A hydrophilic triphenylene-based metal-organic nickel octahedral cage and its preparation method and application

Abstract

The present invention discloses a hydrophilic triphenylene-based metal-organic nickel octahedral cage and its preparation method and application. The general formula of the cage is: [Ni6L8(X) 12 , where X is a monovalent anion and L is a hydrophilic triphenylene-based tridentate pyridine ligand. The preparation method includes the following steps: (1) Using ethyl-substituted tribromotriphenylene, boronic acid ester and 3-bromo-5-ethoxyethyl pyridine as raw materials, tetrakis(triphenylphosphine)palladium as a catalyst, in an organic solvent, under alkaline conditions, under nitrogen protection, reacting at 80-100 °C for 12-24 h to obtain ligand L; (2) Taking ligand L and nickel salt and adding them to a mixed solvent of water and acetonitrile, and stirring for 3-6 hours. The hydrophilic triphenylene-based metal-organic nickel octahedral cage is used as a metal catalyst to efficiently and selectively catalyze the hydrodeuteration reduction reaction at room temperature to synthesize chemicals containing deuterium at specific positions.

Description

Technical Field

[0001] The present invention relates to an octahedral cage, and particularly to a hydrophilic nickel-based metal-organic truxene octahedral cage and its preparation method and application. Background Art

[0002] The reduction hydrogenation reaction of olefins is widely used in the chemical industry. Usually, the method of metal-catalyzed hydrogenation is adopted, and the reaction conditions are harsh. Since deuterated compounds are widely used in the study of reaction mechanisms and have important applications in medicine, functional materials, biomedical imaging, and gene detection, etc., the efficient reduction hydrodeuteration reaction of olefins, especially the selective deuteration of olefin reduction, has always been a hot spot and a difficult point in the field of organic synthesis.

[0003] At present, for the metal-catalyzed reduction hydrodeuteration reaction of olefins reported, deuterium usually only exists at the position where the olefin double bond is located, and other positions contain little or no deuterium. In addition, the metal catalysts used are generally difficult to recycle, and the reaction conditions are harsh and require a relatively high temperature. Summary of the Invention

[0004] Object of the Invention: The first object of the present invention is to provide a hydrophilic nickel-based metal-organic truxene octahedral cage that can efficiently and selectively catalyze the reduction hydrodeuteration reaction; the second object of the present invention is to provide a preparation method of the hydrophilic nickel-based metal-organic truxene octahedral cage; the third object of the present invention is to provide the application of the hydrophilic nickel-based metal-organic truxene octahedral cage in the catalytic hydrodeuteration reaction.

[0005] Technical Solution: A hydrophilic nickel-based metal-organic truxene octahedral cage of the present invention has the general formula: [Ni6L8(X) 12 , where X is a monovalent anion, and L is a hydrophilic truxene-based tridentate pyridine ligand, and the structural formula of L is:

[0006]

[0007] The structure of the octahedral cage is where X is a monovalent anion.

[0008] Preferably, X is BF4 - , ClO4 - , OSO2CF3 - or (CF3SO2)2N - , and the corresponding structural formula of the cage is as follows:

[0009]

[0010] The preparation method of the hydrophilic nickel-based metal-organic truxene octahedral cage of the present invention includes the following steps:

[0011] (1) Using ethyl-substituted tribromotriphenylene, boronic acid ester, and 3-bromo-5-ethoxyethanol pyridine as raw materials, tetrakis(triphenylphosphine)palladium as a catalyst, in an organic solvent, under alkaline conditions, and under nitrogen protection, react at 80 - 100 °C for 12 - 24 h to obtain ligand L. The reaction equation is as follows:

[0012]

[0013] (2) Take ligand L and nickel salt and add them to a mixed solvent of water and acetonitrile. After stirring for 3 - 6 hours, an organonickel octahedral cage is obtained.

[0014] The synthesis method of ethyl-substituted tribromotriphenylene is: using triphenylene as a raw material, through alkylation and bromination reactions, ethyl-substituted tribromotriphenylene is obtained. The synthesis route is as follows:

[0015]

[0016] Preferably, in step (1), the organic solvent is toluene or xylene.

[0017] Preferably, in step (2), the volume ratio of water to acetonitrile is 1 - 5:1.

[0018] The application of the hydrophilic triphenylene-based organonickel octahedral cage of the present invention in the catalytic hydrogen-deuterium reduction reaction.

[0019] The application method is: add the hydrophilic triphenylene-based organonickel octahedral cage, olefin derivative, and pinacol borane to a mixed solvent of heavy water and acetonitrile, and react at 20 - 25 °C for 10 - 24 hours to obtain the product olefin transfer deuteration product. The structural formula is:

[0020] Among them, n = 1 - 3, R1 and R2 are selected from -H, -CH3, -C2H5, -Br, -F, -OCH3, or -COOCH3; the hydrogen-deuterium reduction reaction formula is as follows:

[0021]

[0022] Preferably, the molar ratio of the hydrophilic triphenylene-based organonickel octahedral cage, olefin derivative, and pinacol borane is 0.01 - 0.05:1:1 - 2.

[0023] Preferably, the volume ratio of heavy water to acetonitrile is 0.1 - 0.5:1.

[0024] Mechanism of Invention: Compared with traditional metal catalysts, metal-organic cages have solubility, easily adjustable cavities, and modification properties. The confined cavities can act as "molecular reactors" to bring substrates closer together, thus greatly improving the reaction rate and selectivity. In this invention, a hydrophilic triindene-based metal-organic nickel octahedral cage is designed and synthesized. This type of cage contains 24 alcohol hydroxyl groups and 24 ether bonds, has good hydrophilicity, and has a relatively large cavity. As a catalyst, it can encapsulate longer-chain olefins and pinacol borane, bringing them closer together and thus increasing the reaction rate. The cavity of the metal-organic cage can also encapsulate heavy water, and the nickel metal at the octahedral vertices can coordinate with the substrate olefin to efficiently and selectively catalyze the hydrodeuteration reduction reaction at room temperature to synthesize deuterium-containing chemicals at specific positions.

[0025] Advantages: Compared with the prior art, the present invention has the following remarkable advantages: (1) As a metal catalyst, the hydrophilic triindene-based metal-organic nickel octahedral cage can efficiently and selectively catalyze the hydrodeuteration reduction reaction at room temperature to synthesize deuterium-containing chemicals at specific positions; (2) The preparation method is simple, with (heavy) water as the proton source, and the reaction conditions are mild and the operation is simple; (3) The hydrophilic triindene-based metal-organic nickel octahedral cage can be recycled as a metal catalyst and has good catalytic activity. Description of the Drawings

[0026] Figure 1 It is the structural diagram of the hydrophilic triindene-based metal-organic nickel octahedral cage synthesized in Example 1. Detailed Embodiments

[0027] The technical solutions of the present invention will be further described below in conjunction with the embodiments.

[0028] Example 1

[0029] (1) Preparation of ethyl-substituted tribromo triindene:

[0030] S1: Add 15 mmol of triindene, 90 mmol of potassium tert-butoxide, and 100 ml of DMSO to a 250 ml three-necked flask. Stir at about 0 °C for 15 min, then add 18 mmol of bromoethane. After the temperature rises to room temperature, add 18 mmol of bromoethane and 90 mmol of potassium tert-butoxide after reacting for 30 min, and continue to react for 14 h. Then add 18 mmol of bromoethane and 45 mmol of potassium tert-butoxide, and react for a total of 18 h. After the reaction is completed, extract three times with ethyl acetate. Dry the organic phase with anhydrous magnesium sulfate, filter, and concentrate the filtrate under reduced pressure to obtain the crude product. Then separate it by column chromatography (the eluent is petroleum ether:ethyl acetate = 20:1) to obtain a pale yellow solid, that is, ethyl-substituted triindene, with a yield of 81%.

[0031]

[0032] NMR characterization data: 1 H NMR(CDCl3, 400 MHz, ppm) δ 8.36–8.34 (d, 3H, J=8.6 Hz), 7.47–7.25 (m, 6H), 3.06–2.97 (m, 6H), 2.19–2.11 (m, 6H), 0.22–0.19 (t, 18H, J=7.3 Hz). 13 C NMR(CDCl3, 75 MHz, ppm) δ 152.83, 143.88, 140.66, 138.86, 126.48, 126.09, 124.57, 122.27, 56.74, 29.41, 8.53.

[0033] S2: Add 1 mmol of ether-bond-containing triphenylene, 3.5 mmol of liquid bromine and 50 ml of dichloromethane to a 100 ml round-bottom flask, and react overnight at room temperature. After the reaction, add saturated potassium hydroxide solution to the flask to adjust the pH to about 8, then extract three times with dichloromethane, and obtain a light red solid, namely ethyl-substituted tribromotriphenylene, with a yield of 99%.

[0034]

[0035] NMR characterization data: 1 H NMR(CDCl3, 300 MHz, ppm) δ 8.21–8.12 (d, 3H, J=8.1 Hz), 7.72–7.25 (m, 6H), 3.12–2.72 (m, 6H), 2.30–1.90 (m, 6H), 0.38–0.20 (t, 18H, J=8.1 Hz); 13 C NMR(CDCl3, 75 MHz, ppm) δ 155.02, 143.88, 139.09, 138.09, 129.44, 125.83, 125.56, 121.11, 57.04, 29.28, 8.42.

[0036] (2) Preparation of ligand L

[0037]

[0038] Ethyl-substituted tribromotriphenylene boronic acid ester 3-bromo-5-ethoxyethanol pyridine L

[0039] In a nitrogen atmosphere, 0.50 mmol of ethyl-substituted tribromotriphenylene, 0.50 mmol of pinacol borate, 1.80 mmol of 3-bromo-5-ethoxyethanol pyridine, 3.0 mmol of potassium carbonate, 0.05 mmol of Pd(PPh3)4 and 25 mL of toluene were added to a 100 mL round-bottom flask, and the mixture was refluxed at 120 °C for 48 h. After the reaction was completed, it was cooled to room temperature, quenched with water, extracted three times with dichloromethane, the organic phase was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was separated by column chromatography (eluent: dichloromethane:methanol = 10:1) to obtain a pale yellow solid, namely ligand L, with a yield of 68%.

[0040] Nuclear magnetic characterization data: 1 H NMR (400 MHz, CDCl3) δ 8.61 (ppm) (s, 3H), 8.45 (d, J = 8.2 Hz, 3H,), 8.34 (s, 3H), 7.66 (d, J = 7.8 Hz, 6H), 7.56 (s, 3H), 4.38 (t, 6H), 3.90 (t, 6H), 3.10–3.04 (m, 6H), 2.28–2.22 (m, 6H), 0.28 (t, J = 7.2 Hz, 18H); 13 C NMR (101 MHz, CDCl3) δ 155.22, 153.80, 144.80, 140.92, 140.65, 138.48, 137.37, 136.16, 135.88, 125.51, 125.12, 120.88, 120.16, 71.95, 69.69, 57.09, 29.62, 8.66。

[0041] (2) Preparation of hydrophilic triphenylene-based metal-organic nickel octahedral cage 1

[0042]

[0043] 12 μmol of metal nickel salt Ni(BF4)2 was dissolved in 0.5 mL of acetonitrile; 16 μmol of ligand L was added to a mixed solvent of 7 mL of water and 3 mL of acetonitrile and mixed evenly; the acetonitrile mixture of the metal nickel salt was slowly transferred to the water and acetonitrile mixture of ligand L with a syringe, and stirred at room temperature for 6 h. After the reaction was completed, it was cooled to room temperature, and the reaction solution was concentrated and evaporated to dryness; the obtained solid was washed with ether and dried to obtain cage 1, with a yield of 95%.

[0044] Since nickel is a paramagnetic metal ion, the nuclear magnetic spectral peaks of cage 1 have very low resolution. However, the structural formula of cage 1 was obtained through single crystal X-ray diffraction data, as Figure 1 shown (hydrogen atoms and anions of the cage are deleted for clarity).

[0045] Example 2

[0046] (1) The preparation of ligand L is the same as that in Example 1;

[0047] (2) Preparation of hydrophilic triptycene-based metal-organic nickel octahedral cage 2:

[0048]

[0049] On the basis of Example 1, change the metal nickel salt Ni(BF4)2 to Ni(ClO4)2, and keep the other conditions unchanged.

[0050] Example 3

[0051] (1) The preparation of ligand L is the same as that in Example 1;

[0052] (2) Preparation of hydrophilic triptycene-based metal-organic nickel octahedral cage 3:

[0053]

[0054] On the basis of Example 1, change the metal nickel salt Ni(BF4)2 to Ni(OSO2CF3)2, and keep the other conditions unchanged.

[0055] Example 4

[0056] (1) The preparation of ligand L is the same as that in Example 1;

[0057] (2) Preparation of hydrophilic triptycene-based metal-organic nickel octahedral cage 4:

[0058]

[0059] On the basis of Example 1, change the metal nickel salt Ni(BF4)2 to Ni[(CF3SO2)2N]2, and keep the other conditions unchanged.

[0060] Example 5

[0061] Preparation of N-phenylheptanamide-2-d:

[0062]

[0063] Add 0.05 mmol of triptycene-based metal-organic nickel octahedral cage 1, 1 mmol of N-phenylhept-6-enamide, 1 mmol of pinacol borane and a deuterium oxide / acetonitrile mixed solvent (5 mL of deuterium oxide and 5 mL of acetonitrile) into the flask, and react at room temperature for 10 hours; after the reaction is completed, the reaction solution is extracted with diethyl ether three times, and the raffinate of the reaction can be used for the next catalytic reaction. Combine the extracted organic phases and dry them with anhydrous MgSO4 for 30 minutes, then filter; concentrate the filtrate, purify it by column chromatography and dry it to obtain the product N-phenylheptanamide-2-d with a yield of 90%.

[0064] NMR characterization data: 1 H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 8.1 Hz, 3H), 7.28 (t, J = 7.9 Hz, 2H), 7.07 (t, J = 7.4 Hz, 1H), 2.33 (t, J = 7.6 Hz, 1H), 1.70 (m, 2H), 1.36–1.25 (m, 6H), 0.87 (t, J = 6.8 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 171.79, 138.14, 129.04, 124.23, 119.96, 37.89, 31.67, 29.05, 25.73, 22.61, 14.14; 2 H NMR (61 MHz, CHCl3) δ 2.35.

[0065] Example 6

[0066] Recycling of hydrophilic triphenylene-based metal-organic nickel octahedral cage 1:

[0067] 1 mmol of N-phenylhept-6-enamide, 1 mmol of pinacol borane and the raffinate from the reaction in Example 5 were added to a flask and reacted at room temperature for 10 hours; after the reaction was completed, the reaction solution was extracted three times with diethyl ether, the organic phases were combined and dried over anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate was concentrated, purified by column chromatography and dried to obtain the product N-phenylheptanamide-2-d, with a yield of 90%. The raffinate from the reaction was subjected to the same operation and then used for catalytic recycling, and the product yield was 88%. The catalytic activity of triphenylene-based metal-organic nickel octahedral cage 1 did not decrease significantly.

[0068] Example 7

[0069] Preparation of N-(p-methoxyphenyl)heptanamide-2-d:

[0070]

[0071] 0.01 mmol of triphenylene-based metal-organic nickel octahedral cage 2, 1 mmol of N-(p-methoxyphenyl)hept-6-enamide, 2 mmol of pinacol borane and a deuterium oxide / acetonitrile mixed solvent (6 mL of deuterium oxide and 4 mL of acetonitrile) were added to a flask and reacted at room temperature for 24 hours; after the reaction was completed, the reaction solution was extracted three times with diethyl ether, and the raffinate from the reaction could be used for the next catalytic reaction. The extracted organic phases were combined and dried over anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate was concentrated, purified by column chromatography and dried to obtain the product N-(p-methoxyphenyl)heptanamide-2-d, with a yield of 86%.

[0072] NMR characterization data:1 1H NMR (400 MHz, CDCl3) δ 7.44 (s, 1H), 7.42–7.38 (m, 2H), 6.86–6.80 (m, 2H), 3.77 (s, 3H), 2.33–2.29 (m, 1H), 1.69 (m, 2H), 1.41–1.23 (m, 6H), 0.97–0.78 (m, 3H); 13 13C NMR (101 MHz, CDCl3) δ 171.66, 156.37, 131.23, 121.91, 114.14, 55.55, 37.69, 31.67, 29.07, 29.04, 25.80, 25.73, 22.61, 14.15; 2 1H NMR (61 MHz, CHCl3) δ 2.31.

[0073] Example 8

[0074] Preparation of N-(4-(methoxycarbonyl)phenyl)heptanamide-2-d:

[0075]

[0076] 0.03 mmol of truxene-based organometallic nickel octahedral cage 3, 1 mmol of N-(4-(methoxycarbonyl)phenyl)hept-6-enamide, and 1.5 mmol of pinacolborane were added to a flask along with a deuterium oxide / acetonitrile mixed solvent (8 mL of deuterium oxide and 2 mL of acetonitrile), and the reaction was carried out at room temperature for 16 hours; after the reaction was completed, the reaction solution was extracted three times with diethyl ether. The raffinate of the reaction could be used for the next catalytic reaction. The combined organic phases of the extraction were dried over anhydrous MgSO4 for 30 minutes and then filtered; the filtrate was concentrated, purified by column chromatography, and dried to obtain the product N-(4-(methoxycarbonyl)phenyl)heptanamide-2-d with a yield of 93%.

[0077] NMR characterization data: 1 1H NMR (400 MHz, CDCl3) δ 8.03–7.97 (m, 2H), 7.60 (d, J = 8.8 Hz, 2H), 7.33 (s, 1H), 3.89 (s, 3H), 2.38 (t, J = 7.6 Hz, 1H), 1.78–1.66 (m, 2H), 1.37–1.26 (m, 6H), 0.92–0.85 (m, 3H); 13 13C NMR (101 MHz, CDCl3) δ 171.70, 166.71, 142.21, 130.95, 125.56, 118.76, 52.13, 38.03, 31.62, 28.99, 25.49, 22.58, 14.13; 2 1H NMR (61 MHz, CHCl3) δ 2.37.

[0078] Example 9

[0079] Preparation of N-(4-bromophenyl)heptanamide-2-d:

[0080]

[0081] Add 0.04 mmol of the octahedral cage of truxene-based organometallic nickel 4, 1 mmol of N-(4-bromophenyl)pent-6-enamide, 1.2 mmol of pinacolborane, and a deuterium oxide / acetonitrile mixed solvent (7 mL of deuterium oxide and 3 mL of acetonitrile) into a flask, and react at room temperature for 18 hours; after the reaction is completed, the reaction solution is extracted with diethyl ether three times. The raffinate of the reaction can be used for the next catalytic reaction. The extracted organic phases are combined and dried with anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate is concentrated, purified by column chromatography, and dried to obtain the product N-(4-bromophenyl)heptanamide-2-d with a yield of 91%.

[0082] NMR characterization data: 1 H NMR(400MHz,CDCl3)δ7.41(s,4H),7.38(s,1H),2.35–2.31(m,1H),1.69(m,2H),1.41–1.32(m,2H),1.32–1.25(m,4H),0.92–0.83(m,3H). 13 C NMR(101MHz,CDCl3)δ171.72,137.13,132.00,121.46,116.78,37.86,31.63,29.02,25.60,22.59,14.13. 2 H NMR(61MHz,CHCl3)δ2.33.

[0083] Example 10

[0084] Preparation of N-(4-fluorophenyl)heptanamide-2-d:

[0085]

[0086] Add 0.02 mmol of the octahedral cage of truxene-based organometallic nickel 2, 1 mmol of N-(4-fluorophenyl)hept-6-enamide, 1.6 mmol of pinacolborane, and a deuterium oxide / acetonitrile mixed solvent (5 mL of deuterium oxide and 5 mL of acetonitrile) into a flask, and react at room temperature for 24 hours; after the reaction is completed, the reaction solution is extracted with diethyl ether three times. The raffinate of the reaction can be used for the next catalytic reaction. The extracted organic phases are combined and dried with anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate is concentrated, purified by column chromatography, and dried to obtain the product N-(4-fluorophenyl)heptanamide-2-d with a yield of 86%.

[0087] NMR characterization data: 1 H NMR(400 MHz, CDCl3) δ 7.50–7.43(m, 2H), 7.22(s, 1H), 7.00(t, J = 8.7 Hz, 2H), 2.36–2.31(m, 1H), 1.70(m, 2H), 1.38–1.28(m, 6H), 0.92–0.85(m, 3H); 13 C NMR(101 MHz, CDCl3) δ 171.52, 160.58, 158.16, 134.02, 121.75, 121.67, 115.80, 115.58, 37.77, 31.64, 29.03, 25.66, 22.59, 14.13; 2 H NMR(61 MHz, CHCl3) δ 2.34.

[0088] Example 11

[0089] Preparation of N-(3′-bromo)phenylheptanamide-2-d:

[0090]

[0091] Add 0.02 mmol of trisindenyl nickel octahedral cage 2, 1 mmol of N-(3′-bromo)phenylhept-6-enamide, 1.5 mmol of pinacolborane and a deuterium oxide / acetonitrile mixed solvent (7 mL of deuterium oxide and 3 mL of acetonitrile) into a flask, and react at room temperature for 20 hours; after the reaction is completed, the reaction solution is extracted three times with diethyl ether. The raffinate of the reaction can be used for the next catalytic reaction. The combined organic phases of the extraction are dried with anhydrous MgSO4 for 30 minutes and then filtered; the filtrate is concentrated, purified by column chromatography and dried to obtain the product N-(3′-bromo)phenylheptanamide-2-d with a yield of 85%.

[0092] NMR characterization data: 1 H NMR(400 MHz, CDCl3) δ 7.50–7.43(m, 2H), 7.22(s, 1H), 7.00(t, J = 8.7 Hz, 2H), 2.36–2.31(m, 1H), 1.70(m, 2H), 1.38–1.28(m, 6H), 0.92–0.85(m, 3H); 13 C NMR(101 MHz, CDCl3) δ 171.87, 139.34, 130.32, 127.22, 122.86, 122.67, 118.37, 37.81, 31.62, 28.99, 28.96, 25.60, 25.54, 22.58, 14.11; 2 H NMR(61 MHz, CHCl3) δ 2.33.

[0093] Example 12

[0094] Preparation of N-(3′-trifluoromethyl)phenylheptanamide-2-d:

[0095]

[0096] Add 0.03 mmol of truxene-based organometallic nickel octahedron cage 3, 1 mmol of N-(3′-trifluoromethyl)phenylhept-6-enamide, 1.8 mmol of pinacolborane and a deuterium oxide / acetonitrile mixed solvent (5 mL of deuterium oxide and 5 mL of acetonitrile) into a flask, and react at room temperature for 16 hours; after the reaction is completed, the reaction solution is extracted three times with diethyl ether. The raffinate of the reaction can be used for the next catalytic reaction. The extracted organic phases are combined and dried with anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate is concentrated, purified by column chromatography and dried to obtain the product N-(3′-trifluoromethyl)phenylheptanamide-2-d with a yield of 95%.

[0097] NMR characterization data: 1 H NMR(400MHz,CDCl3)δ7.82(s,1H),7.72(d,J=7.8Hz,2H),7.40(t,J=7.9Hz,1H),7.33(d,J=8.0Hz,1H),2.39–2.34(m,1H),1.71(t,J=7.1Hz,2H),1.36(m,2H),1.32–1.26(m,4H),0.90–0.85(m,3H); 13 C NMR(101MHz,CDCl3)δ172.10,138.58,131.88,131.56,131.24,130.92,129.56,125.28,122.96,122.57,120.80,120.77,116.65,116.61,37.77,31.60,28.98,25.56,22.55,14.07; 2 H NMR(61MHz,CHCl3)δ2.37. 19 F NMR(376MHz,CHCl3)δ-62.68.

[0098] Example 13

[0099] Preparation of N-(3′,5′-dibromo)phenylheptanamide-2-d:

[0100]

[0101] Add 0.02 mmol of the octahedral cage of organometallic nickel of tribenzotriindene 4, 1 mmol of N-(3′,5′-dibromo)phenylhept-6-enamide, 1.3 mmol of pinacolborane and a deuterium oxide / acetonitrile mixed solvent (7 mL of deuterium oxide and 3 mL of acetonitrile) to a flask, and react at room temperature for 24 hours; after the reaction is completed, the reaction solution is extracted three times with diethyl ether. The raffinate of the reaction can be used for the next catalytic reaction. The extracted organic phases are combined and dried with anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate is concentrated, purified by column chromatography and dried to obtain the product N-(3′,5′-dibromo)phenylheptanamide-2-deuterium with a yield of 91%.

[0102] Nuclear magnetic characterization data: 1 H NMR(400MHz,CDCl3)δ7.68(d,J=1.7Hz,2H),7.49(s,1H),7.37(t,J=1.7Hz,1H),2.37–2.32(m,1H),1.71–1.67(m,2H),1.38–1.25(m,6H),0.93–0.83(m,3H); 13 C NMR(101MHz,CDCl3)δ171.92,140.12,130.11,129.65,126.37,123.06,121.36,37.78,31.61,28.96,25.49,22.58,14.13; 2 H NMR(61MHz,CHCl3)δ2.37。

[0103] Example 14

[0104] Preparation of N-(3′,5′-difluoro)phenylheptanamide-2-deuterium:

[0105]

[0106] Add 0.03 mmol of the octahedral cage of organometallic nickel of tribenzotriindene 1, 1 mmol of N-(3′,5′-difluoro)phenylhept-6-enamide, 1.6 mmol of pinacolborane and a deuterium oxide / acetonitrile mixed solvent (5 mL of deuterium oxide and 5 mL of acetonitrile) to a flask, and react at room temperature for 18 hours; after the reaction is completed, the reaction solution is extracted three times with diethyl ether. The raffinate of the reaction can be used for the next catalytic reaction. The extracted organic phases are combined and dried with anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate is concentrated, purified by column chromatography and dried to obtain the product N-(3′,5′-difluoro)phenylheptanamide-2-deuterium with a yield of 88%.

[0107] Nuclear magnetic characterization data: 11H NMR (400 MHz, CDCl3) δ 7.60 (s, 1H), 7.19–7.08 (m, 2H), 6.53 (m, 1H), 2.38–2.32 (m, 1H), 1.74–1.65 (m, 2H), 1.39–1.32 (m, 2H), 1.29 (t, J = 3.1 Hz, 4H), 0.92–0.83 (m, 3H); 13 13C NMR (101 MHz, CDCl3) δ 172.00, 164.54, 164.40, 162.10, 161.95, 140.32, 140.19, 140.06, 102.93, 102.63, 99.69, 99.43, 99.18, 37.85, 31.58, 28.95, 28.92, 25.49, 25.42, 22.54, 14.07; 2 1H NMR (61 MHz, CHCl3) δ 2.35; 19 19F NMR (376 MHz, CDCl3) δ -108.83.

[0108] Example 15

[0109] Preparation of N-phenylhexanamide-2-d:

[0110]

[0111] Add 0.05 mmol of truxene-based organometallic nickel octahedral cage 1, 1 mmol of N-phenylhex-5-enamide, 1.5 mmol of pinacolborane and a mixed solvent of heavy water / acetonitrile (1.8 mL of heavy water and 8.2 mL of acetonitrile) to a flask, and react at room temperature for 10 hours; after the reaction is completed, the reaction solution is extracted with ether three times, and the raffinate of the reaction can be used for the next catalytic reaction. The combined organic phases of the extraction are dried with anhydrous MgSO4 for 30 minutes and filtered; the filtrate is concentrated, purified by column chromatography and dried to obtain the product N-phenylhexanamide-2-d with a yield of 87%.

[0112] NMR characterization data: 1 1H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 7.4 Hz, 2H), 7.44–7.33 (m, 1H), 7.32–7.26 (m, 2H), 7.13–7.03 (m, 1H), 2.35–2.31 (m, 1H), 1.74–1.68 (m, 2H), 1.33 (m, 4H), 0.92–0.86 (m, 3H). 1313C NMR (101 MHz, CDCl3) δ 171.70, 138.09, 129.07, 124.25, 119.90, 37.89, 31.52, 31.49, 25.45, 22.54, 14.05. 2 1H NMR (61 MHz, CHCl3) δ 2.33

[0113] Example 16

[0114] Preparation of N-(4-methoxyphenyl)hexanamide-2-d:

[0115]

[0116] Add 0.01 mmol of truxene-based organometallic nickel octahedral cage 2, 1 mmol of N-(4-methoxyphenyl)hex-5-enamide, 1.8 mmol of pinacolborane and a mixed solvent of heavy water / acetonitrile (2.4 mL of heavy water and 7.6 mL of acetonitrile) to a flask, and react at room temperature for 24 hours; after the reaction is completed, the reaction solution is extracted with diethyl ether three times. The raffinate of the reaction can be used for the next catalytic reaction. The combined organic phases of the extraction are dried with anhydrous MgSO4 for 30 minutes and filtered; the filtrate is concentrated, purified by column chromatography and dried to obtain the product N-(4-methoxyphenyl)hexanamide-2-d with a yield of 85%.

[0117] NMR characterization data: 1 1H NMR (400 MHz, CDCl3) δ δ 7.44–7.37 (m, 3H), 6.86–6.79 (m, 2H), 3.77 (s, 3H), 2.33–2.28 (m, 1H), 1.69 (m, 2H), 1.38–1.30 (m, 4H), 0.93–0.86 (m, 3H). 13 13C NMR (101 MHz, CDCl3) δ 171.62, 156.37, 131.22, 121.91, 114.15, 55.55, 37.65, 31.55, 31.52, 25.52, 22.54, 14.05. 2 1H NMR (61 MHz, CHCl3) δ 2.32.

[0118] Example 17

[0119] Preparation of N-(4-(methoxycarbonyl)phenyl)hexanamide-2-d:

[0120]

[0121] Add 0.04 mmol of the organometallic nickel octahedral cage of tribenzotriindene 3, 1 mmol of N-(p-carboxymethoxyphenyl)hex-5-enamide, 1.3 mmol of pinacol borane, and a deuterium oxide / acetonitrile mixed solvent (2 mL of deuterium oxide and 8 mL of acetonitrile) to a flask, and react at room temperature for 18 hours; after the reaction is completed, the reaction solution is extracted three times with diethyl ether. The raffinate of the reaction can be used for the next catalytic reaction. The combined organic phases of the extraction are dried with anhydrous MgSO4 for 30 minutes and then filtered; the filtrate is concentrated, purified by column chromatography, and dried to obtain the product N-(p-carboxymethoxyphenyl)hexanamide-2-d, with a yield of 91%.

[0122] NMR characterization data: 1 H NMR(400MHz,CDCl3)δδ7.96(s,2H),7.77(s,1H),7.62(d,J=8.8Hz,2H),3.88(s,3H),2.39–2.35(m,1H),1.72(q,J=7.0,6.6Hz,2H),1.32(q,J=3.6Hz,4H),0.92–0.85(m,3H). 13 C NMR(101MHz,CDCl3)δ172.04,166.82,142.39,130.90,125.44,118.88,52.14,37.90,31.47,25.26,22.49,14.00. 2 H NMR(61MHz,CHCl3)δ2.37.

[0123] Example 18

[0124] Preparation of N-(3′-bromo)phenylhexanamide-2-d:

[0125]

[0126] Add 0.02 mmol of the organometallic nickel octahedral cage of tribenzotriindene 2, 1 mmol of N-(3′-bromo)phenylhex-5-enamide, 1.4 mmol of pinacol borane, and a deuterium oxide / acetonitrile mixed solvent (3 mL of deuterium oxide and 7 mL of acetonitrile) to a flask, and react at room temperature for 24 hours; after the reaction is completed, the reaction solution is extracted three times with diethyl ether. The raffinate of the reaction can be used for the next catalytic reaction. The combined organic phases of the extraction are dried with anhydrous MgSO4 for 30 minutes and then filtered; the filtrate is concentrated, purified by column chromatography, and dried to obtain the product N-(3′-bromo)phenylhexanamide-2-d, with a yield of 82%.

[0127] NMR characterization data: 11H NMR (400 MHz, CDCl3) δ 7.78 (s, 1H), 7.58 (s, 1H), 7.42 (d, J = 8.7 Hz, 1H), 7.20 (s, 1H), 7.14 (t, J = 8.0 Hz, 1H), 2.37–2.31 (m, 1H), 1.70 (m, 2H), 1.33 (m, 4H), 0.92–0.86 (m, 3H). 13 13C NMR (101 MHz, CDCl3) δ 171.94, 139.35, 130.32, 127.22, 122.89, 122.66, 118.39, 37.77, 31.47, 31.44, 25.34, 25.28, 22.51, 14.02. 2 1H NMR (61 MHz, CHCl3) δ 2.35.

[0128] Example 19

[0129] Preparation of N-(3′,5′-difluoro)phenylhexanamide-2-d:

[0130]

[0131] Add 0.03 mmol of truxene-based organometallic nickel octahedral cage 4, 1 mmol of N-(3′,5′-difluoro)phenylhex-5-enamide, 1.7 mmol of pinacolborane, and a deuterium oxide / acetonitrile mixed solvent (1.6 mL of deuterium oxide and 8.4 mL of acetonitrile) to a flask, and react at room temperature for 16 hours; after the reaction is completed, the reaction solution is extracted three times with diethyl ether. The raffinate of the reaction can be used for the next catalytic reaction. The combined organic phases of the extraction are dried with anhydrous MgSO4 for 30 minutes and filtered; the filtrate is concentrated, purified by column chromatography, and dried to obtain the product N-(3′,5′-difluoro)phenylhexanamide-2-d with a yield of 89%.

[0132] Nuclear magnetic characterization data: 1 1H NMR (400 MHz, CDCl3) δ 7.76 (s, 1H), 7.14 (m, 2H), 6.53 (m, 1H), 2.37–2.33 (m, 1H), 1.70 (m, 2H), 1.32 (m, 4H), 0.92–0.86 (m, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.16, 164.53, 164.39, 162.09, 161.94, 140.35, 140.22, 140.08, 102.98, 102.69, 99.69, 99.43, 99.18, 37.80, 31.42, 25.23, 22.46, 13.94. 21H NMR (61 MHz, CHCl3) δ 2.36.

[0133] Example 20

[0134] Preparation of N-(4-fluorophenyl)hexanamide-2-d:

[0135]

[0136] Add 0.01 mmol of truxene-based organometallic nickel octahedral cage 2, 1 mmol of N-(4-fluorophenyl)hex-5-enamide, 1.6 mmol of pinacolborane and a mixed solvent of heavy water / acetonitrile (2.8 mL of heavy water and 7.2 mL of acetonitrile) into a flask, and react at room temperature for 24 hours; after the reaction is completed, the reaction solution is extracted with diethyl ether three times, and the raffinate of the reaction can be used for the next catalytic reaction. The combined organic phases of the extraction are dried with anhydrous MgSO4 for 30 minutes and filtered; the filtrate is concentrated, purified by column chromatography and dried to obtain the product N-(4-fluorophenyl)hexanamide-2-d with a yield of 90%.

[0137] Nuclear magnetic characterization data: 1 1H NMR (400 MHz, CDCl3) δ 7.53 (s, 1H), 7.49–7.42 (m, 2H), 7.02–6.93 (m, 2H), 2.35–2.29 (m, 1H), 1.75–1.65 (m, 2H), 1.33 (m, 4H), 0.92–0.86 (m, 3H). 13 13C NMR (101 MHz, CDCl3) δ 171.78, 160.58, 158.16, 134.10, 121.88, 121.80, 115.74, 115.52, 37.66, 31.51, 25.42, 22.51, 14.02. 2 1H NMR (61 MHz, CHCl3) δ 2.33. 19 19F NMR (376 MHz, CDCl3) δ -118.09.

[0138] Example 21

[0139] Preparation of N-(4-ethylphenyl)pentanamide-2-d:

[0140]

[0141] Add 0.02 mmol of the octahedral cage of organometallic nickel with triphenylene, 1 mmol of N-(4-ethylphenyl)pent-4-enamide, 1.3 mmol of pinacolborane and a deuterium oxide / acetonitrile mixed solvent (2.6 mL of deuterium oxide and 7.4 mL of acetonitrile) into a flask, and react at room temperature for 20 hours; after the reaction is completed, the reaction solution is extracted with diethyl ether three times. The raffinate of the reaction can be used for the next catalytic reaction. The extracted organic phases are combined and dried with anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate is concentrated, purified by column chromatography and dried to obtain the product N-(4-ethylphenyl)pentanamide-2-d, with a yield of 87%.

[0142] NMR characterization data: 1 HNMR(400MHz,CDCl3)δ7.41(d,J=8.5Hz,2H),7.35(s,1H),7.12(d,J=8.5Hz,2H),2.59(q,J=7.5Hz,2H),2.32(t,J=7.5Hz,1H),1.72–1.65(m,2H),1.42–1.34(m,2H),1.19(t,J=7.5Hz,3H),0.92(t,J=7.3Hz,3H). 13 C NMR(101MHz,CDCl3)δ171.47,140.34,135.67,128.38,120.08,37.59,28.38,27.84,22.48,15.77,13.92. 2 H NMR(61MHz,CHCl3)δ2.34.

[0143] Example 22

[0144] Preparation of N-(4-bromophenyl)pentanamide-2-d:

[0145]

[0146] Add 0.03 mmol of the octahedral cage of organometallic nickel with triphenylene, 1 mmol of N-(4-bromophenyl)pent-4-enamide, 1.5 mmol of pinacolborane and a deuterium oxide / acetonitrile mixed solvent (2.1 mL of deuterium oxide and 7.9 mL of acetonitrile) into a flask, and react at room temperature for 17 hours; after the reaction is completed, the reaction solution is extracted with diethyl ether three times. The raffinate of the reaction can be used for the next catalytic reaction. The extracted organic phases are combined and dried with anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate is concentrated, purified by column chromatography and dried to obtain the product N-(4-bromophenyl)pentanamide-2-d, with a yield of 85%.

[0147] NMR characterization data: 1HNMR(400MHz, CDCl3) δ 7.40(s, 4H), 7.38(t, J=1.9Hz, 1H), 2.35–2.31(m, 1H), 1.71–1.64(m, 2H), 1.38(m, 2H), 0.92(t, J=7.4Hz, 3H). 13 C NMR(101MHz, CDCl3) δ 171.72, 137.12, 132.01, 121.46, 116.79, 37.59, 27.70, 22.48, 13.94. 2 H NMR(61MHz, CHCl3) δ 2.33.

[0148] Example 23

[0149] Preparation of N-(p-trifluoromethylphenyl)pentanamide-2-d:

[0150]

[0151] Add 0.02 mmol of truxene-based organometallic nickel octahedron cage 4, 1 mmol of N-(p-trifluoromethylphenyl)pent-4-enamide, 1.8 mmol of pinacolborane, and a deuterium oxide / acetonitrile mixed solvent (5 mL of deuterium oxide and 5 mL of acetonitrile) into a flask, and react at room temperature for 12 hours; after the reaction is completed, the reaction solution is extracted with diethyl ether three times. The raffinate of the reaction can be used for the next catalytic reaction. The combined organic phases of the extraction are dried with anhydrous MgSO4 for 30 minutes and filtered; the filtrate is concentrated, purified by column chromatography, and dried to obtain the product N-(p-trifluoromethylphenyl)pentanamide-2-d with a yield of 93%.

[0152] Nuclear magnetic characterization data: 1 HNMR(400MHz, CDCl3) δ 7.75(s, 1H), 7.64(d, J=8.5Hz, 2H), 7.53(d, J=8.3Hz, 2H), 2.37(s, 1H), 1.72–1.65(m, 2H), 1.41–1.34(m, 2H), 0.91(t, J=7.4Hz, 3H). 13 C NMR(101MHz, CDCl3) δ 172.08, 141.14, 126.36, 126.32, 126.29, 126.25, 125.80, 125.51, 122.82, 119.44, 37.60, 27.63, 22.44, 13.87. 2 H NMR(61MHz, CHCl3) δ 2.38. 19 FNMR(376MHz, CDCl3) δ -61.99.

[0153] Example 24

[0154] Preparation of N-(o-methylthiophenyl)valeramide-2-d:

[0155]

[0156] Add 0.04 mmol of truxene-based organometallic nickel octahedral cage 2, 1 mmol of N-(o-methylthiophenyl)pent-4-enamide, 1.2 mmol of pinacolborane, and a deuterium oxide / acetonitrile mixed solvent (1 mL of deuterium oxide and 9 mL of acetonitrile) into a flask, and react at room temperature for 15 hours; after the reaction is completed, the reaction solution is extracted with diethyl ether three times. The raffinate of the reaction can be used for the next catalytic reaction. The extracted organic phases are combined and dried with anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate is concentrated, purified by column chromatography, and dried to obtain the product N-(o-methylthiophenyl)valeramide-2-d with a yield of 91%.

[0157] Nuclear magnetic resonance characterization data: 1 HNMR(400MHz,CDCl3)δ8.32(d,J=8.2Hz,1H),8.30(s,1H),7.46(d,J=7.8Hz,1H),7.32–7.25(m,1H),7.05(t,J=7.6Hz,1H),2.42(t,J=7.6Hz,1H),2.36(s,3H),1.73(p,J=8.3,7.9Hz,2H),1.42(m,2H),0.95(t,J=7.3Hz,3H). 13 C NMR(101MHz,CDCl3)δ171.59,138.48,133.02,129.04,125.06,124.32,120.66,37.94,27.79,22.46,19.04,13.93. 2 H NMR(61MHz,CHCl3)δ2.43.

[0158] Example 25

[0159] Preparation of N-(3′,5′-difluoro)phenylvaleramide-2-d:

[0160]

[0161] Add 0.02 mmol of the metal-organic nickel octahedral cage of triphenylene 4, 1 mmol of N-(3′,5′-difluoro)phenylpent-4-enamide, 1.6 mmol of pinacol borane and a deuterium oxide / acetonitrile mixed solvent (1.9 mL of deuterium oxide and 8.1 mL of acetonitrile) into a flask, and react at room temperature for 20 hours; after the reaction is completed, the reaction solution is extracted three times with diethyl ether. The raffinate of the reaction can be used for the next catalytic reaction. The extracted organic phases are combined and dried with anhydrous MgSO4 for 30 minutes, and then filtered; the filtrate is concentrated, purified by column chromatography and dried to obtain the product N-(3′,5′-difluoro)phenylpentanamide-2-deuterium with a yield of 86%.

[0162] Nuclear magnetic characterization data: 1 1H NMR (400 MHz, CDCl3) δ 7.73 (s, 1H), 7.16–7.09 (m, 2H), 6.52 (m, 1H), 2.37–2.33 (m, 1H), 1.71–1.62 (m, 2H), 1.40–1.32 (m, 2H), 0.91 (t, J = 7.4 Hz, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.14, 164.52, 164.38, 162.08, 161.93, 140.20, 102.97, 102.88, 102.68, 99.70, 99.45, 99.19, 37.57, 27.54, 22.40, 22.38, 13.84. 2 1H NMR (61 MHz, CHCl3) δ 2.38. 19 19F NMR (376 MHz, CDCl3) δ -108.84.

Claims

1. A hydrophilic triphenylene-based metal-organic nickel octahedral cage, characterized in that, The general formula is: [Ni6L8(X) 12 , where X is a monovalent anion and L is a hydrophilic triindenyl tridentate pyridine ligand, and the structural formula of L is: wherein X is BF4 - , ClO4 - , OSO2CF3 - or (CF3SO2)2N - .

2. The hydrophilic triphenylene-based metal-organic nickel octahedral cage according to claim 1, characterized in that, The octahedral cage structure is 3. A method for preparing the hydrophilic truxene-based metal-organic nickel octahedral cage described in claim 1 or 2, characterized in that, It includes the following steps: (1) Using ethyl-substituted tribromotriphenylene, boronic acid ester, and 3-bromo-5-ethoxyethanol pyridine as raw materials, tetrakis(triphenylphosphine)palladium as a catalyst, in an organic solvent, under alkaline conditions, under nitrogen protection, reacting at 80-100 °C for 12-24 hours to obtain ligand L; (2) Taking ligand L and nickel salt and adding them to a mixed solvent of water and acetonitrile, and stirring for 3-6 hours to obtain an organometallic nickel octahedral cage.

4. The preparation method of the hydrophilic triphenylene-based metal-organic nickel octahedral cage according to claim 3, characterized in that, In step (1), the organic solvent is toluene or xylene.

5. The preparation method of the hydrophilic truxene-based metal-organic nickel octahedral cage according to claim 3, characterized in that, In step (2), the volume ratio of water to acetonitrile is 1-5:

1.

6. Application of the hydrophilic triphenylene-based organometallic nickel octahedral cage described in claim 1 or 2 in the hydrogen-deuterium reduction reaction.

7. The application according to claim 6, wherein The application method is: adding the hydrophilic triphenylene-based organometallic nickel octahedral cage, an olefin derivative, and pinacol borane to a mixed solvent of heavy water and acetonitrile, reacting at 20-25 °C for 10-24 hours to obtain an olefin metathesis deuterated product, and the reaction formula is as follows: Among them, n = 1-3, and R1 and R2 are selected from -H, -CF3, -C2H5, -Br, -F, -OCH3, -SCH3, or -COOCH3.

8. The application according to claim 7, wherein The molar ratio of the hydrophilic triphenylene-based organometallic nickel octahedral cage, the olefin derivative, and pinacol borane is 0.01-0.05:1:1-2.

9. The application according to claim 7, characterized in that, The volume ratio of the heavy water to acetonitrile is 0.1-0.5:1.

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