl3): δ7.82-7.75(m,4H),7.41(t,J=7.5Hz,2H),7.36-7.31(m, 8H),7.25-7.15(m,4H),7.03(d,J=8.5Hz,2H),4.64-4.55(m,4H),1.80(s,6H).

[0152] 13 C NMR (100MHz, CDCl3): δ144.7,141.9,141.2,134.3,133.3,132.2,129.2,129.2,128.4,127.6,126.9,126.5,126.0,125.7,40.5,19.4.

[0153] The high-resolution mass spectrometry data of the binaphthyl skeleton ligand in this application example are as follows:

[0154] ESI-HRMS (m / z): [M+H] + calcd for C 36 H 31 S2,527.1862,found:527.1858.

[0155] In summary, the structural formula of the binaphthyl skeleton ligand (3,3′-dibenzyl-2,2′-dimethylthio-1,1′-binaphthyl) in this application example is as follows:

[0156]

[0157] Application Example 2:

[0158] A binaphthyl skeleton catalyst, the preparation method of which is as follows:

[0159] 1) 0.4 mmol of the binaphthyl skeleton ligand (3,3′-dibenzyl-2,2′-dimethylthio-1,1′-binaphthyl) in Application Example 1 and 2 mL of 1,4-dioxane were added to reaction tube A, and the atmosphere in the reaction tube was replaced with nitrogen three times. After cooling to -78°C, 1.2 mmol of n-butyl lithium was added, and the mixture was stirred at -78°C for 1 h at a stirring rate of 600 rpm. 8 mmol of nitrobenzene was then added to the reaction system, and stirring was continued at -78°C for 5 h. min, then 4 mL of methanol was added and stirring was continued for 5 min, then the reaction was quenched with hydrochloric acid (concentration was 1.0 mol / L), and then extracted with 5 mL of ethyl acetate for 3 times, the organic phases were combined and filtered, and the filtrate was concentrated under reduced pressure, and then purified by column chromatography. The eluent used for column chromatography separation and purification was composed of petroleum ether and ethyl acetate in a volume ratio of 20:1 to obtain 3,3′-dibenzyl-[1,1′-binaphthyl]-2,2′-diol (yield: 47%);

[0160] 2) 0.05 mmol of 3,3′-dibenzyl-[1,1′-binaphthyl]-2,2′-diol and 1 mL of pyridine were added to reaction tube B, and the atmosphere in the reaction tube was replaced with nitrogen three times. After cooling to 0°C, 0.15 mmol of phosphorus oxychloride was added, and the mixture was stirred at 80°C for 6 h at a stirring rate of 600 rpm. After cooling to 0°C, 2 mL of water was added, and the mixture was stirred at 105°C for 12 h. The reaction was quenched with hydrochloric acid (concentration of 1.0 mol / L), and extracted three times with 5 mL of a mixed solvent of dichloromethane and methanol (dichloromethane:methanol volume ratio of 5:1). The organic phases were combined, filtered, and the filtrate was concentrated under reduced pressure. The mixture was then separated and purified by column chromatography. The eluent used for column chromatography separation and purification consisted of dichloromethane and methanol in a volume ratio of 15:1, to obtain a binaphthyl skeleton catalyst (yield: 63%).

[0161] The nuclear magnetic resonance hydrogen spectrum of the binaphthyl skeleton catalyst in this application example is as follows Figure 17 As shown, the carbon NMR spectrum is as follows Figure 18 As shown, the NMR phosphorus spectrum is as follows Figure 19 shown.

[0162] Spectrum analysis:

[0163] 1 H NMR (400MHz, CDCl3): δ7.60 (d, J=7.8Hz, 2H), 7.33 (d, J=7.2Hz, 3H), 7.28-7.10 (m, 5H), 7.04-6.73 (m, 10H), 4.34-3.95 (m, 4H), 2.63 (s, 1H).

[0164] 13 C NMR (100MHz, CDCl3): δ147.6 (d, J=10.0Hz), 139.7, 133.4, 131.3, 131.0, 129. 9,129.4,128.2,127.9,126.9,125.8,125.5,125.0,122.3(d,J=2.0Hz),36.0.

[0165] 31 P NMR (162MHz, CDCl3): δ5.19-4.71(m).

[0166] The high-resolution mass spectrometry data of the binaphthyl skeleton catalyst in this application example are as follows:

[0167] ESI-HRMS (m / z): [MH] - calcd for C 34 H 24O4P,527.1418,found:527.1414.

[0168] In summary, the structural formula of the binaphthyl skeleton catalyst (3,3′-dibenzyl-1,1′-binaphthol phosphate) in this application example is as follows:

[0169]

[0170] The above embodiments are preferred implementations of the present invention, but the implementations of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A 2,2′-dihalo-1,1′-binaphthyl compound, characterized in that: The structural formula is as follows: Where R 1 is one of hydrogen and tert-butyl, R 2 is one of methyl, isobutyl, phenyl, benzyl, 4-fluorophenyl and 4-chlorophenyl, and X is one of chlorine and bromine.

2. The 2,2′-dihalogen-1,1′-binaphthyl compound according to claim 1, characterized in that: The 2,2'-dihalogen-1,1'-binaphthyl compound is One of them.

3. A method for preparing the 2,2′-dihalogen-1,1′-binaphthyl compound according to claim 1, characterized in that: The following steps are involved: 1) dispersing an alkyne bromide compound and a palladium catalyst in a solvent to react, wherein the structural formula of the alkyne bromide compound is Then the product is separated to obtain the intermediate product; 2) The intermediate product, the halogen source and the catalyst are dispersed in a solvent for reaction, and then the product is separated and purified to obtain a 2,2'-dihalogen-1,1'-binaphthyl compound.

4. The preparation method according to claim 3, wherein: In step 1), the molar ratio of the alkynyl bromide compound to the palladium catalyst is 1:0.01-1.

5. The preparation method according to claim 3 or 4, characterized in that: The palladium catalyst in step 1) is at least one of palladium bromide, palladium chloride, bis(acetonitrile)palladium dichloride, dibenzonitrilepalladium dichloride, palladium acetate, and palladium trifluoroacetate.

6. The preparation method according to claim 3 or 4, characterized in that: Step 1) The reaction is carried out at a temperature of 20°C to 80°C and a reaction time of 8h to 36h.

7. The preparation method according to claim 3, wherein: The molar ratio of the acetylene bromide compound in step 1), the halogen source in step 2), and the catalyst in step 2) is 1:0.5-5:0.01-1.

8. The preparation method according to claim 3 or 7, characterized in that: The halogen source in step 2) is one of N-bromosuccinimide, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chlorosuccinimide, and N-chlorophthalimide; the catalyst in step 2) is at least one of R-binaphthol phosphate and S-binaphthol phosphate.

9. The preparation method according to claim 3 or 7, characterized in that: Step 2) The reaction is carried out at a temperature of 0°C to 50°C and a reaction time of 2h to 24h.

10. Use of the 2,2'-dihalo-1,1'-binaphthyl compound according to claim 1 or 2 in the preparation of a binaphthyl skeleton ligand or a binaphthyl skeleton catalyst.

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