CN116693373A - Chiral binaphthyl enantiomer macrocyclic arene, and synthetic method and application thereof - Google Patents

Chiral binaphthyl enantiomer macrocyclic arene, and synthetic method and application thereof Download PDF

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CN116693373A
CN116693373A CN202310448560.2A CN202310448560A CN116693373A CN 116693373 A CN116693373 A CN 116693373A CN 202310448560 A CN202310448560 A CN 202310448560A CN 116693373 A CN116693373 A CN 116693373A
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compound
mapped
chiral binaphthyl
arene
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欧光川
曾飞
唐琳俐
丁满花
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Hunan University of Science and Engineering
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Abstract

The invention discloses chiral binaphthyl-mapped macrocyclic arene, and a preparation method and application thereof. Chiral binaphthyl-mapped macrocyclic aromatic compounds have the following structural formulas RR-1 and SS-1:the selective recognition of iodine anions is better than that of AcO ‑ 、NO 3‑ 、ClO 4 ‑ 、HSO 4 ‑ 、Br ‑ 、PF 6 ‑ 、H 2 PO 4 ‑ 、BF 4 ‑ 、CO 3 F 3 S ‑ The plasma anions, and the identification process can generate macroscopic color change, and can be used for detecting iodine anions.

Description

Chiral binaphthyl enantiomer macrocyclic arene, and synthetic method and application thereof
Technical Field
The invention relates to a macrocyclic arene, in particular to a chiral binaphthyl-mapped macrocyclic arene, a synthesis method thereof and application of the chiral binaphthyl-mapped macrocyclic arene as a molecular probe in detection of iodine anions in a solution system, and belongs to the technical field of small organic molecular materials.
Background
Negative ions are ubiquitous and play an important role in the human body. For example, iodine is a raw material for synthesizing thyroid hormone, and can promote metabolism of substances, regulate metabolism of proteins, fats and sugars, and contribute to regulation of metabolism of water and salts. However, iodine deficiency can lead to goiter or hypothyroidism. However, the most common effects of periodate on thyroid function are iodinated goiter (IH) and periodate hyperthyroidism. In addition, in the case of the optical fiber, 129 I - and 130 the radioisotope of I-is considered to be harmful to the environment. Therefore, the development of an iodine anion receptor and a sensor for detecting iodine anions has great value and has attracted considerable interest.
The development of supermolecular chemistry is driven by the continuous synthesis of novel macrocyclic host molecules and their unique molecular recognition properties. Over the past few decades, various macrocyclic hosts have been developed and exhibit excellent recognition properties for anions such as fluoride, nitrate, oxyacids and other anions. Prominent examples are Sessler's cuppyrrole, farnham's fluorinated macrocyclic ether, flood's triazolidine, sindbusiil macrocycle of Sindelar, beer's rotaxane and chordin, etc. Most strategies involve the incorporation of anions by utilizing hydrogen bonding provided by specific binding sites, thereby providing size and shape selectivity in a variety of media. However, there are relatively few reports of building up the macrocyclic ring of the iodonium anion receptor, because the iodonium anion has a large diameter and a low electron density, and it is difficult to form hydrogen bonds and anion-pi interactions. The literature (Angew.Chem., int.Ed.,2008,47,788;Angew.Chem, int.Ed.,2008,47,2649;Angew.Chem, int. Ed.,
2008,47,3740; J.am.chem.Soc.,2008,130,10895.) elucidates neutral C-H … anion interactions, which have attracted great interest and rapid development by chemists. Literature
(Science,2019,365,159；Chem.Soc.Rev.,2010,39,1262；Chem.Commun.,
2012,48,5065.) discloses triazole macrocycles and cages, and it was found that these exhibit strong affinity for anions through neutral C-H … anion interactions. Literature (Org).
Lett.,2020,22,4878；J.Am.Chem.Soc.,2020,142,20182；Angew.Chem.Int.
Ed.,2022, e 202209778.) reports the recognition of anions in water by molecular cages through neutral C-H … anion interactions. Literature (org.lett., 2016,18,5054.) demonstrates that pre-organized rigid macrocyclic [4] carbazoles can act as iodide anion receptors through neutral C-H … anion interactions. Despite these pioneering reports, macrocyclic host molecules with selective recognition of iodide anions have been rarely reported.
Disclosure of Invention
Aiming at the defects of the prior art, the first object of the invention is to provide chiral binaphthyl enantiomer macrocyclic arene which has a large number of neutral aryl C-H bonds and a special cavity structure, has selective recognition and complexation effects on iodine anions, has macroscopic color change after complexing the iodine anions, and is particularly suitable for detecting the iodine anions in a solution system.
The second aim of the invention is to provide a synthesis method of chiral binaphthyl-mapped macrocyclic arene, which is simple, mild in condition and high in yield, and is beneficial to expanding production.
A third object of the present invention is to provide the use of a chiral binaphthyl-mapped macrocyclic aromatic hydrocarbon comprising AcO - 、NO 3- 、ClO 4 - 、HSO 4 - 、Br - 、PF 6 - 、H 2 PO 4 - 、BF 4 - 、CO 3 F 3 S - The iodine anions in the solution system of the plasma anions have selective recognition and complexation effects, and the color change visible to naked eyes after the iodine anions are complexed can be used for detecting the iodine anions in the solution system.
In order to achieve the above technical object, the present invention provides a chiral binaphthyl-enantiomer macrocyclic arene comprising RR-1 and/or SS-1 compounds;
the chiral binaphthyl-enantiomer macrocyclic aromatic hydrocarbon RR-1 and SS-1 provided by the invention have box-shaped structures, the cavity sizes are about 10.100 multiplied by 9.000 and 9.000 multiplied by 9.000 respectively, and RR-1 and SS-1 both contain a large number of neutral aryl C-H bonds and can be used as an iodine anion receptor to realize complexation of iodine anions, and particularly, the chiral binaphthyl-enantiomer macrocyclic aromatic hydrocarbon RR-1 and SS-1 have selective recognition effect on complex anion solution systems, and the RR-1 and SS-1 compounds have obvious macroscopic color change after complexing the iodine anions, so that the RR-1 and SS-1 compounds can be used for detecting the iodine anions.
The invention also provides a synthesis method of chiral binaphthyl-mapped macrocyclic arene, which comprises the steps of carrying out a suzuki coupling reaction on 2, 4-dimethoxy phenylboronic acid and an R-3 or S-3 compound to obtain the R-2 or S-2 compound; r-2 or S-2 and paraformaldehyde are subjected to condensation reaction to obtain RR-1 or SS-1 structural compounds;
the structural formula of the R-3 compound is as follows:
the structural formula of the S-3 compound is as follows:
the structural formula of the R-2 compound is as follows:
the structural formula of the S-2 compound is as follows:
the synthesis method of chiral binaphthyl enantiospecific macrocyclic arene can be realized through two-step reactions of suzuki coupling and condensation, and has the advantages of simple synthesis method and higher product yield.
As a preferred embodiment, the 2, 4-dimethoxyphenylboronic acid and the R-3 or S-3 compound are combined in Pd (PPh) 3 ) 4 And reacting for 12-36 hours at the temperature of 85-95 ℃ under the catalysis of CuI. Further preferably, the reaction is carried out at a temperature of 90℃for 24 hours.
As a more preferable scheme, the molar ratio of sodium carbonate to R-3 or S-3 compound is 1 (2-3).
As a more preferable embodiment, the molar ratio of 2, 4-dimethoxyphenylboronic acid to R-3 or S-3 compound is 1 (2-2.5).
As a more preferable embodiment, pd (PPh 3 ) 4 And CuI is added in catalytic amounts, for example 5 to 20mol%.
As a preferred scheme, in a dichloromethane solution system, the R-2 or S-2 compound and paraformaldehyde are reacted for 0.4 to 0.6 hours at room temperature under the catalysis of boron trifluoride diethyl ether. The addition amount of boron trifluoride diethyl etherate is 1 to 1.5 times of the molar amount of R-2 or S-2.
As a more preferred embodiment, the molar ratio of the R-2 or S-2 compound to paraformaldehyde is 1 (2 to 4).
The specific synthetic route of the chiral binaphthyl-mapped macrocyclic arene is as follows:
the invention also provides an application of the chiral binaphthyl-mapped macrocyclic arene as a molecular probe in detection of iodine anions in a solution system. The selective recognition effect of chiral binaphthyl-mapped macrocyclic aromatic hydrocarbon on iodine negative ions is obviously superior to that of other anions, such as AcO - 、NO 3- 、ClO 4 - 、HSO 4 - 、Br - 、PF 6 - 、H 2 PO 4 - 、BF 4 - 、CO 3 F 3 S - Etc., and the identification process may be visually observed, such as a change in color of the solution from colorless to light orange. Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the chiral binaphthyl-mapped macrocyclic aromatic hydrocarbon provided by the invention has a large number of neutral aryl C-H bonds and a special cavity structure, and has selective recognition and complexation effects on iodine anions, such as those containing AcO - 、NO 3- 、ClO 4 - 、HSO 4 - 、Br - 、PF 6 - 、H 2 PO 4 - 、BF 4 - 、CO 3 F 3 S - The solution system of the plasma anions can be used for identifying and complexing the iodide anions with high selectivity and generating macroscopic color change, and can be used for detecting the iodide anions in the solution system.
The synthesis method of chiral binaphthyl-mapped macrocyclic arene is simple, mild in condition and high in yield, and is beneficial to expansion of production.
Drawings
FIGS. 1 a) and b) are energy minimization structures of RR-1 and SS-1 simulated by a Gaussian computer program; c) CD spectra for RR-1 (black line) and SS-1 (red line).
In FIG. 2 a) is RR-1 (1.00X 10) -2 mM) in chloroform mixed solution, RR-1 and TBAX (X=AcO) - 、NO 3- 、ClO 4 - 、HSO 4 - 、Br - 、I - 、PF 6 - 、H 2 PO 4 - 、BF 4 - 、CO 3 F 3 S - ) (5.0 equivalents); b) Is SS-1 (1.00X 10) -2 mM) in chloroform mixed solution, SS-1 and TBAX (x=aco - 、NO 3- 、ClO 4 - 、HSO 4 - 、Br - 、I - 、PF 6 - 、H 2 PO 4 - 、BF 4 - 、CO 3 F 3 S - ) (5. Equivalent), the illustrations show photographs of the colors of these mixed solutions。
FIG. 3 a) is free RR-1 and b) is part of RR-1 1 H NMR spectrum (400 MHz, CDCl) 3 298K), 1.0 equivalent, c) is free TBAI, [ RR-1 ]] 0 ＝4.0mmol/L。
FIG. 4 is a Gaussian computer program modeling the energy minimization structures of RR-1/iodide and SS-1/iodide.
FIG. 5 shows RR-1 and SS-1 compounds 1 H NMR 13 C NMR。
Detailed Description
The following specific examples are intended to further illustrate the present invention, but not to limit the scope of the claims.
In the examples below, all reactions were carried out in oven-dried glassware. Commercial reagents were used without further purification. The chromatographic column adopts 100-200 mesh silica gel for separation.
R-3 and S-3 in the examples below were prepared according to the literature (org. Biomol. Chem.; 2011,9,2938.).
Example 1
R-3 (4.70 g,10 mmol), na 2 CO 3 (2.96 g,28 mmol), 2, 4-dimethoxyphenylboronic acid (4.00 g,22 mmol), a catalytic amount of CuI (21 mg) and tetrakis (triphenylphosphine) palladium (320 mg) were added to a mixture containing 100mL of CH 3 CH 2 Stirring in a flask of OH in N 2 Stirring for 24h at 90 ℃ under protection. After evaporation of the solvent, the mixture was extracted with dichloromethane (3×50 mL) and washed successively with water and brine. Organic layer in anhydrous Na 2 SO 4 Dried over and evaporated. The mixture was separated by silica gel column chromatography using methylene chloride/petroleum ether (4:1) as eluent to give compound R-2 (3.99 g, yield 68%) as a yellow solid.
1 H NMR(400MHz,Chloroform-d)δ8.01(d,J＝10.3Hz,4H),7.46(dd,J＝17.5,8.9Hz,4H),7.36(d,J＝8.4Hz,2H),7.19(d,J＝8.8Hz,2H),6.61(d,J＝7.6Hz,4H),3.88(s,6H),3.82(d,J＝2.2Hz,12H). 13 C NMR(101MHz,CDCl 3 )δ160.2,157.6,155.0,133.6,132.9,131.5,129.5,129.3,128.6,127.8,124.9,123.7,119.6,114.3,104.7,99.0,57.0,55.6,55.5.HRMS(APCI)m/z:[M+H] + calcd for C 38 H 35 O 6 ,587.2434；found,587.2428.
Example 2
S-3 was used instead of R-3 in example 1, with the other conditions and steps being the same.
Compound S-2 was obtained as a yellow solid (4.10 g, yield 70%).
1 H NMR(400MHz,Chloroform-d)δ8.09–7.97(m,4H),7.46(dd,J＝17.1,8.9Hz,4H),7.36(d,J＝8.2Hz,2H),7.19(d,J＝8.8Hz,2H),6.61(d,J＝7.5Hz,4H),3.88(s,6H),3.86–3.73(m,12H). 13 C NMR(101MHz,CDCl 3 )δ160.2,157.6,155.0,133.6,132.9,131.5,129.5,129.3,128.6,127.8,124.9,123.7,119.6,114.3,104.7,99.0,57.0,55.56,55.5.HRMS(APCI)m/z:[M+H] + calcd for C 38 H 35 O 6 ,587.2434；found,587.2431.
Example 3
To a mixture of R-2 (1.17 g,2.0 mmol) and paraformaldehyde (180 mg,6.0 mmol) in dichloromethane (150 mL) was added boron trifluoride diethyl ether (0.3 mL,2.4 mmol). Stirring at room temperature for 0.5h, and adding 150ml of water to quench the reaction. The organic layer was separated using anhydrous MgSO 4 And (5) drying. The solvent was removed in vacuo and the residue was separated by silica gel column chromatography (eluent: 2:1 DCM/petroleum ether) to give RR-1 as a yellow solid product (538 mg, 45%).
1 H NMR(400MHz,Chloroform-d)δ7.90(d,J＝9.0Hz,4H),7.84(s,4H),7.39(d,J＝9.0Hz,4H),7.26(s,4H),7.01–6.93(m,8H),6.60(s,4H),3.97(s,4H),3.93(s,12H),3.81(s,12H),3.76(s,12H). 13 C NMR(101MHz,CDCl 3 )δ157.6,155.8,154.8,133.7,132.7,132.1,129.3,129.2,128.7,127.5,124.6,122.7,121.4,119.6,114.1,96.0,57.0,56.0,55.9,27.8.HRMS(APCI)m/z:[M+H] + calcd for C 78 H 69 O 12 ,1197.4789；found,1197.4785.
Example 4
S-2 was used instead of R-2 in example 1, with the other conditions and steps being the same.
Compound SS-1 was obtained as a yellow solid (491 mg, yield 41%).
1 H NMR(400MHz,Chloroform-d)δ7.90(d,J＝9.0Hz,4H),7.83(s,4H),7.39(d,J＝9.0Hz,4H),7.26(s,4H),7.01–6.93(m,8H),6.60(s,4H),3.97(s,4H),3.93(s,12H),3.81(s,12H),3.76(s,12H). 13 C NMR(101MHz,CDCl 3 )δ157.6,155.8,154.8,133.7,132.7,132.1,129.3,129.2,128.73,127.5,124.6,122.7,121.4,119.6,114.1,96.0,57.0,55.9,55.9,27.8.HRMS(APCI)m/z:[M+H] + calcd for C 78 H 69 O 12 ,1197.4789；found,1197.4785.
The structural formulas of SS-1 and SS-2 synthesized in example 3 and example 4 are as follows:
from FIG. 1 c) it can be seen that the CD spectra of RR-1 and SS-1 show mirror images, which provides strong evidence that the enantiomerically pure macrocycles are provided.
The structure of RR-1 and SS-1 was known from Gaussian 09, and 6-311G was chosen as the basis, as shown in FIGS. 1 a and b, with both RR-1 and SS-1 having box-like structures with cavity sizes of approximately 10.100X 9.000 and 9.000X 9.000, respectively.
As shown in FIG. 2 a, after 5.0 equivalents of tetrabutylammonium salt (TBAX, X=AcO) was added to the mixture using a commercially available tetrabutylammonium salt (TBAX) as an anion source - 、NO 3- 、ClO 4 - 、HSO 4 - 、Br - 、I - 、PF 6 - 、H 2 PO 4 - 、BF 4 - 、CO 3 F 3 S - ) RR-1 was added to chloroform and the solution containing RR-1 and TBAI changed color from colorless to pale orange while the other solutions remained colorless. This apparent color change indicates that interactions between RR-1 and TBAI may have occurred. Ultraviolet-visible spectrum experiments further revealed the interaction behavior of RR-1 with TBAX. After addition of 5.0 equivalents of TBAI, the absorption was significantly enhanced at 300nm and 350nm, and a new absorption band appeared at 375nm, indicating the formation of RR-1/iodide complex in solution. On the other hand, no change in absorption spectrum was observed after the addition of the other TBAX. All of the upper partsThe results indicate that RR-1 has the ability to selectively recognize iodide anions over other test anions. Similar to RR-1, SS-1 also showed selective recognition of iodide anions over other tested anions, as shown by b in FIG. 2.
RR-1 and TBAI in a molar ratio of 1:1 were mixed in CDCl 3 After that, in 1 A new set of proton signals different from RR-1 and TBAI were observed on the H NMR spectrum, indicating the formation of a new complex RR-1/iodide, as shown in FIG. 3. Protons b and e corresponding to RR-1 were shifted up by 0.006 and 0.004ppm, respectively, which may be attributed to the formation of neutral C-H … anionic interactions between RR-1 and TBAI. Only protons b and e corresponding to RR-1 are displaced, probably the recognition of iodide by RR-1 occurs outside the cavity. In addition, with ring [4]]The recognition of iodide by carbazole (which is a slow process occurring inside the cavity) is different, and the recombination and de-recombination between RR-1 and TBAI is a fast exchange process on the NMR time scale at room temperature. This difference may be due to the recognition of iodide by RR-1 through neutral C-H … anion interactions outside the cavity. To further understand the complexation process between RR-1 and TBAI, then proceed with 1 H NMR spectroscopic titration experiments. By monitoring the change in proton b corresponding to RR-1 after TBAI addition, a 1:1 complex was formed between RR-1 and TBAI by molar ratio mapping. Binding constant Ka for complex RR-1/iodide was 132.8.+ -. 33.8M as measured using BindFit software -1 . SS-1 and TBAI also formed a 1:1 complex of SS-1/iodide by the same method, and the binding constant was calculated as ka=
119.1±32.6M -1 。
The energy minimization optimization of RR-1/iodide and SS-1/iodide further supports the formation of neutral C-H … anion interactions. As shown in FIG. 4 a, the iodide anion is located outside the cavity of RR-1 by C-H … anion interactions, at distances 3.307 and 3.123, respectively. Only protons b and e corresponding to RR-1 are involved in hydrogen bond formation with the iodide anion, which is consistent with the shift of protons b and e in nmr hydrogen spectroscopy experiments. In the structure of complex SS-1/iodide, the iodide anion is also located outside the cavity of SS-1 by C-H … anion interaction, at distances 3.307 and 3.123, respectively, as shown in FIG. 4 b.
In conclusion, the invention successfully designs and synthesizes the chiral binaphthyl enantiomerically pure macrocyclic aromatic RR-1 and SS-1. RR-1 and SS-1 were tested for their ability to act as anion receptors by means of ultraviolet-visible spectrum and nuclear magnetic resonance hydrogen spectrum. RR-1 and SS-1 were found to be able to selectively bind iodide anions in a 1:1 manner. Of the 10 anions tested, neutral C-H. Anionic interactions play an important role in the formation of RR-1/iodine and SS-1/iodine anion complexes. The complexation of iodide with RR-1 or SS-1 was observed visually and the color of the solution changed from colorless to pale orange.

Claims (7)

1. A chiral binaphthyl-mapped macrocyclic aromatic hydrocarbon, characterized in that: comprising RR-1 and/or SS-1 compounds;
2. the method for synthesizing chiral binaphthyl-mapped macrocyclic arene according to claim 1, wherein the method comprises the following steps: 2, 4-dimethoxy phenylboronic acid and an R-3 or S-3 compound are subjected to suzuki coupling reaction to obtain an R-2 or S-2 compound; r-2 or S-2 and paraformaldehyde are subjected to condensation reaction to obtain RR-1 or SS-1 structural compounds;
the structural formula of the R-3 compound is as follows:
the structural formula of the S-3 compound is as follows:
the structural formula of the R-2 compound is as follows:
the structural formula of the S-2 compound is as follows:
3. the method for synthesizing chiral binaphthyl-mapped macrocyclic arene according to claim 2, wherein the method comprises the following steps: in sodium carbonate ethanol solution system, 2, 4-dimethoxy phenylboronic acid and R-3 or S-3 compound are mixed in Pd (PPh) 3 ) 4 And reacting for 12-36 hours at the temperature of 85-95 ℃ under the catalysis of CuI.
4. A method for synthesizing chiral binaphthyl-mapped macrocyclic aromatic hydrocarbon according to claim 3, characterized in that: the molar ratio of the sodium carbonate to the R-3 or S-3 compound is 1 (2-3);
the molar ratio of the 2, 4-dimethoxy phenylboronic acid to the R-3 or S-3 compound is 1 (2-2.5).
5. The method for synthesizing chiral binaphthyl-mapped macrocyclic arene according to claim 2, wherein the method comprises the following steps: in a dichloromethane solution system, the R-2 or S-2 compound and paraformaldehyde react for 0.4 to 0.6 hour at room temperature under the catalysis of boron trifluoride diethyl ether.
6. The method for synthesizing chiral binaphthyl-mapped macrocyclic arene according to claim 5, wherein the method comprises the following steps: the molar ratio of the R-2 or S-2 compound to the paraformaldehyde is 1 (2-4).
7. Use of a chiral binaphthyl-mapped macrocyclic arene according to claim 1, characterized in that: the method is used as a molecular probe for detecting iodine anions in a solution system.
CN202310448560.2A 2023-04-24 2023-04-24 Chiral binaphthyl enantiomer macrocyclic arene, and synthetic method and application thereof Pending CN116693373A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115322201A (en) * 2022-07-15 2022-11-11 湖南科技学院 Macrocyclic column aromatic compound and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115322201A (en) * 2022-07-15 2022-11-11 湖南科技学院 Macrocyclic column aromatic compound and preparation method and application thereof
CN115322201B (en) * 2022-07-15 2024-01-26 湖南科技学院 Macrocyclic column aromatic compound, and preparation method and application thereof

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