CN115403522A - Biphenyl quinoline skeleton compound with C2 axis chirality, chiral isomer thereof, preparation method and application thereof - Google Patents
Biphenyl quinoline skeleton compound with C2 axis chirality, chiral isomer thereof, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic synthesis, and discloses a C2-axis chiral biphenyl quinoline skeleton compound and a chiral isomer thereof, wherein the compound comprises a 10, 10 '-biphenyl quinoline skeleton compound and a chiral isomer thereof, and 6,6',7,7',8,8',9,9 '-octahydro-10, 10' -biphenyl quinoline skeleton compound and a chiral isomer thereof, and the compound has good application prospects in the fields of catalysis, photoelectric materials, medicines, pesticides, dyes and the like; the invention also provides a preparation method of the compound and application of the compound.
Description
Technical Field
The invention relates to the fields of catalysis, photoelectric materials, medicines, pesticides, dyes and the like, in particular to a biphenyl quinoline skeleton compound with C2 axis chirality and a chiral isomer thereof, and a preparation method and application thereof.
Background
The pyridine and quinoline compound as a nitrogen-containing heterocyclic compound widely exists in nature, has various biological activities, and is good in stability and easy to prepare. Such materials typically have the following applications: (1) Pyridine and quinoline compounds are intermediates for synthesizing many drugs such as antimalarial drugs, antipyretic analgesics, local anesthetics, antibacterial drugs, etc.; (2) Due to the characteristics of low toxicity, high efficiency, environmental friendliness, various structural changes and the like, quinoline and derivatives thereof are widely applied to pesticide research, particularly as herbicides or insecticides; (3) Quinoline compounds with a substituent at the 2-position or the 4-position can also be used as dyes, for example, the simplest aniline is 2- (4' -amino-phenyl) -4-methylquinoline, and the photosensitive area is different along with the difference of the size and the structure of a conjugated system, so that the quinoline compounds with different substituents can be used for preparing dyes with different colors; (4) The pyridine and quinoline compounds have good coordination effect, can form a metal complex with various metal ions, and the metal complex has a large conjugated system, plays an important role in trace metal detection and biological analysis, and can be used as a metal ligand to catalyze various organic reactions; (4) The complex formed by the quinoline compound and the metal can also be used for research on electroluminescent devices, the complex has good electron transmission characteristics and is an ideal material in organic electroluminescence, because the quinoline ring is an electron-deficient aromatic ring and has good electron transmission performance, and the pi electron cloud density of the quinoline ring is adjusted by changing the size of a conjugated system of the quinoline derivative, so that the emission wavelength of the complex formed by the quinoline compound and the metal is adjusted, and light with different colors is emitted.
Correspondingly, naphthalene, anthracene, binaphthyl and dianthracene are typical chromophoric groups and have important application in organic photoelectric materials, and the binaphthyl and dianthracene compounds with the C2-axis chiral structure can participate in synthesis of various photoelectric materials and can be widely applied to various fields such as luminescent molecular devices, fluorescent probes and the like. For example, korean patent (KR 1020140096227 a) which has been published on a binaphthyl compound containing a diarylamine (represented by formula 1) was used to investigate its light emitting effect in an OLED, probably because the compound has high stereoselectivity due to the large included angle between naphthyl groups, effectively preventing the close packing of molecules, thereby improving light emitting efficiency in an emission layer doped in the OLED; binaphthyl compounds (shown as formula 2) with a C2 axis, such as binaphthol and binaphthylamine, also have a large pi conjugated system and a controllable dihedral angle between naphthalene rings, so that the binaphthyl compounds have high luminous efficiency and can be used as photoelectric functional materials, and as phenolic hydroxyl groups and amino groups on the naphthalene rings can perform various reactions, various functional groups are usually derived at the position to realize structural regulation and modification, so that different functional effects are exerted; in 1980, a binaphthyl structure compound 2,2 '-bis (diphenylphosphine) -1,1' -Binaphthyl (BINAP) (shown in a formula 3) is disclosed for the first time by Noyori J.Am.chem.Soc. [1980,102,7932-7934] of Japanese scientists, the structure containing a large conjugated naphthalene ring can be used for preparing a room-temperature phosphorescent material, the luminescent color of the material can be regulated and controlled by deriving the structure, and the material can be matched with various metals for various chiral catalytic reactions to show good enantioselectivity; in 2021, japanese scholars issued a dibenzocarbazole compound having axial chirality (as shown in formula 4) on org.lett. [2021,23,1349-1354], and had excellent Circular Polarization Luminescence (CPL) characteristics, which was of great importance in optical materials.
Similarly, bipyridine and biquinoline compounds with a C2 axis chiral structure and different positions are nitrogen-containing heterocyclic compounds with important functions, can form a metal complex of a conjugated system with various metal ions, and are widely applied to a plurality of fields of medicines, biological analysis, luminescent materials and the like.
The representative bipyridine compound phenanthroline (shown as formula 5) has a bidentate ligand and a tricyclic rigid conjugated plane structure, has very rich electron cloud density on a nitrogen atom, can be well coordinated with metal ions, can even be coordinated with rare earth ions to generate a very strong fluorescence effect, and is often used for preparing a fluorescent probe and synthesizing other fluorescent materials.
The biquinoline compound also has good photoelectric characteristics, and a scientist (J.org.chem. [1952,17,471-472 ]) synthesizes a 1,1' -biquinoline (shown as a formula 6) compound as early as 1952, but the chiral isomer of the structure is generally unstable and extremely easy to racemize, so that no chiral compound with a similar structure is reported at present; this structure was later oxidized (j.heterocyclic. Chem. [1992,29,931-933 ]) to exist as a more stable oxy-nitrogen compound structure (as shown in formula 7); several 4,4' were also reported by japanese scientists in j.sci.induster.res. [1959,18b,496 ]; 5,5';6,6' -biquinoline metal complex, the study of its photochromic property, and the synthesis of high-quality dye as intermediate; a diphenyl-substituted 6,6' -biquinoline compound (shown as a formula 8) capable of emitting blue light is developed at the university of Washington in 2004 (appl.Phys.Lett. [2005,86,061-106 ]), and the electron transport material provides a wide application prospect for developing more efficient OLEDs.
In addition, the bipyridine and the biquinoline compounds can also be used as (chiral) metal ligands to form chiral catalysts to participate in asymmetric reactions catalyzed by various (chiral) metal catalysts. In 1998, the Nakajima group in J.Am.chem.Soc. [1998,120,6419-6420] published chiral 2,2' -biquinoline nitroxide ligand (shown in formula 9), which was successfully applied to the reaction of aldehyde and allyl chlorosilane to obtain the allylated product of aldehyde with high ee value; four years later, denmark et al, J.Am.chem.Soc. [2002,124,4233-4235] published 2,2' -bipyridine ligand (shown in formula 10) with ortho-position containing large steric hindrance substituent, activated the olefin by coordinating with silicon atom in substrate silicon enol ether to generate Aldol reaction; zhou Yonggui of the institute of Onagawa, zhongkojic, in 2015, discloses a bipyridine ligand (shown in formula 11) on Angew. Chem. Int. Ed. [2015,54,11956-11960], and is successfully applied to asymmetric catalytic reaction in which diazo compounds participate; chiral 6,6 '-dihydroxy-5,5' -biquinoline with C2 axis chirality (shown as formula 12) was reported by Guangzhou university in S.C. Chan. Chirality [2000.12,510-513] in 2000, and was successfully applied to catalytic reactions such as asymmetric epoxidation and asymmetric alkylation.
In conclusion, a great deal of research on the synthesis and application of bipyridyl and biquinoline in the prior art has been carried out, which proves that the bipyridyl and biquinoline have great application in the aspects of electronic light-emitting devices, dyes and participating in asymmetric catalysis as metal ligands or organic small molecules, however, the biphenyl and quinoline skeleton compound with C2 axis chirality, the chiral isomer structural analogue thereof and the synthesis and application of the stable chiral isomer thereof, which have larger conjugated structure, different coordination points and coordination capacity and stable structure, are not reported.
Disclosure of Invention
The first purpose of the invention is to provide a novel structure C 2 Axial chiral 10, 10 '-biphenylquinolines DL- (I), 6,6',7,7',8,8',9,9 '-octahydro-10, 10' biphenylquinolines DL- (II) and their corresponding optical chiral isomers.
The second object of the present invention is to provide the above-mentioned composition having C 2 The preparation method of the axial chiral 10, 10 '-biphenyl quinoline DL- (I), 6,6',7,7',8,8',9,9 '-octahydro-10, 10' biphenyl quinoline DL- (II) and the corresponding optical chiral isomers thereof has the characteristics of short synthetic route, simplicity and convenience in operation, easiness in obtaining raw materials and the like, and the quinoline skeleton compound can be simply and efficiently prepared by the method.
Third object of the inventionIs to provide the above-mentioned compound having C 2 Use of axially chiral 10, 10 '-biphenylquinolines DL- (I), 6,6',7,7',8,8',9,9 '-octahydro-10, 10' biphenylquinolines DL- (II) and their corresponding optical chiral isomers.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention firstly provides a biphenyl quinoline skeleton compound with C2 axis chirality and a chiral isomer thereof, which are shown as a formula (I) or a formula (II):
formula (I) includes the racemate shown in formula DL- (I) and all possible chiral isomers shown in formulas (R) - (I) and (S) - (I);
the formula (II) comprises a racemate shown as a formula DL- (II) and all possible chiral isomers shown as formulas (R) - (II) and formulas (S) - (II);
wherein, the chiral isomers shown in the formulas (R) - (I) and (S) - (I) and the chiral isomers shown in the formulas (R) - (II) and (S) - (II) comprise chiral centers shown in the formulas (R) - (I) and (S) - (I), chiral centers introduced by substituent groups, all possible axial chiral centers formed by special rigid (steric) groups and the like.
In formula (I) and formula (II):
R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 each independently selected from:
a hydrogen atom;
C 1 ～C 30 alkyl of (C) 1 ～C 30 Silyl group of C 1 ～C 30 Haloalkyl, C 2 ～C 30 Alkenyl of, C 2 ～C 30 An alkynyl group;
halogen, hydroxyl, alkoxy, acyloxy, mercapto, thioether, nitro, carbonyl, carboxyl, ester, substituted or unsubstituted amino, imino, cyano, phosphonate, phosphine, amide, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl;
substituted or unsubstituted C 6 ～C 50 Aryl of (a); substituted or unsubstituted C 6 ～C 50 And aryl of (1); substituted or unsubstituted C 6 ～C 50 A fused aryl group of (a);
substituted or unsubstituted C 7 ～C 50 Aralkyl group of (1); substituted or unsubstituted C 7 ～C 50 An aralkyloxy group of (a); substituted or unsubstituted C 7 ～C 50 An aralkylthio group of (a);
aromatic heterocyclic group, heterocyclic group or condensed heterocyclic group. Thiophene, benzothiophene, arylthiophene, carbazole, benzocarbazole, arylcarbazole, pyridine, benzopyridine (quinoline), isoquinoline, benzoquinoline, arylquinoline, arylisoquinoline, fluorene, furan, benzofuran, arylfuran, pyrrole, indole, arylpyrrole, and the like are preferred.
Compared with the traditional (bi) quinoline compounds, the biphenyl quinoline skeleton compounds shown in the formulas (I) and (II) have two benzene (parallel) rings or (parallel) cyclohexane-shaped rigid skeletons, and the electronic conjugation effect of the compounds and the regulation and control capability of compound included angles, spatial configurations, conformations and the like are improved. The compound has more excellent optical and photoelectric properties and coordination capability than the traditional (bi) quinoline compound. Specifically, the method comprises the following steps:
the compound shown in the formula (I) has the following excellent properties:
(1) As a photoelectric material with excellent performance: the compound (I) increases a benzene ring structure in a condensed mode on the basis of a quinoline structure unit to form a large conjugated structure similar to anthracene, and the large conjugated structure has a lower HOMO energy level, so that the energy range is reduced, the electron injection is easier, the energy required by the electron transition is smaller, the absorption wavelength is correspondingly lengthened, and the compound (I) can be used for preparing corresponding photoelectric materials; the anthracene derivative is a basic material which can be applied to an organic light-emitting component, has the advantages of high fluorescence quantum efficiency, good stability and the like, and is a scarce n-type blue light material;
(2) As a metal coordination material with excellent performance: the structure of the compound (I) similar to anthracene further enhances the conjugation effect of the compound, so that electrons on nitrogen atoms are dispersed to the whole conjugation system, the basicity of the compound is weakened, the compound has stronger p-pi conjugation effect, and the compound is more easily coordinated with metal ions; meanwhile, the size of the dihedral angle of the whole compound can be regulated and controlled by controlling various substituents on a benzene ring, so that the coordination capacity and the regulation and control capacities of a chiral environment, a spatial configuration, a conformation and the like are improved.
The compound shown in the formula (II) has the following excellent properties:
(1) As a photoelectric material with excellent performance: the existence of cyclohexane increases the solubility of the compound in an organic solvent, and is more beneficial to processing and molding in the application of photoelectric materials.
(2) As a metal coordination material with excellent performance: cyclohexane is not a planar structure and can exist in a closed-loop chair-type or ship-type conformation, so that dihedral angle regulation factors of the whole compound are increased, and a plurality of cyclohexane structures have latent chiral centers, so that the configuration of the compound and the regulation factors of chiral environment are richer, and the compound has more reaction sites than common bipyridine and biquinoline, and can be used as a (chiral) organic synthon to synthesize a new (chiral) catalyst and material.
Preferably, in the biphenyl quinoline skeleton compound having C2 axis chirality and the chiral isomers thereof of the present invention:
c substituted as described above 6 ～C 50 Aryl of (a); substituted C 6 ～C 50 And aryl of (1); substituted C 6 ～C 50 A fused aryl group of (a); substituted C 7 ～C 50 Aralkyl group of (1); substituted C 7 ～C 50 An aralkyloxy group of (a); substituted C 7 ～C 50 In the aralkyl mercapto group, the substituent is selected from thiophene, benzothiophene and aryl benzothiophene; carbazole, benzocarbazole, arylcarbazole; pyridine, benzopyridine, isoquinoline, benzoquinoline, aroquinoline, aroisoquinoline; fluorene; furan, benzofuran, arylbenzofuran; pyrrole, indole, arylpyrrole; pyrazole, benzopyrazole, arylpyrazole;oxazole, benzoxazole, arooxazole; isoxazoles, benzisoxazoles, arylisoxazoles; thiazoles, benzothiazoles, arylthiazoles; isothiazole, benzisothiazole, aroisothiazole; imidazole, benzimidazole, arylimidazole; pyrans, benzopyrans, arylpyrans; pyridazine, benzopyridazine, arylpyridazine; pyrimidines, benzopyrimidines, arylpyrimidines; pyrazine, benzopyrazines, arylpyrazines; phenazine, benzophenazine, arylphenazine; thiazines, benzothiazines, arylthiazines; pteridines, benzopteridines, arylpteridines; acridine, benzacridine, aroacridine; phenothiazine, benzophenothiazine, or arylphenothiazine;
the above-mentioned substituted amino group means that two H's of the amino group are substituted with an arbitrary alkyl group or aryl group.
Further preferably, the biphenyl quinoline skeleton compound with C2 axis chirality and the chiral isomer thereof of the invention are shown as formula (I) -A or formula (II) -A:
the formula (I) -A comprises a racemate shown as formula DL- (I) -A and all possible chiral isomers shown as formulas (R) - (I) -A and (S) - (I) -A;
the formula (II) -A comprises a racemate shown as a formula DL- (II) -A and all possible chiral isomers shown as formulas (R) - (II) -A and (S) - (II) -A;
further, in addition to the above (I) -A, the group R5 is further defined, and the compound represented by the formula (I) -B or the formula (I) -C is preferred:
the formula (I) -B comprises a racemate shown as the formula DL- (I) -B and all possible chiral isomers shown as the formula (R) - (I) -B and the formula (S) - (I) -B;
the formula (I) -C comprises a racemate shown as a formula DL- (I) -C and all possible chiral isomers shown as formulas (R) - (I) -C and (S) - (I) -C;
in the formula (I) -C, R 5 ' with R 1 ～R 8 As such, selected from any of the following:
a hydrogen atom;
C 1 ～C 30 alkyl of (C) 1 ～C 30 Silane group of (C) 1 ～C 30 Haloalkyl, C 2 ～C 30 Alkenyl of, C 2 ～C 30 Alkynyl;
halogen, hydroxyl, alkoxy, acyloxy, mercapto, thioether, nitro, carbonyl, carboxyl, ester, substituted or unsubstituted amino, imino, cyano, phosphonate, phosphine, amide, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl;
substituted or unsubstituted C 6 ～C 50 Aryl of (a); substituted or unsubstituted C 6 ～C 50 And aryl of (1); substituted or unsubstituted C 6 ～C 50 The fused aryl group of (1);
substituted or unsubstituted C 7 ～C 50 Aralkyl group of (1); substituted or unsubstituted C 7 ～C 50 An aralkyloxy group of (a); substituted or unsubstituted C 7 ～C 50 An aralkylthio group of (a);
an aromatic heterocyclic group, a heterocyclic group or a fused heterocyclic group.
Still more preferably, the biphenyl quinoline skeleton compound having C2-axis chirality and the chiral isomers thereof according to the present invention are characterized in that the racemate represented by DL- (i) and the racemate represented by DL- (ii) are selected from the compounds represented by any one of the following structural formulas, and correspondingly, all possible chiral isomers corresponding to the compounds represented by any one of the following structural formulas are also preferred chiral compounds according to the present invention:
the invention further provides a preparation method of the biphenyl quinoline skeleton compound with C2 axis chirality and the chiral isomer thereof, which comprises the following steps:
in the above formula:
when the formula (4) is selected from racemes, the formula (I) is DL- (I), and the formula (II) is DL- (II);
when the formula (4) is selected from chiral R compounds, the formula (I) is (R) - (I), the formula (II) is (R) - (II), and all possible chiral isomers with different configurations caused by configuration and conformation change;
when formula (4) is selected from chiral S compounds, formula (I) is (S) - (I), formula (II) is (S) - (II), and all possible chiral isomers with different configurations caused by configuration and conformation changes.
Specifically, when 10, 10' -biphenylquinoline (I) is prepared, reactant (4) is selected from [1,1' -binaphthyl ] -2,2' -diamine; when preparing 6,6',7,7',8,8',9,9' -octahydro-10, 10' biphenylquinoline (II), reactant (4) is selected to be 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl ] -2,2' -diamine.
When the reactant (4) is racemate, the corresponding products (I) and (II) are racemate; when the reactant (4) is a chiral body, the corresponding products (I) and (II) are chiral bodies; in practice, the chiral configuration and the optical purity of the reactant (4) can be controlled to obtain the target product with corresponding chiral configuration and optical purity.
In the above preparation method, the catalyst is selected from protonic acid or Lewis acid; the protonic acid comprises hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, perchloric acid, aqueous hydrochloric acid solution, aqueous sulfuric acid solution, aqueous phosphoric acid solution, aqueous nitric acid solution, aqueous p-toluenesulfonic acid solution or aqueous perchloric acid solution; the Lewis acid comprises stannic chloride, scandium trichloromethane sulfonate, ferric chloride or zinc chloride.
The hydrochloric acid aqueous solution, the sulfuric acid aqueous solution, the phosphoric acid aqueous solution, the nitric acid aqueous solution, the p-toluenesulfonic acid aqueous solution, or the perchloric acid aqueous solution may be an aqueous solution having any concentration.
More preferably, the catalyst is selected from aqueous hydrochloric acid or sulfuric acid, and the concentration of the aqueous hydrochloric acid or sulfuric acid is preferably > 5%.
The amount of the catalyst used in the present invention is preferably 1 to 3 equivalents, preferably 2 equivalents, to the raw material (4). When the amount is less than 1 equivalent, the reaction speed is too slow, and when the amount is more than 1 equivalent, the reaction speed is too fast.
In the preparation method, the solvent is selected from one or more of aromatic hydrocarbon, halogenated alkyl, ether or ester and is mixed in any proportion. Preferably at least one of toluene, chlorobenzene, 1,4-dioxane, butyl acetate, and methylene chloride.
The dosage of the solvent is preferably 2 to 10 times of the weight of the substrate, the reaction effect is poor when the dosage is less than 2 times, the yield is low, and when the dosage is more than 10 times, the concentration is too dilute, the reaction speed is slow and resources are wasted.
The invention also provides application of the biphenyl quinoline skeleton compound with C2 axis chirality and the chiral isomer thereof, which is used for any one of the following applications:
(1) Due to the existence of C2 axis chirality and the wide coordination capability of quinoline, the chiral quinoline can be used as a metal ligand or a chiral metal ligand to form asymmetric reactions catalyzed by chiral catalysts participating in various metal catalysts or chiral metal catalysts;
(2) Due to the existence of a pyridine ring in quinoline, the quinoline can be used as chiral Lewis base and an organic small molecular catalyst to catalyze organic reaction or asymmetric organic reaction;
(3) Due to the reactivity of the pyridine structure, the pyridine can react at different sites, so that the pyridine can be used as an organic synthon or a chiral organic synthon to synthesize a new catalyst or a chiral catalyst;
(4) Pyridine phase transfer catalysts or chiral pyridine chiral phase transfer catalysts are synthesized by pyridine derivation;
(5) Based on a biquinoline unit and a C2 symmetrical super-conjugated structure, the compound has the capability of electron transfer and transmission and can be used as a photoelectric material;
(6) The fluorescent probe has a tricyclic rigid conjugated planar structure and a bidentate ligand structure similar to those of phenanthroline, so that the electron cloud density on a nitrogen atom is increased, and the fluorescent probe has a strong fluorescent effect and can be used for preparing fluorescent probes and synthesizing other fluorescent materials;
(7) Two nitrogen atoms on a coplanar surface are coordinated with metal ions, so that the central ions of the metal are in a stable state and can be used for trace metal detection;
(8) For use as novel dyes;
(9) Useful as pharmaceuticals, pesticides and intermediates thereof;
(10) Is used for fine chemical materials.
The invention has the beneficial effects that:
1. the biphenyl quinoline skeleton compounds shown in the formulas (I) and (II) have good optical and electrical properties, and can be used for preparing photoelectric materials; the compound has all C of bipyridine and biquinoline 2 The axis chiral structure is also a super-conjugated structure like binaphthyl, so that the electron cloud density of the whole compound is high, the compound has better light-emitting property and electron transmission property, and the whole molecular system shows an electric absorption property due to the existence of a pyridine ring and can be used as an unusual n-type semiconductor material;
2. the biphenyl quinoline skeleton compound shown in the formulas (I) and (II) has good coordination capacity, can form a complex with various metal ions, and is a good metal ligand and a good catalyst: the compound can regulate and control the included angle of the whole compound structure by regulating a substituent group, and has excellent coordination capacity due to the two pyridine ring structures, so that the compound can be complexed with various metals to form various (chiral) metal catalysts for catalyzing asymmetric reactions, and can also be independently used as chiral Lewis base and organic micromolecule catalysts for catalyzing various asymmetric reactions; in addition, the structure has more reaction sites than common bipyridyl and biquinoline, and can be used as a (chiral) organic synthon to synthesize new (chiral) catalysts and materials.
3. The preparation method is directly synthesized by one step from (chiral R or S or racemate) [1,1 '-binaphthyl ] -2,2' -diamine or (chiral R or S or racemate) 5,5',6,6',7,7',8,8' -octahydro- [1,1 '-binaphthyl ] -2,2' -diamine and alpha, beta unsaturated aldehyde or ketone in proper acidic conditions and solvents, and has the characteristics of short synthetic route, simple and convenient operation, easily obtained raw materials and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention is further described with reference to specific embodiments below.
Example 1
This example provides a 10, 10' -biphenylquinoline derivative (Ia) having C2-axis chirality and a method for preparing the same.
The synthetic route is as follows:
the preparation process comprises the following steps:
0.5g (1.76 mmol) of [1,1' -binaphthyl]-2,2' -diamine (BINAM) was placed in a 50ml single neck bottle with 20ml of 55% sulfuric acid and heated. Then, a solution containing 0.37g (4.40 mmol) of trans-3-penten-2-one (3a 1 ，R 3 ＝CH 3 ) 10ml of toluene solution, the color of the system is changed into brownish red, after the dripping is finished, the system is continuously heated to the reflux temperature and stirred. After 8h, TLC is used for detecting the raw material [1,1' -binaphthyl]The reaction was completed with-2,2' -diamine. Separating liquid, taking the lower layer of water phase, adding sodium hydroxide solution to adjust alkalinity, extracting the product by dichloromethane, removing dichloromethane by rotary evaporation to obtain a crude product, and separating and purifying by column chromatography to obtain the product (Ia).
The characterization data for (Ia) are: mp is 267-268 ℃; 1 H NMR(400MHz,CDCl 3 )δ8.66(s,2H),8.11(d,J＝8.5Hz,2H),7.46–7.35(m,2H),7.15–7.03(m,4H),7.01(d,J＝1.2Hz,2H),2.84(d,J＝1.1Hz,6H),2.24(s,6H)； 13 C NMR(101MHz,CDCl 3 )δ158.7,144.1,143.3,135.5,133.8,130.9,128.7,127.7,125.7,125.4,125.0,122.8,122.1,26.0,19.2；ESI-MS:calculated[C 30 H 24 N 2 + Na] + :435.1837,found:435.1838.
example 2
The raw material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 1 was changed to its R-type chiral isomer (R-BINAM) under the same conditions. The chiral product (R) - (Ia) was obtained in equivalent yield.
Optical rotation data of (R) - (Ia): [ alpha ] to] 20 D＝85.1(c＝1.00,CH 2 Cl 2 )。
Example 3
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 1 was changed to its S-type chiral isomer (S-BINAM) under the same conditions. The chiral products (S) - (Ia) were obtained in equal yields.
Examples 4 to 7
The solvent toluene in example 1 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, and dichloromethane, respectively, under the same conditions. The product (Ia) was obtained in comparable yields.
Examples 8 to 13
The sulfuric acid in example 1 was replaced with hydrochloric acid, perchloric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (Ia) was obtained in comparable yields.
Example 14
This example provides a 10, 10' -biphenylquinoline derivative (ib) having C2-axis chirality and a method for preparing the same.
The synthetic route is shown in reference to example 1;
the preparation process comprises the following steps: the compound of (3a 1 ，R 3 ＝CH 3 ) The procedure was changed to (3 b: r is 1 ，R 3 = Ph), i.e. 0.5g (1.76 mmol) [1,1' -binaphthyl]Reaction of-2,2' -diamine (BINAM) with 0.92g (4.40 mmol) chalcone, otherwise unchanged, gives (Ib).
The characterization data for (Ib) are: mp is 195-196 ℃; 1 H NMR(400MHz,CDCl 3 )δ8.67(s,2H),8.07(d,J＝8.3Hz,2H),7.83–7.74(m,6H),7.66(dd,J＝16.6,9.3Hz,6H),7.46(t,J＝8.3Hz,8H),7.24–7.07(m,8H)； 13 C NMR(101MHz,CDCl 3 )δ155.6,149.2,139.7,139.4,134.3,131.8,130.0,129.1,129.0,128.8,128.5,128.4,128.2,127.4,126.0,125.5,125.4,124.6,118.2；ESI-MS:calculated[C 50 H 32 N 2 + H] + :661.2644,found:661.265.
example 15
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 14 was changed to its R-type chiral isomer (R-BINAM) under the same conditions. The chiral products (R) - (Ib) are obtained in equivalent yields.
Optical rotation data of (R) to (Ib): [ alpha ] of] 20 D ＝-107.4(c＝1.00,CH 2 Cl 2 )。
Example 16
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 14 was changed to its S-type chiral isomer (S-BINAM) under the same conditions. The chiral products (S) - (Ib) were obtained in equal yields.
Example 17 to example 20
The solvent toluene in example 14 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (Ib) is obtained in comparable yields.
Examples 21 to 26
The sulfuric acid in example 14 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (Ib) is obtained in comparable yields.
Example 27
This example provides a 10, 10' -biphenylquinoline derivative (ic) having chirality at the C2 axis and a method for preparing the same.
The synthetic route is shown in reference to example 1;
the preparation process comprises the following steps: the compound of (3a 1 ，R 3 ＝CH 3 ) The procedure was changed to (3 c: r 1 ，R 3 ＝o-C 4 H 3 S), i.e. 0.5g (1.76 mmol) [1,1' -binaphthyl]-2,2' -diamine (BINAM) with 0.97g (4.40 mmol) 1,3-di (thien-2-yl) -2-propen-1-oneReacting under the same conditions to obtain the (ic).
The characterization data for (ic) are: mp is 153-154 ℃; 1 H NMR(400MHz,CDCl 3 )δ8.08(d,J＝8.5Hz,2H),7.94(d,J＝8.7Hz,2H),7.92–7.85(m,2H),7.81(s,2H),7.67–7.58(m,6H),7.56(dd,J＝3.8,1.1Hz,2H),7.54–7.46(m,2H),7.43–7.32(m,4H),7.12–7.05(m,2H)； 13 C NMR(101MHz,CDCl 3 )δ151.9,146.2,143.7,142.6,141.8,139.4,135.1,133.8,132.9,132.1,129.7,129.3,129.0,128.8,128.3,128.1,127.9,127.9,127.3,127.3,126.9,126.1,126.1,125.2,124.6,122.0,118.6,118.0,116.7；ESI-MS:calculated[C 42 H 24 N 2 S 4 +H] + :685.0901,found:685.0917.
example 28
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 27 was changed to its R-type chiral isomer (R-BINAM) under the same conditions. The chiral products (R) - (IC) were obtained in equal yields.
Optical rotation data of (R) to (ic): [ alpha ] to] 20 D ＝22(c＝1.00,CH 2 Cl 2 )。
Example 29
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 27 was changed to its S-type chiral isomer (S-BINAM) under the same conditions. The chiral products (S) - (IC) were obtained in equivalent yields.
Examples 30 to 33
The solvent toluene in example 27 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (ic) was obtained in equivalent yield.
Examples 34 to 39
The sulfuric acid in example 27 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (ic) was obtained in equivalent yield.
Example 40
This example provides a 10, 10' -biphenylquinoline derivative (id) having C2-axis chirality and a method for preparing the same.
The synthetic route is shown in reference to example 1;
the preparation process comprises the following steps: the compound of (3a 1 ，R 3 ＝CH 3 ) The procedure was changed to (3 d: r 1 ，R 3 ＝o-C 5 H 4 N), i.e. 0.5g (1.76 mmol) [1,1' -binaphthyl]Reaction of-2,2' -diamine (BINAM) with 0.92g (4.40 mmol) of 1,3-bis (pyridin-2-yl) -2-propen-1-one, otherwise unchanged, gives (Id).
The characterization data for (id) are: mp is 243-244 ℃; 1 H NMR(400MHz,CDCl 3 )δ8.99–8.92(m,2H),8.89(d,J＝6.6Hz,2H),8.68(d,J＝5.1Hz,2H),8.61–8.55(m,2H),8.07(d,J＝8.5Hz,2H),7.94(d,J＝8.7Hz,2H),7.91–7.87(m,6H),7.69–7.59(m,2H),7.59–7.45(m,6H),7.36(m,2H)； 13 C NMR(101MHz,CDCl 3 )δ157.9,156.2,155.9,149.8,148.7,147.2,143.8,142.4,137.2,136.9,135.2,133.7,133.4,132.8,129.5,129.0,128.2,127.9,127.1,126.9,126.3,126.2,126.1,125.3,125.2,124.8,124.1,123.3,122.2,122.0,118.9,118.5,116.7；ESI-MS:calculated[C 46 H 28 N 6 +H] + :665.2454,found:665.2391.
EXAMPLE 41
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 40 was changed to its R-type chiral isomer (R-BINAM) under the same conditions. The chiral products (R) - (Id) were obtained in equivalent yields.
Optical rotation data of (R) - (Id): [ alpha ] to] 20 D ＝-6.0(c＝1.00,CH 2 Cl 2 )。
Example 42
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 40 was changed to its S-type chiral isomer (S-BINAM) under the same conditions. The chiral products (S) - (Id) were obtained in equal yields.
Examples 43 to 46
The solvent toluene in example 40 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (id) was obtained in equivalent yield.
Example 47 to example 52
The sulfuric acid in example 40 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (id) was obtained in equivalent yield.
Example 53
This example provides a 10, 10' -biphenylquinoline derivative (ie) having C2-axis chirality and a method for preparing the same.
The synthetic route is shown in reference to example 1;
the preparation process comprises the following steps: the compound of (3a 1 ，R 3 ＝CH 3 ) The procedure was changed to (3 e: r 1 ，R 3 ＝p-C 5 H 4 N), i.e. 0.5g (1.76 mmol) [1,1' -binaphthyl]Reaction of-2,2' -diamine (BINAM) with 0.92g (4.40 mmol) of 1,3-bis (pyridin-4-yl) -2-propen-1-one, otherwise unchanged, gives (ie).
The characterization data for (ie) are: mp is 256-257 ℃; 1 H NMR(400MHz,CDCl 3 )δ9.01–8.89(m,4H),8.60–8.45(m,6H),8.05(d,J＝8.5Hz,2H),7.96(d,J＝8.7Hz,2H),7.89(d,J＝8.1Hz,2H),7.82(s,2H),7.58–7.51(m,2H),7.47–7.36(m,2H),7.28(d,J＝2.6Hz,2H),7.13–7.03(m,2H),6.75(d,J＝8.5Hz,2H)； 13 C NMR(101MHz,CDCl 3 )δ153.7,150.5,150.4,147.3,146.5,145.9,143.5,142.4,135.0,134.8,133.9,132.9,129.4,129.2,128.3,128.1,127.8,127.1,126.3,125.3,124.8,124.5,124.2,122.2,121.3,118.5,117.5,115.9；ESI-MS:calculated[C 46 H 28 N 6 ] + :664.2375,found:664.2567.
example 54
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 53 was changed to its R-type chiral isomer (R-BINAM) under the same conditions. The chiral products (R) - (ie) were obtained in equal yields.
Optical rotation data of (R) to (ie): [ alpha ] to] 20 D ＝35.4(c＝1.00,CH 2 Cl 2 )。
Example 55
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 53 was changed to its S-type chiral isomer (S-BINAM) under the same conditions. The chiral products (S) - (ie) were obtained in equal yields.
Examples 56 to 59
The solvent toluene in example 53 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (ie) was obtained in equivalent yield.
Examples 60 to 65
The sulfuric acid in example 53 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (ie) was obtained in equivalent yield.
Example 66
This example provides a 10, 10' -biphenylquinoline derivative (if) having chirality at C2 axis and a method for preparing the same.
The synthetic route is shown in reference to example 1;
the preparation process comprises the following steps: the compound of (3a 1 ，R 3 ＝CH 3 ) The procedure was changed to (3 f: r is 1 ，R 3 ＝OC 2 H 5 ) I.e., 0.5g (1.76 mmol) [1,1' -binaphthyl]Reaction of-2,2' -diamine (BINAM) with 0.63g (4.40 mmol) of 3-ethoxyacrylate, otherwise unchanged, gives (if).
The characterization data for (if) are: mp is 283-284 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.74(dd,J＝8.0,1.3Hz,2H),7.66–7.53(m,4H),7.36(dd,J＝8.0,7.2Hz,2H),7.11(d,J＝8.4Hz,2H),2.39(s,6H)； 13 C NMR(101MHz,CDCl 3 )δ209.1,184.4,178.1,171.2,169.4,167.5,165.2,164.9,162.7,162.5,162.2,66.4；ESI-MS:calculated[C 26 H 16 N 2 O 4 + H] + :421.1188,found:421.1156.
example 67
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 66 was changed to its R-type chiral isomer (R-BINAM) under the same conditions. The chiral products (R) - (if) were obtained in equal yields.
Example 68
The starting material [1,1 '-binaphthyl ] -2,2' -diamine (BINAM) in example 66 was changed to its S-type chiral isomer (S-BINAM) under the same conditions. The chiral products (S) - (if) were obtained in equal yields.
Examples 69 to 72
The solvent toluene in example 66 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (if) is obtained in comparable yields.
Examples 73 to 78
The sulfuric acid in example 66 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (if) was obtained in equivalent yield.
Example 79
The embodiment provides a 6,6',7,7',8,8',9,9' -octahydro-10, 10' -biphenylquinoline derivative (II g) with C2 axis chirality and a preparation method thereof.
The synthetic route is as follows:
the preparation process comprises the following steps:
0.5g (1.71 mmol) 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine was placed in a 50ml single neck flask with 20ml of 55% sulfuric acid and heated to 95 ℃. Then, an aqueous solution containing 0.38g (6.85 mmol) of acrolein (3g 1 ，R 3 10ml of toluene, the color of the system changed to red brown, and the heating and stirring were continued after the dropwise addition. After 8h, TLC is used for detecting the raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]The reaction was completed with-2,2' -diamine. Separating, taking the lower water phase, adding sodium hydroxide solution to adjust alkalinity, extracting the product with dichloromethane, removing dichloromethane by rotary evaporation to obtain a crude product, and separating and purifying by column chromatography to obtain a product (II g).
The characterization data of (IIg) are: mp is 298-299 ℃; 1 H NMR(400MHz,CDCl 3 )δ8.67(dd,J＝4.2,1.7Hz,1H),8.67(dd,J＝4.2,1.7Hz,1H),8.08(dd,J＝8.2,1.7Hz,1H),8.08(dd,J＝8.2,1.7Hz,1H),7.63(s,1H),7.63(s,1H),7.29–7.16(m,1H),7.23(dd,J＝8.2,4.2Hz,1H),3.10(dd,J＝9.9,5.9Hz,2H),3.10(dd,J＝9.9,5.9Hz,2H),2.29(dd,J＝13.4,6.8Hz,2H),2.29(dd,J＝13.4,6.8Hz,2H),1.84(dt,J＝10.7,4.7Hz,2H),2.09–1.21(m,4H),1.76–1.61(m,2H)； 13 C NMR(75MHz,CDCl 3 )δ149.3,145.6,138.2,136.8,136.7,135.3,126.7,126.4,119.9,30.5,28.0,23.6,22.5；ESI-MS:calculated[C 26 H 24 N 2 +H] + :365.2018,found:365.2034.
example 80
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 79 were mixed]-2,2' -diamine (H) 8 BINAM) to its R-type chiral isomer (R-H) 8 BINAM), other conditions are the same. The chiral products (R) - (IIg) were obtained in equal yields.
Optical rotation data of (R) to (IIg): [ alpha ] of] 20 D ＝86.50(c＝1.00,CH 2 Cl 2 )。
Example 81
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 79 were mixed]-2,2' -diamine (H) 8 BINAM) to its S-type chiral isomer (S-H) 8 BINAM), other conditions being the same. The chiral products (S) - (II g) were obtained in equal yields.
Example 82 to example 85
The solvent toluene in example 79 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (II g) was obtained in equivalent yield.
Examples 86 to 91
The sulfuric acid in example 79 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (IIg) was obtained in equivalent yield.
Example 92
The embodiment provides 6,6',7,7',8,8',9,9' -octahydro-10, 10' -biphenylquinoline derivatives (IIh) with C2 axis chirality and a preparation method thereof.
The synthetic route is shown in part in reference example 79;
the preparation method comprises the following specific steps: the mixture of (3g 1 ，R 3 = H) to (3H: r 1 ＝CH 3 ，R 3 = H), i.e. 0.5g (1.71 mmol) 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 BINAM) was reacted with 0.48g (6.85 mmol) of trans-butenal, and the other conditions were not changed to obtain (IIh).
The characterization data of (IIh) are: mp is 228-229 ℃;1H NMR (400MHz, CDCl) 3 )δ7.90(d,J＝8.3Hz,2H),7.51(s,2H),7.05(d,J＝8.3Hz,2H),3.20–2.88(m,4H),2.39(s,6H),2.37–2.26(m,2H),2.22–2.08(m,2H),1.86–1.75(m,4H),1.72–1.45(m,4H)； 13 C NMR(75MHz,CDCl 3 )δ157.0,145.4,138.4,136.6,135.5,135.0,125.3,124.5,120.6,30.4,28.2,25.6,23.6,22.4；ESI-MS:calculated[C 28 H 28 N 2 +H] + :393.2331,found:393.2347.
Example 93
The starting materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 92 were mixed]-2,2' -diamine (H) 8 BINAM) to its R-type chiral isomer (R-H) 8 BINAM), other conditions are the same. The chiral products (R) - (IIh) are obtained in equal yield.
Optical rotation data of (R) to (IIh): [ alpha ] of] 20 D ＝120.54(c＝1.00,CH 2 Cl 2 )。
Example 94
The starting materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 92 were mixed]-2,2' -diamine (H) 8 BINAM) to its S-type chiral isomer (S-H) 8 BINAM), other conditions being the same. The chiral products (S) - (IIh) are obtained in equal yield.
Example 95 to example 98
The solvent toluene in example 92 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, under the same conditions. The product (IIh) was obtained in equivalent yield.
Examples 99 to 104
The sulfuric acid in example 92 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, under the same conditions as above. The product (IIh) was obtained in equivalent yield.
Example 105
The embodiment provides a 6,6',7,7',8,8',9,9' -octahydro-10, 10' -biphenylquinoline derivative (II i) with C2 axis chirality and a preparation method thereof.
The synthetic route is shown in part with reference to example 79;
the preparation process comprises the following steps: the mixture of (3g 1 ，R 3 = H) to (3 i: r 1 ，R 3 ＝CH 3 ) I.e., 0.5g (1.71 mmol) of 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 BINAM) was reacted with 0.35g (6.85 mmol) of trans-3-penten-2-one under otherwise unchanged conditions to give (IIi).
The characterization data of (II i) are: mp is 281-282 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.68(s,2H),6.88(s,2H),3.17–2.92(m,4H),2.59(s,6H),2.43–2.24(m,8H),2.12(dt,J＝17.1,6.0Hz,2H),1.78(dd,J＝13.0,7.5Hz,4H),1.63(m,4H)； 13 C NMR(101MHz,CDCl 3 )δ156.5,145.1,142.3,137.8,137.5,135.0,124.5,121.4,121.3,30.7,28.2,25.5,23.2,23.1,18.7；ESI-MS:calculated[C 30 H 32 N 2 +H] + :421.2644,found:421.2669.
example 106
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 105 were mixed]-2,2' -diamine (H) 8 -BINAM) to be changed into R type chiral isomer (R-H) 8 BINAM), other conditions are the same. The chiral products (R) - (II) are obtained in equal yield.
Optical rotation data of (R) to (II): [ alpha ] of] 20 D ＝161.9(c＝1.00,CH 2 Cl 2 )。
Example 107
The feedstock 5,5',6,6',7,7',8 of example 105 was mixed8 '-octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 BINAM) to its S-type chiral isomer (S-H) 8 BINAM), other conditions are the same. The chiral products (S) - (II i) were obtained in equal yields.
Examples 108 to 111
The solvent toluene in example 105 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (IIi) was obtained in equivalent yield.
Examples 112 to 117
The sulfuric acid in example 105 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, under the same conditions as above. The product (IIi) was obtained in equivalent yield.
Example 118
The embodiment provides a 6,6',7,7',8,8',9,9' -octahydro-10, 10' -biphenylquinoline derivative (IIj) with C2 axis chirality and a preparation method thereof.
The synthetic route is shown in part with reference to example 79;
the preparation method comprises the following specific steps: the mixture of (3g 1 ，R 3 = H) to (3 j: r 1 ，R 3 ＝C 2 H 5 ) I.e., 0.5g (1.71 mmol) of 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 BINAM) was reacted with 0.48g (6.85 mmol) of 4-hepten-3-one, otherwise unchanged, to give (IIj).
The characterization data of (IIj) are as follows: mp is 147-148 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.75(s,2H),6.94(s,2H),3.18–2.97(m,8H),2.64(q,J＝7.5Hz,4H),2.41(m,2H),2.19(dt,J＝17.1,5.9Hz,2H),1.82(m,4H),1.75–1.57(m,4H),1.42(t,J＝7.5Hz,6H),1.04(t,J＝7.5Hz,6H)； 13 C NMR(101MHz,CDCl 3 )δ161.1,148.1,145.1,137.7,134.9,123.8,120.9,118.2,31.7,30.9,28.2,25.0,23.3,23.3,14.0,13.2；ESI-MS:calculated[C 34 H 40 N 2 +H] + :477.3270,found:477.3272.
example 119
The method of example 118Feedstock 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 -BINAM) to be changed into R type chiral isomer (R-H) 8 BINAM), other conditions are the same. The chiral products (R) - (IIj) are obtained in equal yield.
Optical rotation data of (R) to (IIj): [ alpha ] to] 20 D ＝154.0(c＝1.00,CH 2 Cl 2 )。
Example 120
The starting materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 118 were mixed]-2,2' -diamine (H) 8 BINAM) to its S-type chiral isomer (S-H) 8 BINAM), other conditions are the same. The chiral products (S) - (IIj) are obtained in equal yield.
Examples 121 to 124
The solvent toluene in example 118 was replaced with chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, under the same conditions. The product (IIj) was obtained in equivalent yield.
Example 125 to example 130
The sulfuric acid in example 118 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, under the same conditions as above. The product (IIj) was obtained in equivalent yield.
Example 131
The embodiment provides 6,6',7,7',8,8',9,9' -octahydro-10, 10' -biphenylquinoline derivatives (II k) with C2 axis chirality and a preparation method thereof.
The synthetic route is shown in part with reference to example 79;
the preparation process comprises the following steps: the mixture of (3g 1 ，R 3 = H) to (3 k: r 1 ，R 3 ＝CH(CH 3 ) 2 ) I.e., 0.59g (1.71 mmol) of 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 BINAM) was reacted with 0.48g (6.85 mmol) 2,6-dimethyl-4-hepten-3-one, otherwise unchanged, to give (IIk).
The characterization data of (IIk) are: mp is 128-129 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.82(s,2H),7.04(s,2H),3.80(dt,J＝13.5,6.8Hz,2H),3.26–3.01(m,4H),2.98–2.77(m,2H),2.58–2.39(m,2H),2.29(dt,J＝17.0,5.7Hz,2H),1.97–1.79(m,4H),1.70(m,4H),1.45(dd,J＝6.8,3.5Hz,12H),1.09(d,J＝6.8Hz,6H),0.99(d,J＝6.9Hz,6H)； 13 C NMR(101MHz,CDCl 3 )δ164.3,152.4,145.2,138.4,137.1,134.6,123.2,120.4,113.5,36.4,31.0,28.6,27.5,23.5,23.2,22.5,21.8；ESI-MS:calculated[C 38 H 48 N 2 +H] + :533.3896,found:533.3894.
example 132
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 131]-2,2' -diamine (H) 8 BINAM) to its R-type chiral isomer (R-H) 8 BINAM), other conditions are the same. The chiral products (R) - (IIk) are obtained in equal yield.
Optical rotation data of (R) to (IIk): [ alpha ] to] 20 D ＝217.4(c＝1.00,CH 2 Cl 2 )。
Example 133
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 131]-2,2' -diamine (H) 8 BINAM) to its S-type chiral isomer (S-H) 8 BINAM), other conditions are the same. The chiral products (S) - (IIk) were obtained in equal yields.
Examples 134 to 137
The solvent toluene in example 131 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (IIk) was obtained in equivalent yield.
Example 138 to example 143
The sulfuric acid in example 131 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (IIk) was obtained in equivalent yield.
Example 144
The embodiment provides a 6,6',7,7',8,8',9,9' -octahydro-10, 10' -biphenylquinoline derivative (II l) with C2 axis chirality and a preparation method thereof.
The synthetic route is shown in part with reference to example 79;
the preparation process comprises the following steps: the mixture of (3g 1 ，R 3 = H) was changed to (3 l: r 1 ＝OC 2 H 5 ，R 3 ＝CH 3 ) I.e., 0.59g (1.71 mmol) of 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 -BINAM) was reacted with 0.49g (6.85 mmol) of 4-ethoxy-3-buten-2-one, otherwise conditions were unchanged, to give (IIl).
Characterization data for (II l) are: mp is 322-323 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.84(s,2H),7.49(s,2H),6.42(s,2H),2.91(t,J＝6.1Hz,4H),2.48(s,6H),2.18(t,J＝6.2Hz,4H),1.82–1.73(m,4H),1.69(dd,J＝9.9,5.6Hz,4H)； 13 C NMR(101MHz,CDCl 3 )δ162.0,148.7,14.0,133.6,133.0,125.7,120.5,119.3,118.8,29.6,27.3,22.5,22.4,19.1；ESI-MS:calculated[C 28 H 28 N 2 O 2 +H] + :425.2229,found:425.2236.
example 145
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 144 were mixed]-2,2' -diamine (H) 8 BINAM) to its R-type chiral isomer (R-H) 8 BINAM), other conditions are the same. The chiral products (R) - (IIl) were obtained in equal yields.
Optical rotation data of (R) to (IIl): [ alpha ] of] 20 D ＝-164.4(c＝1.00,CH 2 Cl 2 )。
Example 146
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 144 were mixed]-2,2' -diamine (H) 8 BINAM) to its S-type chiral isomer (S-H) 8 BINAM), other conditions are the same. The chiral products (S) - (IIl) were obtained in equal yields.
Examples 147 to 150
The solvent toluene in example 144 was replaced with chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (II l) was obtained in equivalent yield.
Examples 151 to 156
The sulfuric acid in example 144 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (II l) was obtained in equivalent yield.
Example 157
The embodiment provides 6,6',7,7',8,8',9,9' -octahydro-10, 10' -biphenylquinoline derivatives (IIm) with C2 axis chirality and a preparation method thereof.
The synthetic route is shown in part with reference to example 79;
the preparation method comprises the following specific steps: the mixture of (3g 1 ，R 3 = H) to (3 m: r 1 ，R 3 = Ph), i.e. 0.59g (1.71 mmol) 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 BINAM) was reacted with 0.89g (6.85 mmol) of chalcone, otherwise unchanged, to give (IIm).
The characterization data of (IIm) are: mp is 184-185 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.84(dd,J＝7.5,2.0Hz,4H),7.69(d,J＝5.7Hz,4H),7.67–7.61(m,4H),7.61–7.47(m,6H),7.25(dd,J＝9.0,3.2Hz,6H),3.19–2.91(m,4H),2.80–2.60(m,2H),2.44(dt,J＝17.0,5.6Hz,2H),1.91–1.62(m,8H)； 13 C NMR(101MHz,CDCl 3 )δ153.7,147.9,145.9,139.9,139.5,138.8,138.0,136.7,129.8,128.9–128.1(m),127.9,127.0,124.0,123.4,117.4,31.0,28.6,23.3；ESI-MS:calculated[C 50 H 40 N 2 +H] + :669.3270,found:669.3271.
example 158
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 157 were mixed]-2,2' -diamine (H) 8 BINAM) to its R-type chiral isomer (R-H) 8 BINAM), other conditions are the same. The chiral products (R) - (IIm) are obtained in equal yield.
Optical rotation data of (R) to (IIm): [ alpha ] to] 20 D ＝-21.8(c＝1.00,CH 2 Cl 2 )。
Example 159
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 157 were mixed]-2,2' -diamine (H) 8 BINAM) to its S-type chiral isomer (S-H) 8 BINAM), other conditions are the same. The chiral products (S) - (IIm) are obtained in equal yield.
Examples 160 to 163
The solvent toluene in example 157 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (IIm) was obtained in equivalent yield.
Examples 164 to 169
The sulfuric acid in example 157 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (IIm) was obtained in equivalent yield.
Example 170
This example provides a synthesis of 6,6',7,7',8,8',9,9' -octahydro-10, 10' -biphenylquinoline derivative (IIn) with C2 axis chirality.
The synthetic route is shown in part with reference to example 79;
the preparation method comprises the following specific steps: the reaction mixture of (3g 1 ，R 3 = H) to (3 n: r 1 ，R 3 ＝o-C 4 H 3 S), i.e. 0.59g (1.71 mmol) 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 BINAM) was reacted with 0.94g (6.85 mmol) 1,3-di (thien-2-yl) -2-propen-1-one, otherwise unchanged, to give (IIn).
The characterization data of (IIn) are: mp is 188-189 ℃; 1 H NMR(400MHz,CDCl 3 )δ8.19(s,2H),7.82(s,2H),7.72–7.59(m,6H),7.46–7.41(m,2H),7.37(m,2H),7.13(dd,J＝5.0,3.7Hz,2H),3.38–3.16(m,4H),2.92–2.79(m,2H),2.58(m,2H),2.08–1.93(m,6H),1.84(dd,J＝14.4,6.1Hz,2H)； 13 C NMR(101MHz,CDCl 3 )δ164.3,152.4,145.2,138.4,137.1,134.6,123.2 120.4,113.5,36.4,31.0,28.6,27.5,23.5,23.2,22.5,21.8；ESI-MS:calculated[C 42 H 32 N 2 S 4 +H] + :693.1527,found:693.1532.
example 171
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1 '-binaphthyl ] -2,2' -diamine (H8-BINAM) in example 170 were changed to its R-type chiral isomer (R-H8-BINAM) under the same conditions. The chiral products (R) - (IIn) are obtained in equal yield.
Optical rotation data of (R) to (IIn): [ alpha ] to] 20 D ＝24.9(c＝1.00,CH 2 Cl 2 )。
Example 172
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 170 were mixed]-2,2' -diamine (H) 8 BINAM) to its S-type chiral isomer (S-H8-BINAM), and the other conditions are the same. The chiral products (S) - (IIn) are obtained in equal yield.
Example 173
The solvent toluene in example 170 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (IIn) was obtained in equivalent yield.
Example 177
The sulfuric acid in example 170 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (IIn) was obtained in equivalent yield.
Example 183
The embodiment provides a 6,6',7,7',8,8',9,9' -octahydro-10, 10' -biphenylquinoline derivative (IIo) with C2 axis chirality and a preparation method thereof.
The synthetic route is shown in part with reference to example 79;
the preparation process comprises the following steps: the reaction mixture of (3g 1 ，R 3 = H) to (3 o: r 1 ＝o-C 5 H 4 N，R 3 ＝o-C 5 H 4 N), i.e. 0.59g (1.71 mmol) 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 -BINAM) was reacted with 0.90g (6.85 mmol) 1,3-di (pyridin-2-yl) -2-propen-1-one, otherwise conditions were unchanged, to give (IIo).
The characterization data of (IIo) are: mp is 222-223 ℃; 1 H NMR(400MHz,CDCl 3 )δ8.88(d,J＝4.8Hz,2H),8.54(d,J＝2.9Hz,4H),8.02(s,2H),7.97–7.85(m,4H),7.79(d,J＝7.7Hz,2H),7.55(m,2H),7.45–7.38(m,2H),7.14(dd,J＝7.3,4.8Hz,2H),3.17–3.00(m,4H),2.62–2.47(m,2H),2.35(dt,J＝17.4,5.9Hz,2H),1.91–1.62(m,8H)； 13 C NMR(101MHz,CDCl 3 )δ158.3,156.6,153.3,149.3,148.4,145.8,145.7,138.9,137.9,137.8,136.7,136.6,125.1,124.2,123.3,123.2,122.6,121.5,117.8,31.1,28.5,23.1,23.0；ESI-MS:calculated[C 46 H 36 N 6 +H] + :673.3080,found:673.3099.
example 184
The feedstock 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 183 was added]-2,2' -diamine (H) 8 BINAM) to its R-type chiral isomer (R-H) 8 BINAM), other conditions being the same. The chiral products (R) - (IIo) are obtained in equal yield.
Optical rotation data of (R) to (IIo): [ alpha ] of] 20 D ＝66.8(c＝1.00,CH 2 Cl 2 )。
Example 185
The feedstock 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 183 was added]-2,2' -diamine (H) 8 BINAM) to its S-type chiral isomer (S-H) 8 BINAM), other conditions are the same. The chiral products (S) - (IIo) are obtained in equal yield.
Example 186 to example 189
The solvent toluene in example 183 was replaced by chlorobenzene, 1,4-dioxane, butyl acetate and dichloromethane, respectively, under the same conditions. The product (IIo) was obtained in equivalent yield.
Examples 190 to 195
The sulfuric acid in example 183 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (IIo) was obtained in equivalent yield.
Example 196
The embodiment provides a 6,6',7,7',8,8',9,9' -octahydro-10, 10' -biphenylquinoline derivative (IIp) with C2 axis chirality and a preparation method thereof.
The synthetic route is shown in part with reference to example 79;
the preparation process comprises the following steps: the mixture of (3g 1 ，R 3 = H) to (3 o: r is 1 ＝p-C 5 H 4 N，R 3 ＝p-C 5 H 4 N), i.e. 0.59g (1.71 mmol) 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl]-2,2' -diamine (H) 8 BINAM) was reacted with 0.90g (6.85 mmol) 1,3-bis (pyridin-4-yl) -2-propen-1-one under otherwise unchanged conditions to give (IIp).
The characterization data of (IIp) are: mp is 387 to 388 ℃; 1 H NMR(400MHz,CDCl 3 )δ8.75(d,J＝5.8Hz,4H),8.39(d,J＝6.0Hz,4H),7.54(s,2H),7.44(dd,J＝9.0,6.0Hz,8H),7.39(s,2H),3.21–2.96(m,4H),2.61–2.35(m,4H),1.98–1.69(m,8H)； 13 C NMR(101MHz,CDCl 3 )δ150.6,149.0,148.9,145.4,144.9,144.8,144.6,138.8,137.7,137.0,123.3,122.7,122.2,120.1,116.0,30.0,27.6,22.0；ESI-MS:calculated[C 46 H 36 N 6 +H] + :673.3080,found:673.3093.
example 197
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 196]-2,2' -diamine (H) 8 BINAM) to its R-type chiral isomer (R-H) 8 BINAM), other conditions are the same. The chiral products (R) - (IIp) were obtained in equal yields.
Optical rotation data of (R) to (IIp): [ alpha ] to] 20 D ＝-273.6(c＝1.00,CH 2 Cl 2 )。
Example 198
The raw materials 5,5',6,6',7,7',8,8' -octahydro- [1,1' -binaphthyl in example 196]-2,2' -diamine (H) 8 BINAM) to its S-type chiral isomer (S-H) 8 BINAM), other conditions are the same. The chiral products (S) - (IIp) were obtained in equal yields.
Examples 199 to 202
The solvent toluene in example 196 was replaced with chlorobenzene, 1,4-dioxane, butyl acetate, dichloromethane, respectively, and the other conditions were the same. The product (IIp) was obtained in equivalent yield.
Examples 203 to 208
The sulfuric acid in example 196 was replaced with hydrochloric acid, nitric acid, ferric chloride, zinc chloride, p-toluenesulfonic acid, phosphoric acid, respectively, and the other conditions were the same. The product (IIp) was obtained in equivalent yield.
In conclusion, the biphenyl quinoline or octahydro-benzo-quinoline skeleton compound prepared by the invention can simultaneously meet the characteristics of short synthetic route, simple and convenient operation, easily obtained raw materials and the like, and has good application prospect.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A biphenyl quinoline skeleton compound with C2 axis chirality and a chiral isomer thereof are characterized by being shown as a formula (I) or a formula (II):
formula (I) includes the racemate shown in formula DL- (I) and all possible chiral isomers shown in formulas (R) - (I) and (S) - (I);
the formula (II) comprises a racemate shown as a formula DL- (II) and all possible chiral isomers shown as formulas (R) - (II) and formulas (S) - (II);
in formula (I) and formula (II):
R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 each independently selected from:
a hydrogen atom;
C 1 ～C 30 alkyl of (C) 1 ～C 30 Silyl group of C 1 ～C 30 Haloalkyl, C 2 ～C 30 Alkenyl of, C 2 ～C 30 An alkynyl group;
halogen, hydroxyl, alkoxy, acyloxy, mercapto, thioether, nitro, carbonyl, carboxyl, ester, substituted or unsubstituted amino, imino, cyano, phosphonate, phosphine, amide, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl;
substituted or unsubstituted C 6 ～C 50 Aryl of (2); substituted or unsubstituted C 6 ～C 50 And aryl of (1); substituted or unsubstituted C 6 ～C 50 A fused aryl group of (a);
substituted or unsubstituted C 7 ～C 50 Aralkyl group of (1); substituted or unsubstituted C 7 ～C 50 An aralkyloxy group of (a); substituted or unsubstituted C 7 ～C 50 Aralkyl mercapto group of (a);
aromatic heterocyclic group, heterocyclic group or condensed heterocyclic group.
2. Biphenyl quinoline skeleton compound having C2 axis chirality and chiral isomers thereof according to claim 1, wherein said substituted C 6 ～C 50 Aryl of (a); substituted C 6 ～C 50 And aryl of (1); substituted C 6 ～C 50 The fused aryl group of (1); substituted C 7 ～C 50 Aralkyl group of (1); substituted C 7 ～C 50 An aralkyloxy group of (a); substituted C 7 ～C 50 In the mercapto group of the aralkyl group of (A),
the substituent is selected from thiophene, benzothiophene and arylthiophene; carbazole, benzocarbazole, arylcarbazole; pyridine, benzopyridine, isoquinoline, benzoquinoline, aroquinoline, aroisoquinoline; fluorene; furan, benzofuran, arylfuran; pyrrole, indole, arylpyrrole; pyrazole, benzopyrazole, arylpyrazole; oxazole, benzoxazole, arooxazole; isoxazoles, benzisoxazoles, arylisoxazoles; thiazoles, benzothiazoles, arylthiazoles; isothiazole, benzisothiazole, arylisothiazole; imidazole, benzimidazole, arylimidazole; pyrans, benzopyrans, arylpyrans; pyridazine, benzopyridazine, arylpyridazine; pyrimidines, benzopyrimidines, arylpyrimidines; pyrazine, benzopyrazines, arylpyrazines; phenazine, benzophenazine, arylphenazine; thiazines, benzothiazines, arylthiazines; pteridines, benzopteridines, arylpteridines; acridine, benzacridine, and benzacridine; phenothiazine, benzophenothiazine or arylphenothiazine.
3. The biphenyl quinoline skeleton compound having C2 axis chirality and the chiral isomers thereof according to claim 1, wherein the compound is represented by formula (I) -A or formula (II) -A:
the formula (I) -A comprises a racemate shown as formula DL- (I) -A and all possible chiral isomers shown as formulas (R) - (I) -A and (S) - (I) -A;
the formula (II) -A comprises a racemate shown as a formula DL- (II) -A and all possible chiral isomers shown as formulas (R) - (II) -A and (S) - (II) -A;
4. the biphenyl quinoline skeleton compound having C2 axis chirality and the chiral isomers thereof according to claim 3, wherein the compound is represented by formula (I) -B or formula (I) -C:
the formula (I) -B comprises a racemate shown as a formula DL- (I) -B and all possible chiral isomers shown as a formula (R) - (I) -B and a formula (S) - (I) -B;
the formula (I) -C comprises a racemate shown as a formula DL- (I) -C and all possible chiral isomers shown as formulas (R) - (I) -C and (S) - (I) -C;
in the formula (I) -C, R 5 ' is selected from:
a hydrogen atom;
C 1 ～C 30 alkyl of (C) 1 ～C 30 Silyl group of C 1 ～C 30 Haloalkyl, C 2 ～C 30 Alkenyl of, C 2 ～C 30 An alkynyl group;
halogen, hydroxyl, alkoxy, acyloxy, mercapto, thioether, nitro, carbonyl, carboxyl, ester, substituted or unsubstituted amino, imino, cyano, phosphonate, phosphine, amide, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl;
substituted or unsubstituted C 6 ～C 50 Aryl of (a); substituted or unsubstituted C 6 ～C 50 And aryl of (1); substituted or unsubstituted C 6 ～C 50 A fused aryl group of (a);
substituted or unsubstituted C 7 ～C 50 Aralkyl of (4); substituted or unsubstituted C 7 ～C 50 An aralkyloxy group of (a); substituted or unsubstituted C 7 ～C 50 An aralkylthio group of (a);
aromatic heterocyclic group, heterocyclic group or condensed heterocyclic group.
5. The biphenyl quinoline skeleton compound having C2 axis chirality and its chiral isomers according to any of claims 1 to 4, wherein the compound is selected from racemates represented by any of the following structures or all possible chiral isomers corresponding to racemates represented by any of the following structures;
6. the method for preparing the biphenyl quinoline skeleton compound with C2 axis chirality and its chiral isomer according to any of claims 1 to 5, characterized by the following synthetic route:
in the above formula:
when the formula (4) is selected from racemes, the formula (I) is DL- (I), and the formula (II) is DL- (II);
when the formula (4) is selected from chiral R compounds, the formula (I) is (R) - (I), the formula (II) is (R) - (II), and all possible chiral isomers with different configurations caused by configuration and conformation change;
when formula (4) is selected from chiral S compounds, formula (I) is (S) - (I), formula (II) is (S) - (II), and all possible chiral isomers with different configurations caused by configuration and conformation changes.
7. The method for preparing a biphenyl quinoline skeleton compound having C2 axis chirality and chiral isomers thereof according to claim 6, wherein the catalyst is selected from protonic acid or lewis acid; the protonic acid comprises hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, perchloric acid, aqueous hydrochloric acid solution, aqueous sulfuric acid solution, aqueous phosphoric acid solution, aqueous nitric acid solution, aqueous p-toluenesulfonic acid solution or aqueous perchloric acid solution; the Lewis acid includes stannic chloride, scandium trichloromethane sulfonate, zinc chloride or ferric chloride.
8. The method for preparing a biphenyl quinoline skeleton compound having C2 axis chirality and chiral isomers thereof according to claim 7, wherein the catalyst is selected from hydrochloric acid or sulfuric acid.
9. The preparation method of the biphenyl quinoline skeleton compound with C2 axis chirality and the chiral isomers thereof according to claim 6, wherein the solvent is selected from one or a mixture of any more of aromatic hydrocarbons, halogenated alkanes, ethers or esters.
10. Use of the biphenyl quinoline skeleton compounds having C2 axis chirality and the chiral isomers thereof according to any of claims 1 to 5, for any of the following applications:
(1) As a metal ligand or a chiral metal ligand, a chiral catalyst is formed to participate in asymmetric reactions catalyzed by various metal catalysts or chiral metal catalysts;
(2) As chiral Lewis base and organic small molecular catalyst to catalyze organic reaction or asymmetric organic reaction;
(3) As an organic synthon or a chiral organic synthon to synthesize a new catalyst or a chiral catalyst;
(4) As a synthetic pyridine phase transfer catalyst or a chiral pyridine chiral phase transfer catalyst;
(5) As a photovoltaic material;
(6) The method is used for preparing fluorescent probes and synthesizing other fluorescent materials;
(7) As trace metal detection material;
(8) As a novel dye;
(9) As pharmaceuticals, pesticides and intermediates thereof;
(10) As a fine chemical material.
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Citations (4)
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| CN108658841A (en) * | 2018-02-07 | 2018-10-16 | 中国农业大学 | A kind of carbazole compound and preparation method thereof |
| CN109748841A (en) * | 2019-01-08 | 2019-05-14 | 浙江工业大学 | A method of catalysis asymmetric syntheses chiral beta-aminoketone derivative |
| CN111925356A (en) * | 2020-08-17 | 2020-11-13 | 华东理工大学 | Synthesis method and application of chiral quinoline-imidazoline ligand |
| CN112521333A (en) * | 2019-09-17 | 2021-03-19 | 中国科学院大连化学物理研究所 | Synthesis method of chiral 2, 3-disubstituted tetrahydroquinoline derivative |
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| CN108658841A (en) * | 2018-02-07 | 2018-10-16 | 中国农业大学 | A kind of carbazole compound and preparation method thereof |
| CN109748841A (en) * | 2019-01-08 | 2019-05-14 | 浙江工业大学 | A method of catalysis asymmetric syntheses chiral beta-aminoketone derivative |
| CN112521333A (en) * | 2019-09-17 | 2021-03-19 | 中国科学院大连化学物理研究所 | Synthesis method of chiral 2, 3-disubstituted tetrahydroquinoline derivative |
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