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

Abstract

The invention discloses a 2, 2 '-dihalo-1, 1'-binaphthalene compound as well as a synthesis method and application of the 2, 2 '-dihalo-1, 1'-binaphthalene compound. 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 phenyl, R2 is one of methyl, isobutyl, phenyl, benzyl, 4-chlorphenyl and 4-bromophenyl, R3 is one of hydrogen, methyl, methoxyl and fluorine, and X is one of bromine and iodine. A series of brand new 2, 2 '-dihalo-1, 1'-binaphthalene compounds are synthesized, the compounds have unique advantages in construction of binaphthalene skeleton ligands and binaphthalene skeleton catalysts, and the synthesis method has the advantages that raw materials are easy to obtain, reaction conditions are mild, substrate universality is wide, operation is simple, industrial production is easy, and the like. The method is suitable for large-scale industrial production and application.

Description

Technical Field

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

[0002] The binaphthalene structure is a structural unit of great value and can be used in the fields of pesticides, pharmaceuticals, and materials (Chem. Soc. Rev. 2021, 50, 2968; Angew. Chem. Int. Ed. 2023, 62, e202303128; ACS. Catal. 2022, 12, 4918). The site-specific functionalization of halo-substituted binaphthalene compounds also has unique advantages in constructing ligands and catalysts (Chem. Rev. 2021, 121, 4805; J. Am. Chem. Soc. 2021, 143, 12335). Polyhalo-substituted binaphthalene compounds have important value (Eur. J. Org. Chem. 2024, 27, e202300826), but their synthesis remains a great challenge.

[0003] Currently, the synthesis of dihalo-substituted binaphthalene compounds still relies on the late-stage halogenation of binaphthalene compounds. For example: the Sandmeyer reaction (Tetrahedron: Asymmetry 2013, 24, 894) and electrophilic halogenation reactions (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. The ring-opening cleavage of cyclic diaryl halonium salts (Angew. Chem. Int. Ed. 2015, 54, 8736; Chem. 2018, 4, 599) is a good method for constructing halo-substituted biaryl compounds, but there are still some defects. For example: the synthesis steps of cyclic halonium salts of binaphthalene 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 polyhalo-substituted binaphthalene compounds all have obvious defects and are still difficult to be applied in large-scale industrial production.

[0004] Therefore, it is of great significance to develop a synthesis method of 2,2'-dihalo-1,1'-binaphthalene compounds with easily available raw materials, mild reaction conditions, wide substrate applicability, simple operation, and easy industrial production. Summary of the Invention

[0005] The object of the present invention is to provide a 2,2'-dihalo-1,1'-binaphthalene compound, a synthesis method thereof, and an application thereof.

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

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

[0008] In the formula, R 1 is one of hydrogen and phenyl, and R 2 is one of methyl, isobutyl, phenyl, benzyl, 4-chlorophenyl, and 4-bromophenyl, and R 3 is one of hydrogen, methyl, methoxy, and fluorine, and X is one of bromine and iodine.

[0009] Preferably, the 2,2′-dihalo-1,1′-binaphthalene compound is

[0010] one of them.

[0011] A synthesis method of the 2,2′-dihalo-1,1′-binaphthalene compound as described above includes the following steps:

[0012] 1) Disperse the iodoacetylene compound, palladium catalyst, acid-binding agent, and additive in a solvent for reaction. The structural formula of the iodoacetylene compound is Then perform product separation to obtain an intermediate product;

[0013] 2) Disperse the intermediate product and the halogen source in a solvent for reaction, and then perform product separation and purification to obtain the 2,2′-dihalo-1,1′-binaphthalene compound.

[0014] Preferably, in step 1), the molar ratio of the iodoacetylene compound, palladium catalyst, acid-binding agent, and additive is 1:0.01 - 1:0.5 - 5:0.2 - 2.

[0015] Preferably, the iodoalkyne compound in step 1) is one of 4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol, 2-benzyl-4-iodo-1-phenylbut-3-yn-2-ol, 4-iodo-2-methyl-1,1-diphenylbut-3-yn-2-ol, 4-iodo-1-(2-methoxyphenyl)-2-methylbut-3-yn-2-ol, 3-benzyl-1-iodo-5-methylhex-1-yn-3-ol, 4-iodo-2-phenyl-1-(p-tolyl)but-3-yn-2-ol, 2-(4-chlorophenyl)-4-iodo-1-phenylbut-3-yn-2-ol, 2-(4-bromophenyl)-4-iodo-1-phenylbut-3-yn-2-ol, 1-(4-fluorophenyl)-4-iodo-2-methylbut-3-yn-2-ol, 2-benzyl-4-iodo-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, diphenylcyanopalladium dichloride, palladium acetate, palladium trifluoroacetate.

[0017] Preferably, the acid-binding agent in step 1) is at least one of sodium bicarbonate, sodium carbonate, sodium acetate, sodium bisulfite.

[0018] Preferably, the additive in step 1) is at least one of benzoquinone, 1,8-dibromophenanthrene-9,10-dione, 2,6-dimethylbenzoquinone.

[0019] Preferably, the solvent in step 1) is at least two of toluene, fluorobenzene, chlorobenzene, dichloromethane, 1,2-dichloroethane, acetonitrile, water.

[0020] Preferably, the reaction in step 1) is carried out at a temperature of 20°C to 60°C for a reaction time of 8 h to 36 h.

[0021] Preferably, the molar ratio of the iodoalkyne compound in step 1) to the halogen source in step 2) is 1:0.5 to 5.

[0022] Preferably, the halogen source in step 2) is at least one of iodine chloride, N-iodosuccinimide, N-iodophthalimide, N-bromosuccinimide, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin.

[0023] More preferably, the halogen source in step 2) is one of iodine chloride, N-bromophthalimide.

[0024] Preferably, the solvent in step 2) is at least one of toluene, fluorobenzene, dichloromethane, 1,2-dichloroethane, acetonitrile.

[0025] Preferably, the reaction in step 2) is carried out at a temperature of 0 °C to 50 °C for a reaction time of 2 min to 20 h.

[0026] Preferably, the purification method in step 2) is column chromatography purification.

[0027] Preferably, the eluent used for the column chromatography purification is one of petroleum ether and a petroleum ether - ethyl acetate mixture.

[0028] Use of a 2,2′ - dihalo - 1,1′ - binaphthalene compound as described above in the preparation of a binaphthalene - framework ligand or a binaphthalene - framework catalyst.

[0029] Preferably, the binaphthalene - framework ligand is one of 3,3′ - dibenzyl - [1,1′ - binaphthalene] - 2,2′ - diol and 3,3′ - dibenzyl - 2,2′ - dimethoxy - 1,1′ - binaphthalene.

[0030] Preferably, the binaphthalene - framework catalyst is 3,3′ - dibenzyl - 1,1′ - binaphthol phosphate.

[0031] The beneficial effects of the present invention are as follows: The present invention synthesizes a series of brand - new 2,2′ - dihalo - 1,1′ - binaphthalene compounds, which have unique advantages in the construction of binaphthalene - framework ligands and binaphthalene - framework catalysts. Moreover, the synthesis method has the advantages of easily available raw materials, mild reaction conditions, wide substrate generality, simple operation, and easy industrial production, and is suitable for large - scale industrial production and application. Description of the Drawings

[0032] Figure 1 1H NMR spectrum of the 2,2′ - dihalo - 1,1′ - binaphthalene compound in Example 1.

[0033] Figure 2 13C NMR spectrum of the 2,2′ - dihalo - 1,1′ - binaphthalene compound in Example 1.

[0034] Figure 3 1H NMR spectrum of the 2,2′ - dihalo - 1,1′ - binaphthalene compound in Example 9.

[0035] Figure 4 13C NMR spectrum of the 2,2′ - dihalo - 1,1′ - binaphthalene compound in Example 9.

[0036] Figure 5 1H NMR spectrum of the 2,2′ - dihalo - 1,1′ - binaphthalene compound in Example 10.

[0037] Figure 613C NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 10.

[0038] Figure 7 1H NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 11.

[0039] Figure 8 13C NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 11.

[0040] Figure 9 1H NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 12.

[0041] Figure 10 13C NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 12.

[0042] Figure 11 1H NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 13.

[0043] Figure 12 13C NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 13.

[0044] Figure 13 1H NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 14.

[0045] Figure 14 13C NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 14.

[0046] Figure 15 1H NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 15.

[0047] Figure 16 13C NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 15.

[0048] Figure 17 1H NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 16.

[0049] Figure 18 13C NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in Example 16.

[0050] Figure 191H NMR spectrum of the 2,2'-dihalo-1,1'-binaphthyl compound in Example 17.

[0051] Figure 20 13C NMR spectrum of the 2,2'-dihalo-1,1'-binaphthyl compound in Example 17.

[0052] Figure 21 1H NMR spectrum of the binaphthyl skeleton ligand in Application Example 1.

[0053] Figure 22 13C NMR spectrum of the binaphthyl skeleton ligand in Application Example 1.

[0054] Figure 23 1H NMR spectrum of the binaphthyl skeleton ligand in Application Example 2.

[0055] Figure 24 13C NMR spectrum of the binaphthyl skeleton ligand in Application Example 2.

[0056] Figure 25 1H NMR spectrum of the binaphthyl skeleton catalyst in Application Example 3.

[0057] Figure 26 13C NMR spectrum of the binaphthyl skeleton catalyst in Application Example 3.

[0058] Figure 27 31P NMR spectrum of the binaphthyl skeleton catalyst in Application Example 3. Detailed implementation manners

[0059] The present invention will be further explained and illustrated below in conjunction with specific embodiments.

[0060] Example 1:

[0061] A 2,2'-dihalo-1,1'-binaphthyl compound, and its synthesis method is as follows:

[0062] 1) Add 0.2 mmol of 4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol, 0.02 mmol of palladium acetate, 0.2 mmol of sodium bicarbonate, 0.1 mmol of 2,6-dimethylbenzoquinone, and 1 mL of water into reaction tube A. Then place the reaction tube in a glove box and fill it with nitrogen. Then add 1.5 mL of toluene into the reaction tube, and stir at 35 °C for 18 h with a stirring rate of 600 rpm. Then add 5 mL of saturated brine into the reaction solution, extract with 5 mL of ethyl acetate for 3 times, combine the organic phases, filter, and take the filtrate for concentration under reduced pressure to obtain an intermediate product;

[0063] 2) Add the intermediate product and 1 mL of dichloromethane to reaction tube B, stir to dissolve, then dissolve 0.2 mmol of iodine chloride in 1 mL of dichloromethane and add it to the reaction tube. Then stir at 35 °C for 5 min with a stirring rate of 600 rpm. Next, add 5 mL of saturated brine and 3 mL of saturated sodium thiosulfate solution to the reaction solution, extract with 5 mL of ethyl acetate three times, combine the organic phases, filter, take the filtrate for concentration under reduced pressure, and then perform column chromatography purification. The eluent used for column chromatography purification is petroleum ether and ethyl acetate, and 2,2′-dihalo-1,1′-binaphthyl compounds are obtained (yield: 28%).

[0064] The 1H NMR spectrum of the 2,2′-dihalo-1,1′-binaphthyl compound in this example is as shown in Figure 1 shown, and the 13C NMR spectrum is as shown in Figure 2 shown.

[0065] Spectrum analysis:

[0066] 1 H NMR(400 MHz, CDCl3): δ 7.79 - 7.72 (m, 4H), 7.17 - 7.12 (m, 2H), 6.31 (d, J = 2.4 Hz, 2H), 3.51 (s, 6H), 2.69 (s, 6H).

[0067] 13 C NMR(100 MHz, CDCl3): δ 157.8, 145.3, 136.2, 132.1, 129.0, 128.9, 127.2, 118.7, 108.8, 105.5, 55.2, 29.7.

[0068] The high-resolution mass spectrometry data of the 2,2′-dihalo-1,1′-binaphthyl compound in this example are as follows:

[0069] ESI-HRMS (m / z): [M + H] + calcd for C 24 H 20 I2O2, 594.9625, found: 594.1622.

[0070] In summary, the structural formula of the 2,2′-dihalo-1,1′-binaphthyl compound (2,2′-diiodo-7,7′-dimethoxy-3,3′-dimethyl-1,1′-binaphthyl) in this example is as follows:

[0071]

[0072] Example 2:

[0073] A method for synthesizing 2,2′-dihalo-1,1′-binaphthalene compounds, except that "toluene" in step 1) is replaced with an equal volume of "1,2-dichloroethane", is exactly the same as Example 1 for the rest.

[0074] After testing, the yield of the 2,2′-dihalo-1,1′-binaphthalene compound in this example is 22%.

[0075] Example 3:

[0076] A method for synthesizing 2,2′-dihalo-1,1′-binaphthalene compounds, except that "toluene" in step 1) is replaced with an equal volume of "dichloromethane", is exactly the same as Example 1 for the rest.

[0077] After testing, the yield of the 2,2′-dihalo-1,1′-binaphthalene compound in this example is 21%.

[0078] Example 4:

[0079] A method for synthesizing 2,2′-dihalo-1,1′-binaphthalene compounds, except that "2,6-dimethylbenzoquinone" in step 1) is replaced with an equal molar amount of "benzoquinone", is exactly the same as Example 1 for the rest.

[0080] After testing, the yield of the 2,2′-dihalo-1,1′-binaphthalene compound in this example is 19%.

[0081] Example 5:

[0082] A method for synthesizing 2,2′-dihalo-1,1′-binaphthalene compounds, except that "2,6-dimethylbenzoquinone" in step 1) is replaced with an equal molar amount of "1,8-dibromophenanthrene-9,10-dione", is exactly the same as Example 1 for the rest.

[0083] After testing, the yield of the 2,2′-dihalo-1,1′-binaphthalene compound in this example is 21%.

[0084] Example 6:

[0085] A method for synthesizing 2,2′-dihalo-1,1′-binaphthalene compounds, except that "sodium bicarbonate" in step 1) is replaced with an equal molar amount of "sodium acetate", is exactly the same as Example 1 for the rest.

[0086] After testing, the yield of the 2,2′-dihalo-1,1′-binaphthalene compound in this example is 24%.

[0087] Example 7:

[0088] A method for synthesizing 2,2′-dihalo-1,1′-binaphthalene compounds, except that the "toluene" in step 1) is replaced with an equal volume of "a mixture of toluene and dichloromethane (the volume ratio of toluene to dichloromethane is 1:1)", and the rest is exactly the same as in Example 1.

[0089] After testing, the yield of 2,2′-dihalo-1,1′-binaphthalene compounds in this example is 24%.

[0090] Example 8:

[0091] A method for synthesizing 2,2′-dihalo-1,1′-binaphthalene compounds, except that the "toluene" in step 1) is replaced with an equal volume of "a mixture of toluene and 1,2-dichloroethane (the volume ratio of toluene to 1,2-dichloroethane is 1:1)", and the rest is exactly the same as in Example 1.

[0092] After testing, the yield of 2,2′-dihalo-1,1′-binaphthalene compounds in this example is 22%.

[0093] Example 9:

[0094] A 2,2′-dihalo-1,1′-binaphthalene compound, except that the "4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol" in step 1) is replaced with an equimolar amount of "2-benzyl-4-iodo-1-phenylbut-3-yn-2-ol" during synthesis, and the rest is exactly the same as in Example 1.

[0095] After testing, the yield of 2,2′-dihalo-1,1′-binaphthalene compounds in this example is 42%.

[0096] The 1H NMR spectrum of the 2,2′-dihalo-1,1′-binaphthalene compound in this example is as Figure 3 shown, and the 13C NMR spectrum is as Figure 4 shown.

[0097] Spectrum analysis:

[0098] 1 H NMR(400MHz,CDCl3): δ = 7.81(d,J = 8.2Hz,2H),7.67(s,2H),7.46(t,J = 7.5Hz,2H),7.37 - 7.32(m,4H),7.31 - 7.26(m,6H),7.22(d,J = 7.2Hz,2H),7.04(d,J = 8.5Hz,2H),4.41(s,4H).

[0099] 1313C NMR (100 MHz, CDCl3): δ 147.2, 140.6, 139.7, 133.2, 131.5, 129.3, 128.7, 128.5, 127.8, 126.7, 126.7, 126.4, 126.3, 108.3, 47.7.

[0100] The high-resolution mass spectrometry data of the 2,2'-dihalo-1,1'-binaphthalene compound in this example are as follows:

[0101] ESI-HRMS (m / z): [M-H] - calcd for C 34 H 24 I2,684.9895, found: 684.9899.

[0102] In summary, the structural formula of the 2,2'-dihalo-1,1'-binaphthalene compound (3,3'-dibenzyl-2,2'-diiodo-1,1'-binaphthalene) in this example is as follows:

[0103]

[0104] Example 10:

[0105] A 2,2'-dihalo-1,1'-binaphthalene compound, except that in step 1) of the synthesis, "4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol" is replaced with an equimolar amount of "4-iodo-2-methyl-1,1-diphenylbut-3-yn-2-ol", and the rest is exactly the same as in Example 1.

[0106] After testing, the yield of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is 15%.

[0107] The nuclear magnetic resonance hydrogen spectrum of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is as Figure 5 shown, and the nuclear magnetic resonance carbon spectrum is as Figure 6 shown.

[0108] Spectrum analysis:

[0109] 1 1H NMR (400 MHz, CDCl3): δ = 7.60 - 7.55 (m, 4H), 7.52 - 7.48 (m, 2H), 7.45 - 7.38 (m, 6H), 7.37 - 7.33 (m, 2H), 7.24 - 7.16 (m, 4H), 2.52 (s, 6H).

[0110] 1313C NMR(100 MHz, CDCl3): δ 146.6, 140.5, 139.0, 135.8, 132.9, 131.2, 130.3, 130.0, 128.5 (d, J = 3.0 Hz, 1C), 127.4, 126.9 (d, J = 15.0 Hz, 1C), 126.8, 126.4, 126.0, 109.8, 28.5.

[0111] The high-resolution mass spectrometry data of the 2,2'-dihalo-1,1'-binaphthalene compound in this example are as follows:

[0112] ESI-HRMS (m / z): [M-H] - calcd for C 34 H 24 I2,684.9895, found: 684.9899.

[0113] In summary, the structural formula of the 2,2'-dihalo-1,1'-binaphthalene compound (2,2'-diiodo-3,3'-dimethyl-4,4'-diphenyl-1,1'-binaphthalene) in this example is as follows:

[0114]

[0115] Example 11:

[0116] A 2,2'-dihalo-1,1'-binaphthalene compound, except that in step 1) of the synthesis, "4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol" is replaced with an equimolar amount of "4-iodo-1-(2-methoxyphenyl)-2-methylbut-3-yn-2-ol", and the rest is exactly the same as in Example 1.

[0117] After testing, the yield of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is 54%.

[0118] The 1H nuclear magnetic resonance spectrum of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is as Figure 7 shown, and the 13C nuclear magnetic resonance spectrum is as Figure 8 shown.

[0119] Spectrum analysis:

[0120] 1 1H NMR (400 MHz, CDCl3): δ = 8.29 (s, 2H), 7.09 (t, J = 8.1 Hz, 2H), 6.81 (d, J = 7.6 Hz, 2H), 6.57 (d, J = 8.5 Hz, 2H), 4.03 (s, 6H), 2.73 (s, 6H).

[0121] 13 13C NMR (100 MHz, CDCl3): δ 155.0, 146.4, 138.0, 132.2, 126.3, 125.5, 121.6, 118.9, 109.1, 104.4, 55.6, 30.0.

[0122] The high-resolution mass spectrometry data of the 2,2'-dihalo-1,1'-binaphthalene compound in this example are as follows:

[0123] ESI-HRMS (m / z): [M+H] + calcd for C 24 H 20 I2O2, 594.9625, found: 594.9620.

[0124] In summary, the structural formula of the 2,2'-dihalo-1,1'-binaphthalene compound (2,2'-diiodo-5,5'-dimethoxy-3,3'-dimethyl-1,1'-binaphthalene) in this example is as follows:

[0125]

[0126] Example 12:

[0127] A 2,2'-dihalo-1,1'-binaphthalene compound, except that in the synthesis, "4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol" in step 1) is replaced with an equimolar amount of "3-benzyl-1-iodo-5-methylhex-1-yn-3-ol", and the rest is exactly the same as in Example 1.

[0128] After testing, the yield of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is 52%.

[0129] The 1H nuclear magnetic resonance spectrum of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is as Figure 9 shown, and the 13C nuclear magnetic resonance spectrum is as Figure 10 shown.

[0130] Spectrum analysis:

[0131] 1 1H NMR (400 MHz, CDCl3): δ = 7.90 (d, J = 8.2 Hz, 2H), 7.79 (s, 2H), 7.52 - 7.46 (m, 2H), 7.25 - 7.19 (m, 2H), 7.00 (d, J = 8.5 Hz, 2H), 2.92 (h, J = 6.8 Hz, 4H), 2.25 - 2.15 (m, 2H), 1.10 - 1.03 (m, 12H).

[0132] 13 13C NMR (100 MHz, CDCl3): δ 147.2, 141.4, 133.1, 131.4, 128.2, 127.6, 126.6, 126.5, 126.4, 108.5, 50.6, 29.1, 22.4, 22.3.

[0133] The high-resolution mass spectrometry data of the 2,2′-dihalo-1,1′-binaphthalene compound in this example are as follows:

[0134] ESI-HRMS (m / z): [M+H] + calcd for C 46 H 35 BrOP, 619.0880, found: 619.0881.

[0135] In summary, the structural formula of the 2,2′-dihalo-1,1′-binaphthalene compound (2,2′-diiodo-3,3′-diisobutyl-1,1′-binaphthalene) in this example is as follows:

[0136]

[0137] Example 13:

[0138] A 2,2′-dihalo-1,1′-binaphthalene compound, except that in the synthesis, "4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol" in step 1) is replaced with an equimolar amount of "4-iodo-2-phenyl-1-(p-tolyl)but-3-yn-2-ol", and the rest is exactly the same as in Example 1.

[0139] After testing, the yield of the 2,2′-dihalo-1,1′-binaphthalene compound in this example is 42%.

[0140] The 1H nuclear magnetic resonance spectrum of the 2,2′-dihalo-1,1′-binaphthalene compound in this example is as Figure 11 shown, and the 13C nuclear magnetic resonance spectrum is as Figure 12 shown.

[0141] Spectrum analysis:

[0142] 1 1H NMR (400 MHz, CDCl3): δ = 7.89 (s, 2H), 7.84 (d, J = 8.3 Hz, 2H), 7.56 - 7.52 (m, 4H), 7.50 - 7.43 (m, 6H), 7.40 - 7.37 (m, 2H), 6.96 (s, 2H), 2.34 (s, 6H).

[0143] 13 13C NMR (100 MHz, CDCl3): δ 146.4, 145.1, 143.4, 137.1, 132.1, 131.3, 129.9, 129.3, 128.0, 127.9, 127.8, 127.5, 125.4, 105.9, 22.1.

[0144] The high-resolution mass spectrometry data of the 2,2'-dihalo-1,1'-binaphthalene compound in this example are as follows:

[0145] ESI-HRMS (m / z): [M-H] - calcd for C 34 H 24 I2 684.9895, found: 684.9894.

[0146] In summary, the structural formula of the 2,2'-dihalo-1,1'-binaphthalene compound (2,2'-diiodo-7,7'-dimethyl-3,3'-diphenyl-1,1'-binaphthalene) in this example is as follows:

[0147]

[0148] Example 14:

[0149] A 2,2'-dihalo-1,1'-binaphthalene compound, except that in the synthesis, "4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol" in step 1) is replaced with an equimolar amount of "2-(4-chlorophenyl)-4-iodo-1-phenylbut-3-yn-2-ol", and the rest is exactly the same as in Example 1.

[0150] After testing, the yield of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is 28%.

[0151] The 1H nuclear magnetic resonance spectrum of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is as Figure 13 shown, and the 13C nuclear magnetic resonance spectrum is as Figure 14 shown.

[0152] Spectrum analysis:

[0153] 1 1H NMR (400 MHz, CDCl3): δ = 7.95 - 7.89 (m, 4H), 7.57 - 7.53 (m, 2H), 7.45 (s, 8H), 7.36 - 7.31 (m, 2H), 7.18 - 7.15 (m, 2H).

[0154] 1313C NMR (100 MHz, CDCl3): δ 147.0, 143.2, 143.1, 133.8, 133.0, 131.9, 131.2, 128.4, 128.2, 128.1, 127.5, 127.2, 126.5, 105.2.

[0155] The high-resolution mass spectrometry data of the 2,2'-dihalo-1,1'-binaphthalene compound in this example are as follows:

[0156] ESI-HRMS (m / z): [M+Na] + calcd for C 32 H 18 Cl2I2Na, 748.8767, found: 748.8763.

[0157] In summary, the structural formula of the 2,2'-dihalo-1,1'-binaphthalene compound (3,3'-bis(4-chlorophenyl)-2,2'-diiodo-1,1'-binaphthalene) in this example is as follows:

[0158]

[0159] Example 15:

[0160] A 2,2'-dihalo-1,1'-binaphthalene compound, except that in the synthesis, "4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol" in step 1) is replaced with an equimolar amount of "2-(4-bromophenyl)-4-iodo-1-phenylbut-3-yn-2-ol", and the rest is exactly the same as in Example 1.

[0161] After testing, the yield of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is 30%.

[0162] The 1H nuclear magnetic resonance spectrum of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is as Figure 15 shown, and the 13C nuclear magnetic resonance spectrum is as Figure 16 shown.

[0163] Spectrum analysis:

[0164] 1 1H NMR (400 MHz, CDCl3): δ = 7.95 - 7.88 (m, 4H), 7.62 - 7.58 (m, 4H), 7.57 - 7.53 (m, 2H), 7.41 - 7.37 (m, 4H), 7.36 - 7.31 (m, 2H), 7.18 - 7.14 (m, 2H).

[0165] 1313C NMR(100MHz,CDCl3): δ 147.0, 143.7, 143.1, 133.0, 131.9, 131.6, 131.0, 128.4, 128.2, 127.6, 127.2, 126.5, 122.0, 105.0.

[0166] The high-resolution mass spectrometry data of the 2,2'-dihalo-1,1'-binaphthalene compound in this example are as follows:

[0167] ESI-HRMS (m / z): [M+H]+ calcd for C 32 H 18 Br2I2, 815.7844, found: 815.7852.

[0168] In summary, the structural formula of the 2,2'-dihalo-1,1'-binaphthalene compound (3,3'-bis(4-bromophenyl)-2,2'-diiodo-1,1'-binaphthalene) in this example is as follows:

[0169]

[0170] Example 16:

[0171] A 2,2'-dihalo-1,1'-binaphthalene compound, except that in the synthesis, "4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol" in step 1) is replaced with an equimolar amount of "1-(4-fluorophenyl)-4-iodo-2-methylbut-3-yn-2-ol", and the rest is exactly the same as in Example 1.

[0172] After testing, the yield of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is 35%.

[0173] The 1H nuclear magnetic resonance spectrum of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is as Figure 17 shown, and the 13C nuclear magnetic resonance spectrum is as Figure 18 shown.

[0174] Spectrum analysis:

[0175] 1 1H NMR (400MHz, CDCl3): δ = 7.88 - 7.81 (m, 4H), 7.27 (d, J = 2.5Hz, 1H), 7.26 - 7.22 (m, 2H), 6.60 - 6.54 (m, 2H), 2.72 (s, 6H).

[0176] 1313C NMR (100 MHz, CDCl3): δ 160.9 (d, J = 250.0 Hz, 1C), 145.5 (d, J = 10.0 Hz, 1C), 138.1 (d, J = 3.0 Hz, 1C), 131.7 (d, J = 10.0 Hz, 1C), 130.4, 129.9 (d, J = 9.0 Hz, 1C), 127.4, 117.2 (d, J = 25.0 Hz, 1C), 109.7 (d, J = 20.0 Hz, 1C), 109.4, 29.7.

[0177] The high-resolution mass spectrometry data of the 2,2'-dihalo-1,1'-binaphthalene compound in this example are as follows:

[0178] ESI-HRMS (m / z): [M+H] + calcd for C 22 H 14 F2I2, 814.8435, found: 814.8433.

[0179] In summary, the structural formula of the 2,2'-dihalo-1,1'-binaphthalene compound (7,7'-difluoro-2,2'-diiodo-3,3'-dimethyl-1,1'-binaphthalene) in this example is as follows:

[0180]

[0181] Example 17:

[0182] A 2,2'-dihalo-1,1'-binaphthalene compound, except that in the synthesis, "4-iodo-1-(4-methoxyphenyl)-2-methylbut-3-yn-2-ol" in step 1) is replaced with an equimolar amount of "2-benzyl-4-iodo-1-phenylbut-3-yn-2-ol", "iodine monochloride" in step 2) is replaced with an equimolar amount of "N-bromophthalimide", and "dichloromethane" in step 2) is replaced with an equal volume of "acetonitrile", and the rest is exactly the same as in Example 1.

[0183] After testing, the yield of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is 48%.

[0184] The 1H nuclear magnetic resonance spectrum of the 2,2'-dihalo-1,1'-binaphthalene compound in this example is as Figure 19 shown, and the 13C nuclear magnetic resonance spectrum is as Figure 20 shown.

[0185] Spectrum analysis:

[0186] 11H NMR (400 MHz, CDCl3): δ = 7.81 (t, J = 8.5 Hz, 2H), 7.72 (s, 1H), 7.65 (s, 1H), 7.46 (t, J = 7.5 Hz, 2H), 7.39 - 7.26 (m, 10H), 7.26 - 7.20 (m, 2H), 7.09 - 7.01 (m, 2H), 4.41 (d, J = 3.1 Hz, 4H).

[0187] 13 13C NMR (100 MHz, CDCl3): δ 142.4, 140.6, 139.7, 139.6, 138.1, 132.6, 131.5, 129.7, 129.3, 129.2, 128.7, 128.6, 128.5, 127.8, 126.8, 126.8, 126.7, 126.5, 126.3, 126.3, 125.8, 47.7, 42.6.

[0188] The high-resolution mass spectrometry data of the 2,2'-dihalo-1,1'-binaphthalene compound in this example are as follows:

[0189] ESI-HRMS (m / z): [M - H] - calcd for C 34 H 23 BrI, 637.0033, found: 637.0032.

[0190] In summary, the structural formula of the 2,2'-dihalo-1,1'-binaphthalene compound (3,3'-dibenzyl-2-bromo-2'-iodo-1,1'-binaphthalene) in this example is as follows:

[0191]

[0192] Application Example 1:

[0193] A binaphthalene skeleton ligand, and its preparation method is as follows:

[0194] 0.4 mmol of the 2,2′-dihalo-1,1′-binaphthyl compound (3,3′-dibenzyl-2-bromo-2′-iodo-1,1′-binaphthalene) in Example 17 and 2 mL of 1,4-dioxane were added to a reaction tube. The atmosphere in the reaction tube was replaced with nitrogen three times, and then cooled to -78 °C. 1.2 mmol of n-butyllithium 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 added, and the mixture was stirred for another 5 min. 4 mL of methanol was added, and the mixture was stirred for another 5 min. The reaction was quenched with hydrochloric acid (concentration: 1.0 mol / L). The reaction solution was extracted with 5 mL of ethyl acetate three times. The organic phases were combined, filtered, and the filtrate was concentrated under reduced pressure and then purified by column chromatography. The eluent used for column chromatography was petroleum ether and ethyl acetate, and the binaphthyl skeleton ligand was obtained (yield: 47%).

[0195] The 1H NMR spectrum of the binaphthyl skeleton ligand in this application example is as shown in Figure 21 shown, and the 13C NMR spectrum is as shown in Figure 22 shown.

[0196] Spectrum analysis:

[0197] 1 H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 8.0 Hz, 2H), 7.71 (s, 2H), 7.35 (d, J = 4.9 Hz, 10H), 7.27 (s, 2H), 7.25 (d, J = 7.2 Hz, 2H), 7.10 (d, J = 8.3 Hz, 2H), 5.17 (s, 2H), 4.25 (s, 4H).

[0198] 13 C NMR (100 MHz, CDCl3): δ 151.5, 140.0, 132.2, 130.8, 130.0, 129.3, 129.0, 128.4, 127.9, 126.7, 126.1, 123.9, 123.9, 110.8, 36.7.

[0199] The high-resolution mass spectrometry data of the binaphthyl skeleton ligand in this application example are as follows:

[0200] ESI-HRMS (m / z): [M-H] - calcd for C 34 H 25 O2, 465.1860, found: 465.1856.

[0201] In summary, the structural formula of the binaphthyl skeleton ligand (3,3′-dibenzyl-[1,1′-binaphthalene]-2,2′-diol) in this application example is as follows:

[0202]

[0203] Application Example 2:

[0204] A binaphthyl framework ligand, and its preparation method is as follows:

[0205] Add 0.05 mmol of the binaphthyl framework ligand (3,3′-dibenzyl-[1,1′-binaphthalene]-2,2′-diol) in Application Example 1, 0.3 mmol of potassium carbonate, and 2 mL of acetone into a reaction tube, then add dropwise 0.3 mmol of methyl iodide, stir at 70 °C for 24 h, then add saturated brine to quench the reaction. The reaction solution is extracted with 5 mL of ethyl acetate for 3 times in total. The organic phases are combined, filtered, the filtrate is taken for concentration under reduced pressure, and then purified by column chromatography. The eluent used for column chromatography is petroleum ether, thus obtaining the binaphthyl framework ligand (yield: 90%).

[0206] The 1H NMR spectrum of the binaphthyl framework ligand in this application example is as shown in Figure 23 and the 13C NMR spectrum is as shown in Figure 24 .

[0207] Spectrum analysis:

[0208] 1 1H NMR (400 MHz, CDCl3): δ 7.79 (d, J = 8.2 Hz, 2H), 7.70 (s, 2H), 7.38 - 7.29 (m, 10H), 7.25 - 7.15 (m, 6H), 4.28 (d, J = 2.3 Hz, 4H), 3.11 (s, 6H).

[0209] 13 13C NMR (100 MHz, CDCl3): δ 155.4, 140.8, 134.8, 133.4, 130.6, 129.9, 129.2, 128.4, 127.6, 126.0, 125.8, 125.7, 124.6, 124.6, 60.6, 36.9.

[0210] The high-resolution mass spectrometry data of the binaphthyl framework ligand in this application example are as follows:

[0211] ESI-HRMS (m / z): [M + H] + C 36 H 31 O2, 495.2319, found: 495.2317.

[0212] In summary, the structural formula of the binaphthyl framework ligand (3,3′-dibenzyl-2,2′-dimethoxy-1,1′-binaphthalene) in this application example is as follows:

[0213]

[0214] Application Example 3:

[0215] A binaphthyl framework catalyst, and its preparation method is as follows:

[0216] Add 0.05 mmol of the binaphthyl framework ligand (3,3'-dibenzyl-[1,1'-binaphthalene]-2,2'-diol) in Application Example 1 and 1 mL of pyridine into a reaction tube. Then displace the atmosphere in the reaction tube three times with nitrogen. After cooling to 0 °C, add 0.15 mmol of phosphorus oxychloride. Then stir at 80 °C for 6 h with a stirring rate of 600 rpm. After cooling to 0 °C, add 2 mL of water. Then stir at 105 °C for 12 h. Then add hydrochloric acid (concentration: 1.0 mol / L) to quench the reaction. The reaction solution is extracted with 5 mL of a mixed solvent of dichloromethane and methanol (volume ratio of dichloromethane to methanol is 5:1) for a total of three times. Combine the organic phases, filter, take the filtrate and concentrate it under reduced pressure, and then perform column chromatography purification. The eluent used for column chromatography purification is composed of dichloromethane and methanol according to a volume ratio of 15:1, thus obtaining the binaphthyl framework catalyst (yield: 63%).

[0217] The 1H NMR spectrum of the binaphthyl framework catalyst in this application example is as Figure 25 shown, the 13C NMR spectrum is as Figure 26 shown, and the 31P NMR spectrum is as Figure 27 shown.

[0218] Spectrum analysis:

[0219] 1 H NMR(400MHz,CDCl3): δ7.58(d,J = 7.9Hz,2H),7.35 - 7.26(m,4H),7.24(d,J = 8.8Hz,2H),7.17 - 7.10(m,2H),6.82(d,J = 21.7Hz,10H),4.10(dd,J = 84.2,15.8Hz,4H),2.32(s,1H).

[0220] 13 C NMR(100MHz,CDCl3): δ147.6(d,J = 10.0Hz),139.8,133.5,131.4,131.0,129.8,129.3,128.2,127.8,126.9,125.7,125.4,124.9,122.3(d,J = 2.0Hz),35.8.

[0221] 3131P NMR (162 MHz, CDCl3): δ 5.97 - 5.31 (m).

[0222] The high-resolution mass spectrometry data of the binaphthyl framework catalyst in this application example are as follows:

[0223] ESI-HRMS (m / z): [M-H] - calcd for C 34 H 24 O4P, 527.1418, found: 527.1414.

[0224] In summary, the structural formula of the binaphthyl framework catalyst (3,3'-dibenzyl-1,1'-binaphthol phosphate) in this application example is as follows:

[0225]

[0226] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A 2,2'-dihalo-1,1'-binaphthalene compound, characterized in that, The structural formula is as follows: In the formula, R 1 is one of hydrogen and phenyl, and R 2 is one of methyl, isobutyl, phenyl, benzyl, 4-chlorophenyl, and 4-bromophenyl, and R 3 is one of hydrogen, methyl, methoxy, and fluorine, and X is one of bromine and iodine.

2. The 2,2'-dihalo-1,1'-binaphthyl compound according to claim 1, characterized in that: The 2,2′-dihalo-1,1′-binaphthyl compound is One of 3. A method for synthesizing a 2,2'-dihalo-1,1'-binaphthalene compound as described in claim 1, characterized in that, It includes the following steps: 1) React the iodoalkyne compound, palladium catalyst, acid scavenger and additive by dispersing them in a solvent. The structural formula of the iodoalkyne compound is Then carry out product separation to obtain the intermediate product; 2) Disperse the intermediate product and the halogen source in a solvent for reaction, and then carry out product separation and purification to obtain 2,2'-dihalo-1,1'-binaphthalene compounds.

4. The synthesis method according to claim 3, characterized in that: The molar ratio of the iodoacetylene compound, palladium catalyst, acid-binding agent, and additive in step 1) is 1:0.01-1:0.5-5:0.2-2.

5. The synthesis 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, diphenylcyanopalladium dichloride, palladium acetate, and palladium trifluoroacetate; the acid-binding agent in step 1) is at least one of sodium bicarbonate, sodium carbonate, sodium acetate, and sodium bisulfite; the additive in step 1) is at least one of benzoquinone, 1,8-dibromophenanthrene-9,10-dione, and 2,6-dimethylbenzoquinone.

6. The synthesis method according to claim 3 or 4, characterized in that: The reaction in step 1) is carried out under the condition that the temperature is 20°C to 60°C, and the reaction time is 8h to 36h.

7. The synthesis method according to claim 3, characterized in that: The molar ratio of the iodoacetylene compound in step 1) to the halogen source in step 2) is 1:0.5-5.

8. The synthesis method according to claim 3 or 7, characterized in that: The halogen source in step 2) is at least one of iodine chloride, N-iodosuccinimide, N-iodophthalimide, N-bromosuccinimide, N-bromophthalimide, and 1,3-dibromo-5,5-dimethylhydantoin.

9. The synthesis method according to claim 3 or 7, characterized in that: The reaction in step 2) is carried out under the condition that the temperature is 0°C to 50°C, and the reaction time is 2min to 20h.

10. Use of a 2,2'-dihalo-1,1'-binaphthalene compound as claimed in claim 1 or 2 in the preparation of a binaphthalene skeleton ligand or a binaphthalene skeleton catalyst.

Images