CN109320507A - Chiral fluorescent chemicals and the preparation method and application thereof based on quinoline amides folded formation - Google Patents

Chiral fluorescent chemicals and the preparation method and application thereof based on quinoline amides folded formation Download PDF

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CN109320507A
CN109320507A CN201811074784.7A CN201811074784A CN109320507A CN 109320507 A CN109320507 A CN 109320507A CN 201811074784 A CN201811074784 A CN 201811074784A CN 109320507 A CN109320507 A CN 109320507A
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江华
郑丹
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Beijing Normal University
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Abstract

The present invention discloses a kind of chiral fluorescent chemicals and the preparation method and application thereof of quinoline amides folded formation.The general structure of the compound as shown in following Formulas I or Formula II,Chiral fluorescent material of the invention has the characteristics that CPL shines, and solubility is good in common organic solvent, and yellow is presented in solution, and stability is good.Its CPL signal strength and luminous intensity can be regulated and controled according to the chain length of compound, realize the purpose for changing CPL intensity and luminous intensity by the length for changing conveyor screw.The compound of the present invention has broad application prospects in the chiral organic luminescent dyes, chiral fluorescence probe and fluorescence identifying field that preparation has circular polarised luminescence property.

Description

Chiral fluorescent chemicals and the preparation method and application thereof based on quinoline amides folded formation
Technical field
The present invention relates to material and preparation fields, Fluoresceinated more particularly, to a kind of chirality based on quinoline amides folded formation Object and preparation method thereof is closed in application.
Background technique
Chiral organic fluorescence materials are a kind of while having chiral and the characteristics of luminescence a kind of organic material concurrently.And have circle inclined The chiral molecules of luminous (CPL) characteristic of shaking is since it is in actinic material, chiral Recognition, display device, optical storage apparatus, hand Property the fields such as light emitting diode, CPL laser and asymmetric light-catalyzed reaction have broad application prospects, and it is standby in recent years It is concerned.
At present in the field, due to organic molecular structure is simple, be easy to derivation, be many kinds of the features such as, and become the neck The hot spot in domain.But since higher dissymmetry factor (g cannot be obtainedlum) and quantum yield and limit in fluorescent material field Application.
The quinoline amides folded formation helicene different from the past for acting on and being formed helical structure based on main pi-pi accumulation, folding It is folded effect mainly by adjacent quinoline ring N atom and between acylamino hydrogen be formed by three central hydrogen bonds act on driving and shape At.Chromophore is introduced in quinoline amides folded formation and thus chiral induction center, folded formation generate the spy of circular polarised luminescence Property.
Summary of the invention
The application technical problems to be solved are to provide a kind of chiral fluorescent chemicals based on quinoline amides folded formation, should Compound has good CPL luminous characteristics, and its CPL signal strength and luminous intensity can be according to the chain progress of the compound Row regulation.
It is Fluoresceinated that the application another to be solved technical problem is to provide a kind of chirality based on quinoline amides folded formation Close the preparation method of object.
It is Fluoresceinated that the application another to be solved technical problem is to provide a kind of chirality based on quinoline amides folded formation Close the application of object.
In order to solve the first technical problem mentioned above, the present invention adopts the following technical scheme that:
A kind of chiral fluorescent chemicals based on quinoline amides folded formation, for example following Formulas I of the general structure of the compound Or shown in Formula II,
In Formulas I or Formula II, R1Alkyl, carbazyl, aromatic radical or substituted aromatic base independently selected from carbon atom number 1-15, Carbazole oxygroup, R2Alkyl, carbazyl, aromatic radical independently selected from carbon atom number 1-15, substituted aromatic base, carbazole oxygroup, virtue Fragrant oxygroup or substituted aroma oxygroup, the substituent group of the substituted aromatic base are alkyl, the carbon atom number 2-15 of carbon atom number 1-15 Alkenyl, R3Alkyl, the alkoxy of carbon atom number 1-15, carbazyl, aromatic radical, substitution independently selected from carbon atom number 1-15 Aromatic radical, carbazole oxygroup, fragrant oxygroup or substituted aroma oxygroup, the one of the substituted aromatic base replaces or multi-substituent is that carbon is former The alkyl of subnumber 1-15, the alkenyl of carbon atom number 2-15, the alkynyl of carbon atom number 2-15, carbon atom number 1-10 alkoxy, R1、 R2And R3It is same or different to each other, n is the integer greater than 1.
As the further improvement of technical solution, the compound includes S type enantiomer and R type enantiomer；Wherein,
The structural formula of S type enantiomer be following formula S-I or formula S-II shown in,
The structural formula of R type enantiomer be following formula R-I or formula R-II shown in,
In formula S-I, formula S-II, formula R-I or formula R-II, R1Alkyl, carbazyl, virtue independently selected from carbon atom number 1-15 Perfume base or substituted aromatic base, R2Alkyl, carbazyl, aromatic radical, substituted aromatic base, carbazole independently selected from carbon atom number 1-15 Oxygroup, fragrant oxygroup or substituted aroma oxygroup, the substituent group of the substituted aromatic base are alkyl, the carbon atom of carbon atom number 1-15 The alkenyl of number 2-15, R3Alkoxy, carbazyl, the fragrance of alkyl, carbon atom number 1-15 independently selected from carbon atom number 1-15 Base, substituted aromatic base, carbazole oxygroup, fragrant oxygroup or substituted aroma oxygroup, a substitution or polysubstituted of the substituted aromatic base Base is the alkane of the alkyl of carbon atom number 1-15, the alkenyl of carbon atom number 2-15, the alkynyl of carbon atom number 2-15, carbon atom number 1-10 Oxygroup, R1、R2And R3It is same or different to each other, n is the integer greater than 1.
As the further improvement of technical solution, the R1Selected from isobutyl group, n 4,8 or 16, the R2For methyl, institute State R3For tert-butyl.
A kind of preparation method of the chiral fluorescent chemicals based on quinoline amides folded formation, the compound are such as formula I above Shown, the preparation method includes the following steps:
1) chiral 2- (2- aminophenyl) oxazole that 4 replace under protection of argon gas, is dissolved in anhydrous methylene chloride, N is added, N- diisopropylethylamine makees alkali, obtains solution a；The carboxylic acid of 4- isobutoxy -8- amino -2- carboxyl quinoline amide polymer is molten In anhydrous methylene chloride, solution b is obtained；The quinoline amides polymer to get single chiral is stirred after solution a, b are mixed；
2) the quinoline amides polymer for the single chiral that under an atmosphere of hydrogen, step 1) is obtained and the palladium carbon of 10% content Be dissolved in ethyl acetate, heating stirring to get the quinoline amides polymer of single chiral amine；
3) under protection of argon gas, anhydrous methylene chloride makees solvent, and n,N-diisopropylethylamine makees alkali, and step 2) is obtained The amine of the quinoline amides polymer of single chiral and pivalyl chloride are stirred at room temperature 2~4 hours to get to change shown in Formulas I Close object.
As the further improvement of technical solution, in the step 1), n,N-diisopropylethylamine, 4- isobutoxy -8- The ratio of the acyl chlorides of amino -2- carboxyl quinoline amide polymer and chiral 2- (2- aminophenyl) oxazole of 4 substitutions is 2~100: 1:0.85~10；
In the step 2), the pressure of hydrogen is 0.8~1.5 megapascal, and the temperature of heating is 40~60 degrees Celsius, and heating is stirred The time mixed is 6~15 hours, the mass ratio of the palladium carbon of the quinoline amides polymer and 10% content of single chiral for 10:1~ 3；
In the step 3), the ratio between amount of substance of amine of quinoline amides polymer of valeryl and single chiral is 1 ~500:1.
A kind of preparation method of the chiral fluorescent chemicals based on quinoline amides folded formation, the compound are such as formula I above Shown, the preparation method includes the following steps:
1) under protection of argon gas, anhydrous methylene chloride makees solvent, and n,N-diisopropylethylamine makees alkali, by 4- isobutoxy- The amine and pivalyl chloride of 8- amino -2- carboxyl quinoline amide polymer, which are stirred at room temperature, obtains fluorescence-causing substance new penta for 2~4 hours Acyl group quinoline amides polymer；
2) the valeryl quinoline amides polymer that step 1) obtains is dissolved in the mixed solvent of tetrahydrofuran and methanol, it will NaOH is added after being dissolved in deionized water, obtains the carboxylic acid of valeryl quinoline amides polymer after 1~4h of heating stirring；
3) carboxylic acid for the valeryl quinoline amides polymer that step 2) obtains under protection of argon gas, is dissolved in anhydrous dichloro Methane is added oxalyl chloride, is stirred at room temperature to obtain the acyl chlorides of valeryl quinoline amides polymer；
4) chiral 2- (2- aminophenyl) oxazole that 4 replace under protection of argon gas, is dissolved in anhydrous methylene chloride, N is added, N- diisopropylethylamine obtains solution c；The acyl chlorides for the valeryl quinoline amides polymer that step 3) obtains is dissolved in anhydrous two Chloromethanes obtains solution d, and stirring is after solution c, d are mixed to get Formulas I compound represented.
As the further improvement of technical solution,
In the step 1), n,N-diisopropylethylamine, 4- isobutoxy -8- amino -2- carboxyl quinoline amide polymer Amine and pivalyl chloride ratio be 2~100:1:0.85~10；
In the step 2), the ratio between tetrahydrofuran, amount of substance of methanol and water are 5~100:1~100:0.1~50； The ratio between amount of substance of valeryl quinoline amides polymer and sodium hydroxide is 1:10~1:20；
In the step 3), the ratio between the carboxylic acid of valeryl quinoline amides polymer and the amount of substance of oxalyl chloride are 1:2 ~100；
In the step 4), the chiral 2- (2- aminophenyl) of the acyl chlorides of valeryl quinoline amides polymer and 4 substitutions The ratio between amount of substance of oxazole is 1:0.85~1.2.
A kind of preparation method of the chiral fluorescent chemicals based on quinoline amides folded formation, the compound are such as formula II above Shown, the preparation method includes the following steps:
1) 4,7- diisobutyl -1,10- Phen -2,9- carboxylic acid under protection of argon gas, is dissolved in anhydrous methylene chloride, Oxalyl chloride is added, is stirred at room temperature to obtain 4,7- diisobutyl -1,10- Phen -2,9- carboxylic acid chloride；
2) amine of chiral quinoline amides polymer under protection of argon gas, is dissolved in anhydrous methylene chloride, N is added, N- bis- is different Propylethylamine obtains solution e；4,7- diisobutyl -1,10- Phen -2,9- the carboxylic acid chloride that step 1) obtains is dissolved in Anhydrous methylene chloride obtains solution f；Stirring is after solution e, f are mixed to get Formula II compound represented.
As the further improvement of technical solution, in the step 1), 4,7- diisobutyl -1,10- Phens -2,9- The ratio between amount of substance of carboxylic acid and oxalyl chloride is 1:5~1000；；
In the step 2), acyl chlorides, the N of 4,7- diisobutyl -1,10- Phen -2,9- carboxylic acids, N- diisopropyl second The ratio between amine and the amount of substance of chiral 2- (2- aminophenyl) oxazole of 4 substitutions are 1:5~1000:2~10.
Invention additionally discloses a kind of based on the chiral fluorescent chemicals of quinoline amides folded formation in chiral luminous organic material Preparation, chiral fluorescence probe preparation and the application in fluorescence identifying field.
Any range documented by the present invention includes any numerical value between end value and end value and end value or end value Between any subrange for being constituted of any number.
Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention The conventional equipment in fields can be used or carried out referring to the prior art of fields.
Compared with prior art, the invention has the following beneficial effects:
The present invention provides a kind of chiral organic molecules and preparation method thereof with circular polarised luminescence.It is provided by the invention Chiral fluorescent material has the characteristics that CPL shines, and solubility is good in common organic solvent, and yellow is presented in solution, stablizes Property is good.The CPL signal strength and luminous intensity of such chirality fluorescent material can be according to shown in formula S-I, R-I, S-II or R-II The chain length of compound is regulated and controled.When the value of n is bigger, CPL signal is stronger, and luminous intensity also increases with it, to realize Length by changing conveyor screw changes the purpose of CPL intensity and luminous intensity.These compounds have circular polarization hair in preparation It has broad application prospects in the chiral organic luminescent dyes of light property, chiral fluorescence probe and fluorescence identifying field.
Detailed description of the invention
Fig. 1 is the circular dichroism figure of compound prepared by embodiment 1；
Fig. 2 is the circular dichroism figure of compound prepared by embodiment 2；
Fig. 3 is the circular dichroism figure of compound prepared by embodiment 3；
Fig. 4 is the circular dichroism figure of compound prepared by embodiment 4；
Fig. 5 is the circular dichroism figure of compound prepared by embodiment 5；
Fig. 6 is the circular dichroism figure of compound prepared by embodiment 6；
Fig. 7 is the circular polarised luminescence spectrum of compound prepared by embodiment 1；
Fig. 8 is the circular polarised luminescence spectrum of compound prepared by embodiment 2；
Fig. 9 is the circular polarised luminescence spectrum of compound prepared by embodiment 3；
Figure 10 is the circular polarised luminescence spectrum of compound prepared by embodiment 4；
Figure 11 is the circular polarised luminescence spectrum of compound prepared by embodiment 5；
Figure 12 is the circular polarised luminescence spectrum of compound prepared by embodiment 6；
Figure 13 is the dissymmetry factor of the circular polarised luminescence spectrum of compound prepared by embodiment 1 with wavelength change；
Figure 14 is the dissymmetry factor of the circular polarised luminescence spectrum of compound prepared by embodiment 2 with wavelength change；
Figure 15 is the dissymmetry factor of the circular polarised luminescence spectrum of compound prepared by embodiment 3 with wavelength change；
Figure 16 is the dissymmetry factor of the circular polarised luminescence spectrum of compound prepared by embodiment 4 with wavelength change；
Figure 17 is the dissymmetry factor of the circular polarised luminescence spectrum of compound prepared by embodiment 5 with wavelength change；
Figure 18 is the dissymmetry factor of the circular polarised luminescence spectrum of compound prepared by embodiment 6 with wavelength change.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this The protection scope of invention.
A kind of chiral fluorescent chemicals based on quinoline amides folded formation of the application, the structure of the raceme of the compound General formula as shown in following Formulas I or Formula II,
In Formulas I or Formula II, R1Alkyl, carbazyl, aromatic radical or substituted aromatic base independently selected from carbon atom number 1-15, Carbazole oxygroup, R2Alkyl, carbazyl, aromatic radical independently selected from carbon atom number 1-15, substituted aromatic base, carbazole oxygroup, virtue Fragrant oxygroup or substituted aroma oxygroup, the substituent group of the substituted aromatic base are alkyl, the carbon atom number 2-15 of carbon atom number 1-15 Alkenyl, R3Alkyl, the alkoxy of carbon atom number 1-15, carbazyl, aromatic radical, substitution independently selected from carbon atom number 1-15 Aromatic radical, carbazole oxygroup, fragrant oxygroup or substituted aroma oxygroup, the one of the substituted aromatic base replaces or multi-substituent is that carbon is former The alkyl of subnumber 1-15, the alkenyl of carbon atom number 2-15, the alkynyl of carbon atom number 2-15, carbon atom number 1-10 alkoxy, R1、 R2And R3It is same or different to each other, n is the integer greater than 1.
According to the certain embodiments of the application, above compound includes S type enantiomer and R type enantiomer.
Wherein, the structural formula of S type enantiomer be following formula S-I or formula S-II shown in,
The structural formula of R type enantiomer be following formula R-I or formula R-II shown in,
In formula S-I, formula S-II, formula R-I or formula R-II, R1Alkyl, carbazyl, virtue independently selected from carbon atom number 1-15 Perfume base or substituted aromatic base, carbazole oxygroup；R2Alkyl, carbazyl, aromatic radical, substitution virtue independently selected from carbon atom number 1-15 Perfume base, carbazole oxygroup, fragrant oxygroup or substituted aroma oxygroup, the substituent group of the substituted aromatic base are the alkane of carbon atom number 1-15 The alkenyl of base, carbon atom number 2-15；R3Alkoxy, the click of alkyl, carbon atom number 1-15 independently selected from carbon atom number 1-15 Oxazolyl, aromatic radical, substituted aromatic base, carbazole oxygroup, fragrant oxygroup or substituted aroma oxygroup, a substitution of the substituted aromatic base Or multi-substituent is the alkyl of carbon atom number 1-15, the alkenyl of carbon atom number 2-15, the alkynyl of carbon atom number 2-15, carbon atom number The alkoxy of 1-10, R1、R2And R3It is same or different to each other, n is the integer greater than 1.
According to the certain embodiments of the application, the structure of compound shown in formula S-I is as shown in following formula S-I1 to S-I3:
In above-mentioned formula S-I1 and formula S-I2, R2Independently selected from methyl, isopropyl, phenyl or benzyl.
According to the certain embodiments of the application, the structure of compound shown in formula S-II is such as following formula S-II1 to S-II3 institute Show:
According to the certain embodiments of the application, the structure of compound shown in formula R-I is as shown in following formula R-I1 to R-I3:
According to the certain embodiments of the application, the structure of compound shown in formula R-II be such as following formula R-II1 extremely
Shown in R-II3:
Further, according to the certain embodiments of the application, compound shown in formula S-I1 be as following formula S-I1-a extremely S-I1-d:
Compound shown in formula S-I1 is in compound shown in formula S-I1-a to S-I1-d, and Chiral Amine is to quinoline amides folded formation There is chiral induction effect, and the chiral induction is complete, thus it is single to have quinoline amides folded formation with optical activation One characteristic chiral and that circular polarised luminescence is presented.
Further, according to the certain embodiments of the application, compound shown in formula S-I2 be as following formula S-I2-a extremely S-I2-d:
Compound shown in formula S-I1 is in compound shown in formula S-I1-a to S-I1-d, and Chiral Amine is to quinoline amides folded formation There is chiral induction effect, and the chiral induction is complete, thus it is single to have quinoline amides folded formation with optical activation One characteristic chiral and that circular polarised luminescence is presented.Further, since the chain length of quinoline amides folded formation increases, chiral induction effect quilt Amplification, the effect of circular polarised luminescence are also amplified therewith.
A kind of preparation method of the chiral fluorescent chemicals based on quinoline amides folded formation of the application, the compound are upper Shown in Formulas I, the preparation method includes the following steps:
1) chiral 2- (2- aminophenyl) oxazole that 4 replace under protection of argon gas, is dissolved in anhydrous methylene chloride, N is added, N- diisopropylethylamine makees alkali, obtains solution a；The carboxylic acid of 4- isobutoxy -8- amino -2- carboxyl quinoline amide polymer is molten In anhydrous methylene chloride, solution b is obtained；The quinoline amides polymer to get single chiral is stirred after solution a, b are mixed；
2) the quinoline amides polymer for the single chiral that under an atmosphere of hydrogen, step 1) is obtained and the palladium carbon of 10% content It is dissolved in ethyl acetate, heating stirring is overnight to get the amine of the quinoline amides polymer of single chiral；
3) under protection of argon gas, anhydrous methylene chloride makees solvent, and n,N-diisopropylethylamine makees alkali, and step 2) is obtained The amine of the quinoline amides polymer of single chiral and pivalyl chloride are stirred at room temperature 2~4 hours to get to change shown in Formulas I Close object.
According to the certain embodiments of the application, in the step 1), n,N-diisopropylethylamine, 4- isobutoxy -8- The ratio of the acyl chlorides of amino -2- carboxyl quinoline amide polymer and chiral 2- (2- aminophenyl) oxazole of 4 substitutions is 2~100: 1:0.85~10；It is preferably in a proportion of 2:1:0.9.Applicant it has been investigated that, using acyl chlorides be condensed method prepare the compound, Reaction step is simple, and yield is more considerable.
According to the certain embodiments of the application, in the step 2), the pressure of hydrogen is 0.8~1.5 megapascal, preferably 1.0 megapascal, the temperature of heating are 40~60 degrees Celsius, and the time of heating stirring is 6~15 hours, the quinoline amides of single chiral The mass ratio of the palladium carbon of polymer and 10% content is 10:1~3；It is preferred that 10:1.Applicant it has been investigated that, the synthetic schemes It operates, post-process simple and fast, yield is higher, low in cost, atom high conversion rate.
According to the certain embodiments of the application, in the step 3), the quinoline amides of valeryl and single chiral are more The ratio between amount of substance of amine of aggressiveness is 1~500:1, preferably 1.2:1.The technical solution is easy to operate, and raw material is easy to get, yield compared with It is high.
The reaction equation of above-mentioned preparation method is as follows:
A kind of another preparation method of the chiral fluorescent chemicals based on quinoline amides folded formation of the application, the chemical combination Object is as shown in formula I above, and the preparation method includes the following steps:
1) under protection of argon gas, anhydrous methylene chloride makees solvent, and n,N-diisopropylethylamine makees alkali, by 4- isobutoxy- The amine and pivalyl chloride of 8- amino -2- carboxyl quinoline amide polymer, which are stirred at room temperature, obtains fluorescence-causing substance new penta for 2~4 hours Acyl group quinoline amides polymer；
2) the valeryl quinoline amides polymer that step 1) obtains is dissolved in the mixed solvent of tetrahydrofuran and methanol, it will NaOH is added after being dissolved in deionized water, obtains the carboxylic acid of valeryl quinoline amides polymer after 1~4h of heating stirring；
3) carboxylic acid for the valeryl quinoline amides polymer that step 2) obtains under protection of argon gas, is dissolved in anhydrous dichloro Methane is added oxalyl chloride, is stirred at room temperature to obtain the acyl chlorides of valeryl quinoline amides polymer；
4) chiral 2- (2- aminophenyl) oxazole that 4 replace under protection of argon gas, is dissolved in anhydrous methylene chloride, N is added, N- diisopropylethylamine obtains solution c；The acyl chlorides for the valeryl quinoline amides polymer that step 3) obtains is dissolved in anhydrous two Chloromethanes obtains solution d, and stirring is after solution c, d are mixed to get Formulas I compound represented.
According to the certain embodiments of the application, in the step 1), n,N-diisopropylethylamine, 4- isobutoxy -8- The amine of amino -2- carboxyl quinoline amide polymer and the ratio of pivalyl chloride are 2~100:1:0.85~10；It is preferred that 2:1:1.2. The technical solution is easy to operate, and raw material is easy to get, and yield is higher.
According to the certain embodiments of the application, in the step 2), the ratio between tetrahydrofuran, methanol and amount of substance of water For 5~100:1~100:0.1~50；It is preferred that 10:1:1；The amount of the substance of valeryl quinoline amides polymer and sodium hydroxide The ratio between be 1:10~1:20.The operation scheme is simple and easy, and post-processing purification is all more simple, and yield is considerable.
According to the certain embodiments of the application, in the step 3), the carboxylic acid of valeryl quinoline amides polymer with The ratio between amount of substance of oxalyl chloride is 1:2~100；It is preferred that 1:2.Applicant it has been investigated that, use oxalyl chloride and carboxylic acid to carry out Reaction, operation, post-processing are simple, and yield is more considerable.
According to the certain embodiments of the application, in the step 4), the acyl chlorides and 4 of valeryl quinoline amides polymer The ratio between substituted amount of substance of chiral 2- (2- aminophenyl) oxazole is 1:0.85~1.2, preferably 1:0.9.Applicant is through grinding Study carefully discovery, prepares the compound using the method that acyl chlorides is condensed, reactivity is high, and reaction step is simple, and yield is more considerable.
The reaction equation of above-mentioned preparation method is as follows:
A kind of preparation method of the chiral fluorescent chemicals based on quinoline amides folded formation of the application, the compound are such as Shown in formula II above, the preparation method includes the following steps:
1) 4,7- diisobutyl -1,10- Phen -2,9- carboxylic acid under protection of argon gas, is dissolved in anhydrous methylene chloride, Oxalyl chloride is added, is stirred at room temperature to obtain 4,7- diisobutyl -1,10- Phen -2,9- carboxylic acid chloride；
2) amine of chiral quinoline amides polymer under protection of argon gas, is dissolved in anhydrous methylene chloride, N is added, N- bis- is different Propylethylamine obtains solution e；4,7- diisobutyl -1,10- Phen -2,9- the carboxylic acid chloride that step 1) obtains is dissolved in Anhydrous methylene chloride obtains solution f；Stirring is after solution e, f are closed to get Formula II compound represented.
According to the certain embodiments of the application, in the step 1), 4,7- diisobutyl -1,10- Phens -2,9- The ratio between amount of substance of carboxylic acid and oxalyl chloride is 1:5~1000, preferably 1:5.Applicant it has been investigated that, use oxalyl chloride and adjacent The reaction of ferrosin dicarboxylic acid compound, reactivity is high, and reaction step is simple, and yield is more considerable.
According to the certain embodiments of the application, in the step 2), 4,7- diisobutyl -1,10- Phens -2,9- Carboxylic acid chloride, N, N- diisopropylethylamine and 4 the ratio between amounts of substance of chiral 2- (2- aminophenyl) oxazole for replacing for 1:5~ 1000:2~10, preferably 1:5:2.Applicant has found after studying, and prepares the compound using the method that acyl chlorides is condensed, reaction is lived Property it is high, reaction step is simple, and yield is more considerable.
The reaction equation of above-mentioned preparation method is as follows:
As described above based on the chiral fluorescent chemicals of quinoline amides folded formation in the system in chiral luminous organic material Have broad application prospects in the preparation of standby, chiral fluorescence probe and fluorescence identifying field.
The invention will be further described for the following examples.Agents useful for same such as nothing is especially said in the embodiment of the present invention Bright is commercially available.
Embodiment 1
Preparation formula S-I1 and formula R-I1 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
1) 254mg A is added in the two-mouth bottle of 50mL, protection gas is made with argon gas, it is anhydrous that above compound is dissolved in 10mL In methylene chloride, 31 μ L of n,N-diisopropylethylamine is successively slowly added to syringe, it is small to be stirred at room temperature 3 by 25 μ L of pivalyl chloride When.The product as yellow powder B of column chromatography separation product, yield 93%；
2) 200mg B is dissolved in the in the mixed solvent of 10mL tetrahydrofuran Yu 2mL methanol in 50mL eggplant-shape bottle, by 72mg NaOH solid is dissolved in 2mL deionized water, after resulting NaOH solution is slowly dropped in the solution of B, by mixed liquor in 40 After heating 2 hours in DEG C oil bath, the dilute hydrochloric acid of 1mol/L, reaction solution are added dropwise into the solution after reaction for B compound complete hydrolysis PH be down to 4~5；Then it is extracted with a large amount of methylene chloride and deionized water, by organic phase anhydrous Na SO4Dry, decompression is steamed It is product C, yield 82% that yellow solid obtained by organic solvent is removed in distillation；
3) by 200mg C in 50mL two-mouth bottle, be dissolved in 10mL anhydrous methylene chloride under argon gas protection, with syringe plus Enter 15 μ L oxalyl chlorides, after being stirred at room temperature two hours, after vacuum distillation removes organic solvent, it is small that continuation vacuumizes two on vacuum pump When, after to be dissolved in 3mL anhydrous methylene chloride under protection of argon gas stand-by；It is 4-R base -2- (the 2- amino of 0.9 equivalent by the amount of substance Phenyl) oxazole or R-4-R-2- (2- aminophenyl) oxazole be dissolved in anhydrous dichloromethane under argon gas protection in 50mL two-mouth bottle Alkane, and be added 31 μ L n,N-diisopropylethylamine, after above-mentioned solution of acid chloride is slowly added to syringe, be stirred overnight at room temperature. Column chromatography separation product both obtains compound described in formula S-I1 or R-I1.Yield is 62%~85%.
When chiral amino oxazolyl phenyl is S-4- methyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-I1-a The compound, yield 62%.The structure detection structure of the compound is as follows:1H NMR(400MHz,CDCl3)δ13.18 (s,1H),12.21(s,1H),11.81(s,1H),11.33(s,1H),9.14(s,1H),8.77(d,1H),8.69(d,1H), 8.63(d,1H),8.15(d,1H),8.09(d,1H),8.02(d,1H),7.97(dd,2H),7.91(d,1H),7.67(dd, 1H),7.61(dd,2H),7.52(dd,1H),7.34(m,2H),7.27(d,1H),7.18(dd,1H),6.90(s,1H),6.81 (s, 1H), 4.46 (m, 1H), 4.36 (m, 1H), 4.14~4.21 (m, 2H), 3.87~3.97 (m, 4H), 3.06 (t, 1H), 2.57 (m, 2H), 2.46 (m, 1H), 2.20~2.37 (m, 4H), 2.02 (m, 1H), 1.19~1.35 (m, 24H), 0.81 (s, 9H),0.48(d,3H).13C NMR(151MHz,CDCl3)δ176.40,163.53,163.03,162.87,162.52, 162.48,162.19,150.43,150.33,149.61,149.06,139.24,138.48,137.91,137.79,137.03, 134.21,134.10,133.72,131.75,129.66,128.41,128.05,127.47,127.00,126.74,126.69, 125.30,122.95,122.55,122.47,122.01,121.60,120.10,117.45,116.99,116.78,116.46, 116.39,116.16,116.11,115.85,114.09,100.05,99.90,98.70,98.09,75.50,75.33, 75.20,69.73,67.43,42.40,39.77,29.77,28.37,28.28,28.24,27.06,19.57,19.40, 19.33.MS(ESI)calculated for C71H76N10O10[M+H]+:1229.5824,found 1229.5442；By detecting As a result it is found that above compound structure is correct.
When chiral amino oxazolyl phenyl is S-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-I1-b The compound, yield 85%.The structure detection structure of the compound is as follows:1H NMR(600MHz,CDCl3)δ13.12 (s,1H),12.18(s,1H),11.53(s,1H),11.28(s,1H),9.13(s,1H),8.70(d,1H),8.68(d,1H), 8.63(d,1H),8.12(d,1H),8.07(d,1H),8.00(d,1H),7.99(d,1H),7.95(d,1H),7.91(d,1H), 7.64-7.66(m,2H),7.59(dd,1H),7.54(td,1H),7.27-7.34(m,4H),7.20(t,1H),6.91(s, 1H),6.84(s,1H),6.64-6.47(m,2H),6.42(s,1H),6.41(s,1H),6.34(t,1H),4.44(dd,1H), 4.37(dd,1H),4.13-4.19(m,2H),3.95(d,2H),3.90(d,1H),3.24(dd,1H),2.50-2.55(m, 2H),2.30-2.40(m,3H),2.14(t,1H),2.10(dd,1H),1.98(dd,1H),1.19-1.33(m,36H),0.80 (s,11H).13C NMR(101MHz,)δ176.41,163.64,163.56,163.37,163.17,162.72,162.56, 162.34,161.95,160.92,150.43,150.39,149.65,149.14,141.24,139.06,138.36,137.96, 137.87,137.83,134.18,134.09,133.96,133.74,131.85,129.73,128.15,127.09,127.06, 126.72,125.79,123.07,122.56,122.52,121.87,121.68,120.29,117.11,117.03,116.77, 116.45,116.26,115.90,114.19,99.89,98.72,98.07,75.54,75.45,75.41,75.16,72.29, 69.23,39.79,29.78,28.38,28.34,28.26,27.09,19.57,19.53,19 .47,19.40.Yield:83% .MS(ESI)calculated for[M+H]+:1291.5975,found 1291.5975；By testing result it is found that above-mentionedization It is correct to close object structure.
When chiral amino oxazolyl phenyl is S-4- isobutyl group -2- (2- aminophenyl) oxazole, products therefrom is formula S-I1- Compound described in c, yield 68%.1H NMR(400MHz,CDCl3)δ13.26(s,1H),12.23(s,1H),11.78(s, 1H),11.35(s,1H),9.16(s,1H),8.74(d,1H),8.13(d,1H),8.63(d,1H),8.14(d,1H),8.07 (d,1H),8.01(d,1H),7.98(d,1H),7.97(d,1H),7.92(d,1H),7.66(dd,1H),7.63(d,1H), 7.62(d,1H),7.53(dd,1H),7.35(s,1H),7.34(d,1H),7.32(s,1H),7.28(d,1H),7.19(dd, 1H),6.91(s,1H),6.83(s,1H),4.43(dd,1H),4.39(dd,1H)4.20(t,1H),4.16(t,1H),3.88- 3.96(m,5H),3.20(t,1H),2.48-2.52(m,2H),2.28-2.36(m,2H),2.22(dd,1H),1.90(dd, 1H),1.20-1.33(m,50H),0.84(s,9H),0.15(dd,6H).13C NMR(101MHz,CDCl3)δ176.42, 163.59,163.10,162.79,162.63,162.13,162.01,161.08,150.47,150.39,149.93,148.98, 139.17,138.42,137.92,137.78,134.10,134.07,133.95,133.69,131.60,129.67,128.09, 126.98,126.85,126.75,122.95,122.49,121.98,121.61,120.00,117.26,116.97,116.48, 116.40,116.15,116.09,115.87,114.09,99.93,98.84,97.91,75.51,75.46,75.33,75.20, 71.68,68.21,39.78,32.88,32.00,29.77,29.44,28.42,28.36,28.27,27.23,27.07, 22.77,20.66,19.56,19.53,19.46,19.42,19.33,18.31,17.47,14 .20.Yield:76%.MS (ESI)calculated for[M+H]+:1257.6131,found 1257.6149；By testing result it is found that above compound Structure is correct.
When chiral amino oxazolyl phenyl is S-4- benzyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-I1-d The compound, yield 74%.1H NMR(600MHz,CDCl3)δ13.12(s,1H),12.18(s,1H),11.53(s, 1H),11.29(s,1H),9.13(s,1H),8.73(d,1H),8.67(d,1H),8.64(d,1H),8.12(d,1H),8.07 (d,1H),7.99(dd,2H),7.94(d,1H),7.89(d,1H),7.65(m,3H),7.59(dd,1H),7.54(dd,1H), 7.33(m,2H),7.29,(m,2H),7.20(dd,1H),6.91(s,1H),6.84(s,1H),6.45(dd,2H),6.42(dd, 2H),6.34(dd,1H),4.44(t,1H),4.38(t,1H),4.16(m,2H),3.94(d,2H),3.94(d,2H),3.24 (t, 1H), 2.53 (m, 2H), 2.34 (m, 4H), 2.14 (m, 2H), 1.98 (dd, 1H), 1.19~1.32 (m, 24H), 0.80 (s, 9H).13C NMR(151MHz,CDCl3)δ176.39,163.54,163.05,162.86,162.55,162.49,162.20, 161.98,161.03,150.45,150.36,149.65,149.09,139.25,138.50,137.94,137.81,137.04, 134.22,134.14,133.74,131.73,129.65,128.40,128.04,127.48,126.99,126.73,126.68, 125.30,122.92,122.57,122.49,122.03,121.63,120.09,117.44,117.00,116.77,116.49, 116.38,116.19,116.09,115.83,114.11,100.06,99.90,98.73,98.12,75.50,75.33, 75.21,69.72,67.41,42.37,39.76,29.75,28.38,28.28,28.23,27.05,19.54,19.51, 19.45,19.37,19.31.MS(ESI)calculated for[M+H]+:1305.6131,found 1305.6149；By examining Result is surveyed it is found that above compound structure is correct.
When chiral amino oxazolyl phenyl is R-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula R-I1 institute The compound stated.Yield is 78%.1H NMR(600MHz,CDCl3)δ13.12(s,1H),12.18(s,1H),11.53(s, 1H),11.28(s,1H),9.13(s,1H),8.70(d,1H),8.68(d,1H),8.64(d,1H),8.13(d,1H),8.07 (d,1H),8.00(d,1H),7.99(d,1H),7.95(d,1H),7.90(d,1H),7.64-7.66(m,2H),7.59(dd, 1H),7.54(td,1H),7.27-7.34(m,4H),7.20(t,1H),6.91(s,1H),6.84(s,1H),6.64-6.47(m, 2H),6.42(s,1H),6.41(s,1H),6.34(t,1H),4.44(dd,1H),4.37(dd,1H),4.13-4.19(m,2H), 3.95(d,2H),3.90(d,1H),3.24(dd,1H),2.50-2.55(m,2H),2.30-2.40(m,3H),2.14(t,1H), 2.10(dd,1H),1.98(dd,1H),1.19-1.33(m,36H),0.80(s,11H).13C NMR(101MHz,)δ176.41, 163.64,163.56,163.37,163.17,162.72,162.56,162.34,161.95,160.92,150.43,150.39, 149.65,149.14,141.24,139.06,138.36,137.96,137.87,137.83,134.18,134.09,133.96, 133.74,131.85,129.73,128.15,127.09,127.06,126.72,125.79,123.07,122.56,122.52, 121.87,121.68,120.29,117.11,117.03,116.77,116.45,116.26,115.90,114.19,99.89, 98.72,98.07,75.54,75.45,75.41,75.16,72.29,69.23,39.79,29.78,28.38,28.34, 28.26,27.09,19.57,19.53,19.47,19.40.Yield:78%.MS (ESI) calculated for [M+H]+: 1291.5975,found 1291.5993；By testing result it is found that above compound structure is correct.
Embodiment 2
Preparation formula S-I2 or R-I2 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
1) 490mg E is added in the two-mouth bottle of 50mL, protection gas is made with argon gas, it is anhydrous that above compound is dissolved in 10mL In methylene chloride, 31 μ L of n,N-diisopropylethylamine is successively slowly added to syringe, 15 μ L of pivaloyl is stirred at room temperature 3 hours. The product as yellow powder F of column chromatography separation product, yield 71%；
2) 400mg F is dissolved in the in the mixed solvent of 10mL tetrahydrofuran Yu 2mL methanol in 50mL eggplant-shape bottle, it will 140mg NaOH solid is dissolved in 2mL deionized water, after resulting NaOH solution is slowly dropped in the solution of F, will be mixed After liquid heats 4 hours in 40 DEG C of oil baths, the dilute hydrochloric acid of 1mol/L is added dropwise into the solution after reaction for F compound complete hydrolysis, The pH of reaction solution is down to 4~5.Then it is extracted with a large amount of methylene chloride and deionized water, by organic phase anhydrous Na SO4It is dry, It is product G that vacuum distillation, which removes yellow solid obtained by organic solvent,；Yield 96%；
3) by 300mg G in 50mL two-mouth bottle, be dissolved in 10mL anhydrous methylene chloride under argon gas protection, with syringe plus Enter 10 μ L oxalyl chlorides, after being stirred at room temperature two hours, after vacuum distillation removes organic solvent, it is small that continuation vacuumizes two on vacuum pump When, after to be dissolved in 3mL anhydrous methylene chloride under protection of argon gas stand-by；It is 4-R base -2- (the 2- amino of 0.9 equivalent by the amount of substance Phenyl) oxazole is dissolved in anhydrous methylene chloride in 50mL two-mouth bottle under argon gas protection, and 31 μ L N, N- diisopropyl second are added Amine, after above-mentioned solution of acid chloride is slowly added to syringe, be stirred overnight at room temperature.It is formula S-I2 or R- that column chromatography separation, which produces, Compound described in I2.Yield is 64%~71%.
When chiral amino oxazolyl phenyl is S-4- methyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-I2-a The compound, yield 65%.The structure detection structure of the compound is as follows:1H NMR(600MHz,CDCl3)δ12.61 (s,1H),11.26(s,1H),11.20(s,1H),10.90(s,1H),10.84(s,1H),10.72(s,1H),10.68(s, 1H),8.62(s,1H),8.29(dd,1H),8.16(dd,1H),8.14(dd,1H),8.02(dd,1H),7.90-7.94(m, 5H),8.86(dd,1H),8.84(dd,1H),7.82(dd,1H),7.81(dd,1H),7.72(dd,1H),7.71(dd,1H), 7.69(dd,1H),7.65(dd,1H),7.35-3.38(m,3H),7.27-7.34(m,4H),7.20(m,2H),7.16(dd, 1H),7.07(dd,1H),7.04(dd,1H),6.92(s,1H),6.89(dd,1H),6.85(s,1H),6.71(s,1H),6.65 (s,1H),6.44(s,1H),6.31(s,1H),6.29(s,1H),6.04(s,1H),4.15-4.18(m,1H),4.10-4.15 (m,3H),4.00-4.07(m,2H),3.78-3.96(m,13H),3.74(t,1H),3.66(t,1H),2.83(t,1H),2.33 ~2.51 (m, 10H), 2.21 (m, 2H), 2.17 (dd, 1H), 1.84 (m, 2H), 1.11-1.34 (m, 50H), 0.51 (s, 9H), 0.22(d,3H).13C NMR(151MHz,CDCl3)δ176.00,163.09,162.96,162.74,162.64,162.49, 162.36,162.26,162.10,161.42,161.35,161.11,160.90,159.97,159.47,159.22,158.85, 149.78,149.71,149.55,149.18,148.78,148.74,148.57,148.31,138.45,138.13,137.72, 137.69,137.40,137.27,137.14,133.65,133.62,133.43,133.10,133.00,132.93,132.56, 131.19,128.91,127.40,126.64,126.52,126.39,126.15,125.84,125.69,125.66,122.60, 122.46,122.26,122.18,122.03,121.92,121.62,121.40,119.88,117.20,116.96,116.79, 116.71,116.61,116.23,116.18,116.03,115.81,115.70,115.64,113.83,99.51,99.10, 98.84,98.57,98.50,98.44,97.88,75.36,75.21,75.17,75.14,75.06,75.03,74.90, 71.11,60.69,39.42,29.75,28.25,28.20,28.17,28.12,28.09,26.79,22.75,21.15, 19.69,19.61,19.53,19.49,19.45,19.34,19.32,19.27.MS(ESI)calculated for[M+2H]2+: 1099.5056,found 1099.5072；By testing result it is found that above compound structure is correct.
When chiral amino oxazolyl phenyl is S-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-I2-b The compound, yield 76%.The structure detection structure of the compound is as follows:1H NMR(600MHz,CDCl3)δ12.51 (s,1H),11.32(s,1H),11.21(s,1H),11.10(s,1H),10.86(s,1H),10.72(s,1H),10.69(s, 1H),8.62(s,1H),8.16(dd,1H),8.15(dd,1H),8.03(dd,1H),7.95(dd,1H),7.94(dd,1H), 7.90-7.92(m,4H),7.82(dd,1H),7.81(dd,1H),7.76(dd,1H),7.74(dd,1H),7.72(dd,1H), 7.70(dd,1H),7.65(dd,1H),7.40(dd,1H),7.35(m,3H),7.29(m,4H),7.17(dd,1H),7.19 (dd,1H),7.05(m,2H),6.93(dd,1H)6.92(s,1H),6.85(s,1H),6.73(s,1H),6.61(dd,1H), 6.60(s,1H),6.51(dd,1H),6.40(s,1H),6.33(s,1H),6.33(s,1H),6.17(s,1H),6.03(s, 1H),4.17(m,1H),4.12(m,2H),4.07(m,3H),4.00(dd,2H),3.89-3.95(m,6H),3.82(m,2H), 3.77(dd,1H),3.71(t,1H),3.65(t,1H),3.14(t,1H),2.75(t,1H),2.62(dd,1H),2.33-2.46 (m,8H),2.20(m,1H),1.09-1.36(m,50H),0.51(s,9H).13C NMR(151MHz,CDCl3)δ176.02, 163.11,162.98,162.80,162.75,162.51,162.20,161.44,160.91,160.69,160.04,159.47, 159.23,158.88,149.81,149.72,149.19,149.07,148.74,148.60,148.31,141.03,138.50, 137.97,137.76,137.67,137.44,137.29,137.15,133.66,133.45,133.03,132.93,132.59, 131.48,129.11,127.89,127.48,126.82,126.66,126.40,126.15,125.88,125.72,125.63, 125.55,122.58,122.27,122.04,121.91,121.44,120.13,117.24,116.99,116.70,116.43, 116.27,116.18,116.05,115.82,113.75,99.52,99.10,98.80,98.43,97.97,75.37,75.24, 75.19,75.11,75.03,74.87,71.92,68.80,39.42,32.00,29.77,29.44,28.26,28.14, 26.78,22.76,19.70,19.62,19.53,19.51,19.45,19.34,19.32,19.27,14.19.MS(ESI) calculated for[M+2H]2+:1130.5134,found 1130.5140；By testing result it is found that above compound structure Correctly.
When chiral amino oxazolyl phenyl is S-4- isopropyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-I2- Compound described in c, yield 67%.The structure detection structure of the compound is as follows:1H NMR(400MHz,CDCl3)δ12.68 (s,1H),11.27(s,2H),11.22(s,1H),10.90(s,1H),10.87(s,1H),10.73(s,1H),10.69(s, 1H),8.63(s,1H),8.24(d,1H),8.17(dd,1H),8.03(dd,1H),7.90-7.93(m,4H),7.88(d,1H), 7.80-7.87(m,4H),7.75(d,1H),7.71(d,1H),7.65(d,1H),7.39(d,1H),7.38(d,1H),7.29- 7.35(m,5H),7.14-7.24(m,3H),7.04(dd,1H),7.03(dd,1H),6.91(s,1H),6.90(dd,1H), 6.85(s,1H),6.73(s,1H),6.66(s,1H),6.46(s,1H),6.31(s,1H),6.27(s,1H),6.03(s,1H), 4.09-4.18(m,6H),3.87-4.05(m,11H),3.77-3.83(m,5H),3.37(t,1H),3.65(t,1H),2.97 (t,1H),2.34-2.53(m,11H),2.22(t,2H),1.64(t,1H)0.96-1.43(m 110H),0.88(s,9H),- 0.07(d,3H),-0.12(d,3H).13C NMR(101MHz,CDCl3)δ176.02,163.09,162.95,162.71, 162.51,162.32,162.27,162.22,161.43,160.89,159.88,159.49,159.26,158.88,149.79, 149.71,149.52,149.23,148.94,148.70,148.57,148.31,138.63,138.04,137.74,137.71, 137.42,137.37,137.27,137.15,133.61,133.43,133.09,133.01,132.93,132.57,131.23, 129.06,127.45,126.65,126.57,126.39,126.16,125.83,125.69,122.60,122.46,122.26, 122.17,122.01,121.92,121.56,121.43,119.74,117.24,117.11,116.99,116.74,116.65, 116.24,116.05,115.80,115.66,113.55,99.52,99.11,98.84,98.54,98.47,98.41,97.83, 75.36,75.21,75.06,74.91,71.27,67.85,39.42,32.62,32.00,29.77,29.43,28.24, 28.21,28.16,28.13,26.78,22.76,19.69,19.61,19.56,19.53,19.45,19.34,19.28, 18.04,17.21,14.19.MS(ESI)calculated for[M+2H]2+:1113.5212,found 1130.5235；By examining Result is surveyed it is found that above compound structure is correct.
When chiral amino oxazolyl phenyl is S-4- benzyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-I2-d The compound, yield 64%.The structure detection structure of the compound is as follows:1H NMR(600MHz,CDCl3)δ12.53 (s,1H),11.22(s,1H),11.19(s,1H),10.98(s,1H),10.83(s,1H),10.83(s,1H),10.72(s, 1H),10.67(s,1H),8.62(s,1H),8.19(m,3H),8.01(dd,1H),7.89-7.93(m,4H),7.79-7.83 (m,4H),7.75(dd,1H),7.71(dd,1H),7.69(dd,1H),7.64(dd,1H),7.37(dd,1H),7.35(dd, 1H),7.33(dd,1H),7.27-7.31(m,3H),7.21(dd,1H),7.19(dd,1H),7.16(dd,1H),7.05(dd, 1H),7.03(dd,1H),6.91(dd,1H),6.90(dd,1H),6.84(s,1H),6.73(s,1H),6.66(s,1H),6.43 (s,1H),6.32(s,1H),6.31(s,1H),6.28(s,1H),6.25(s,1H),6.23(dd,1H),6.20(s,1H), 6.19(s,1H),6.01(s,1H),4.16(t,1H),4.10-4.17(m3H),4.02(t,1H),3.93-3.98(m,4H), 3.77-3.91(m,10H),3.64(t,1H),3.00(t,1H),2.22-2.52(m,8H),1.95(t,1H),1.83-1.87 (dd,2H),1.15-1.35(m,73H),0.50(s,9H).13C NMR(151MHz,CDCl3)δ176.01,163.09, 162.96,162.66,162.62,162.48,162.33,162.27,162.13,161.91,161.43,160.90,160.87, 159.91,159.47,159.23,158.88,149.79,149.71,149.20,149.02,148.63,148.55,148.31, 138.68,138.11,137.71,137.43,137.42,137.36,137.27,137.14,136.91,133.69,133.64, 133.61,133.44,133.11,133.02,132.94,132.61,131.38,129.06,128.21,127.40,127.34, 126.64,126.44,126.38,126.13,125.85,125.71,125.68,125.16,122.64,122.48,122.26, 122.18,122.01,121.98,121.92,121.60,121.41,119.86,117.30,117.19,116.96,116.72, 116.63,116.52,116.26,116.22,116.19,116.06,115.80,115.70,115.63,113.55,99.52, 99.49,99.24,98.82,98.46,98.40,98.05,75.38,75.36,75.19,75.05,75.02,74.92, 69.35,67.08,42.16,39.42,29.77,29.39,28.26,28.25,28.20,28.16,28.13,28.09, 27.29,26.78,22.76,19.70,19.68,19.65,19.54,19.52,19.51,19.48,19.45,19.42, 19.37,19.33,19.31,19.27,19.26,14.18,0.06.MS(ESI)calculated for[M+2H]2+: 1137.5212,found 1137.5234；By testing result it is found that above compound structure is correct.
When chiral amino oxazolyl phenyl is R-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula R-I2 institute The compound stated, yield 76%.The structure detection structure of the compound is as follows:1H NMR(600MHz,CDCl3)δ12.51(s, 1H),11.33(s,1H),11.21(s,1H),11.10(s,1H),10.86(s,1H),10.72(s,1H),10.69(s,1H), 8.62(s,1H),8.16(dd,1H),8.15(dd,1H),8.03(dd,1H),8.14(dd,1H),7.96(dd,1H),7.94 (dd,1H),7.90-7.92(m,4H),7.81(dd,1H),7.81(dd,1H),7.77(dd,1H),7.75(dd,1H),7.72 (dd,1H),7.70(dd,1H),7.65(dd,1H),7.40(dd,1H),7.35(m,3H),7.29(m,4H),7.17(dd, 1H),7.19(dd,1H),7.05(m,2H),6.93(dd,1H)6.92(s,1H),6.85(s,1H),6.73(s,1H),6.61 (dd,1H),6.60(s,1H),6.51(dd,1H),6.40(s,1H),6.33(s,1H),6.33(s,1H),6.17(s,1H), 6.03(s,1H),4.17(m,1H),4.12(m,2H),4.07(m,3H),4.00(dd,2H),3.89-3.95(m,6H),3.82 (m,2H),3.76(t,1H),3.71(t,1H),3.65(t,1H),3.14(t,1H),2.75(t,1H),2.62(dd,1H), 2.33-2.46(m,8H),2.20(m,1H),1.09-1.36(m,50H),0.51(s,9H).13C NMR(151MHz,CDCl3)δ 176.03,163.11,162.98,162.80,162.75,162.51,162.41,162.27,162.20,162.14,161.44, 160.91,160.69,160.04,159.47,159.23,158.88,149.81,149.71,149.18,149.07,148.74, 148.60,148.30,141.02,138.50,137.97,137.76,137.67,137.44,137.29,137.14,133.66, 133.45,133.03,132.93,132.58,131.49,130.97,129.11,128.91,127.89,127.48,126.82, 126.66,126.48,126.40,126.15,125.89,125.73,125.64,125.55,122.58,122.27,122.21, 122.03,121.91,121.44,120.13,117.24,116.99,116.90,116.75,116.70,116.43,116.27, 116.18,116.05,115.83,115.75,115.65,113.75,99.52,99.10,98.80,98.53,98.42, 97.96,75.35,75.24,75.19,75.11,75.03,74.87,71.92,68.80,65.64,39.42,32.00, 30.66,29.77,29.44,28.26,28.16,28.12,26.79,22.77,19.68,19.62,19.53,19.51, 19.46,19.34,19.33,19.27,14.19,13.80.MS(ESI)calculated for[M+2H]2+:1130.5134, found 1130.5148；By testing result it is found that above compound structure is correct.
Embodiment 3
Preparation formula S-I3 or R-I3 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
1) by 200mg L in 50mL two-mouth bottle, be dissolved in 3mL anhydrous methylene chloride under argon gas protection, with syringe plus Enter 5 μ L oxalyl chlorides, after being stirred at room temperature two hours, after vacuum distillation removes organic solvent, it is small that continuation vacuumizes two on vacuum pump When, after to be dissolved in 1mL anhydrous methylene chloride under protection of argon gas stand-by；It is 4-R base -2- (the 2- amino of 0.9 equivalent by the amount of substance Phenyl) oxazole is dissolved in anhydrous methylene chloride in 50mL two-mouth bottle under argon gas protection, and 11 μ L N, N- diisopropyl second are added Amine, after above-mentioned solution of acid chloride is slowly added to syringe, be stirred overnight at room temperature.Column chromatography separation product both obtains compound M, Yield is 61%~63%.
2) it is dissolved in 5mL ethyl acetate after mixing 150mg compound M with the palladium carbon solid of 10% content of 15mg, this is molten Liquid gas pressure is that heating stirring is stayed overnight in 1.0 megapascal hydrogen；Preferably, reaction temperature is 60 DEG C；Reaction solution is cooled down afterwards, passes through silicon Diatomaceous earth filters out the palladium carbon solid after reaction, solvent is distilled off in resulting filtrate decompression, gained yellow solid is compound N.Yield is 89~95%；
3) 490mg N is added in the two-mouth bottle of 25mL, protection gas is made with argon gas, it is anhydrous that above compound is dissolved in 10mL In methylene chloride, it is slowly added to 10 μ L of n,N-diisopropylethylamine with syringe, 8 μ L of pivalyl chloride is stirred at room temperature 3 hours；Column The product as yellow powder O of chromatography separation product, as S-I3 or R-I3 compound represented.Yield 64~71%.
When chiral amino oxazolyl phenyl is S-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-I3 institute The compound stated, yield 71%.The structure detection structure of the compound is as follows:1H NMR(600MHz,CDCl3)δ12.27(s, 1H),10.92(s,1H),10.78(s,1H),10.77(s,1H),10.40(s,1H),10.36(s,1H),10.25(s,1H), 10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s,1H),10.02(s,1H),9.99(s,1H),9.96 (s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H),7.97(d,1H),7.92(d,1H),7.73-7.79(m, 6H),7.68-7.71(m,5H),7.59-7.65(m,12H),7.55(d,1H),7.50(d,1H),7.39(d,1H),7.31(d, 1H),7.20(d,1H),7.18(d,1H),7.07-7.12(m,3H),6.94-7.00(m,9H),6.92(d,1H),6.91(d, 1H),6.90(d,1H),6.86(d,1H),6.85(d,1H),6.75-6.81(7H),6.67(s,1H),6.65(s,1H),6.50 (dd,1H),6.48(s,1H),6.45(s,1H),6.41(d,1H),6.40(d,1H),6.27(dd,1H),6.06(s,1H), 6.03(s,1H),6.01(s,1H),6.00(s,1H),5.93(s,1H),5.90(s,1H),5.87(s,1H),5.79(s,1H), 5.77(s,1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.73(s,1H),5.70(s,1H),3.95(m,2H), 3.83-3.87(m,2H),3.74-3.79(m,5H),3.63-3.71(m,16H),3.49-3.60(m,15H),3.00(t,1H), 2.52(t,1H),2.42(dd,1H),2.71-2.31(m,20H),1.25(s,104H),1.00-1.21(m,144H),0.84- 0.94(m,30H).MS(MALDI)calculated for C244H246N34O34[M+H]+:4196.86,found 4196.13.； By testing result it is found that above compound structure is correct.
When chiral amino oxazolyl phenyl is R-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula R-I3 institute The compound stated, yield 64%.The structure detection structure of the compound is as follows:1H NMR(600MHz,CDCl3)δ12.27(s, 1H),10.92(s,1H),10.78(s,1H),10.77(s,1H),10.40(s,1H),10.36(s,1H),10.25(s,1H), 10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s,1H),10.02(s,1H),9.99(s,1H),9.96 (s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H),7.97(d,1H),7.92(d,1H),7.73-7.79(m, 6H),7.68-7.71(m,5H),7.59-7.65(m,12H),7.55(d,1H),7.50(d,1H),7.39(d,1H),7.31(d, 1H),7.20(d,1H),7.18(d,1H),7.07-7.12(m,3H),6.94-7.00(m,9H),6.92(d,1H),6.91(d, 1H),6.90(d,1H),6.86(d,1H),6.85(d,1H),6.75-6.81(7H),6.67(s,1H),6.65(s,1H),6.50 (dd,1H),6.48(s,1H),6.45(s,1H),6.41(d,1H),6.40(d,1H),6.27(dd,1H),6.06(s,1H), 6.03(s,1H),6.01(s,1H),6.00(s,1H),5.93(s,1H),5.90(s,1H),5.87(s,1H),5.79(s,1H), 5.77(s,1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.73(s,1H),5.70(s,1H),3.95(m,2H), 3.83-3.87(m,2H),3.74-3.79(m,5H),3.63-3.71(m,16H),3.49-3.60(m,15H),3.00(t,1H), 2.52(t,1H),2.42(dd,1H),2.71-2.31(m,20H),1.25(s,104H),1.00-1.21(m,144H),0.84- 0.94(m,30H).MS(MALDI)calculated for C244H246N34O34[M+H]+:4196.86,found 4196.99；By Testing result is it is found that above compound structure is correct.
Embodiment 4
Preparation formula S-II1 or R-II1 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
1) by 200mg compound I in 50mL two-mouth bottle, it is dissolved in 5mL anhydrous methylene chloride under argon gas protection, with injection 34 μ L oxalyl chlorides are added in device, and after being stirred at room temperature two hours, after vacuum distillation removes organic solvent, continuation vacuumizes on vacuum pump Two hours, after to be dissolved in 1mL anhydrous methylene chloride under protection of argon gas stand-by.It is the 4-R base -2- (2- of 0.9 equivalent by the amount of substance Aminophenyl) oxazole is dissolved in anhydrous methylene chloride in 50mL two-mouth bottle under argon gas protection, and 65 μ L N, N- diisopropyls are added Base ethamine, after above-mentioned solution of acid chloride is slowly added to syringe, be stirred overnight at room temperature；Column chromatography separation product both obtains chemical combination Object J；Yield is 71%~85%；
2) it is dissolved in 10mL ethyl acetate after mixing 200mg compound J with the palladium carbon solid of 10% content of 20mg, by this Solution air pressure is that heating stirring is stayed overnight in atmosphere of hydrogen.The palladium carbon solid after reaction is filtered out by diatomite, by resulting filter Liquid vacuum distillation removes solvent, and gained yellow solid is compound K；Yield is 91~95%；
3) by 20mg P in 50mL two-mouth bottle, it is dissolved in 5mL anhydrous methylene chloride under argon gas protection, is added with syringe 10 μ L oxalyl chlorides, after being stirred at room temperature two hours, after vacuum distillation removes organic solvent, it is small that continuation vacuumizes two on vacuum pump When, after to be dissolved in 3mL anhydrous methylene chloride under protection of argon gas stand-by.By the amount of substance be 2.0 equivalents compound K in 50mL two Anhydrous methylene chloride is dissolved in mouthful bottle under argon gas protection, and 21 μ L n,N-diisopropylethylamine are added, after will be upper with syringe It states solution of acid chloride to be slowly added to, be stirred overnight at room temperature；Column chromatography separation product is chemical combination described in formula S-II1 or R-II1 Object；Yield is 41%~51%.
When chiral amino oxazolyl phenyl is S-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-II1 institute The compound stated, yield 41%.The structure detection structure of the compound is as follows:1H NMR(600MHz,CDCl3)δ12.35(s, 2H),12.04(s,2H),11.03(s,2H),10.97(s,2H),10.81(s,2H),8.10(dd,2H),8.09(dd,2H), 8.00(d,2H),7.92(d,2H),7.80(d,2H),7.68(d,1H),7.64(d,1H),7.56(d,1H),7.47(d,1H), 7.47(s,1H),7.42(d,1H),7.33(d,1H),7.04-7.19(m,6H),7.07(dd,2H),6.88(dd,2H),6.58 (d,2H),6.54(s,2H),6.52(d,2H),6.48(d,2H),6.43(s,2H),6.26(s,2H),6.14(s,2H),6.13 (s,2H),6.11(s,2H),6.07(s,2H),3.84-3.91(m,16H),3.73-3.79(m,6H),3.64-3.66(m, 4H),3.09(t,2H),2.74(dd,2H),2.36-2.50(m,10H),2.22-2.29(m,4H),2.12-2.15(m,2H), 1.23-1.33(m,160H).13C NMR(151MHz,CDCl3)δ162.68,162.61,162.10,162.06,161.84, 161.75,161.58,160.53,159.78,159.74,159.55,148.90,148.81,148.48,148.21,147.43, 142.52,141.18,138.61,138.02,137.75,137.03,136.68,133.72,133.44,133.18,133.10, 131.21,129.18,127.85,127.32,126.73,126.45,126.22,125.54,122.26,121.55,121.46, 121.10,120.82,119.98,119.82,119.00,116.91,116.71,116.64,116.21,115.98,115.04, 113.68,99.63,98.41,98.13,97.56,75.28,75.17,75.04,74.81,71.85,68.76,32.00, 29.85,29.77,29.68,29.40,29.32,28.35,28.29,28.24,28.21,28.08,27.29,25.61, 22.76,19.80,19.75,19.68,19.59,19.55,19.42,19.31,14.18,1.09,0.07.MS(ESI) calculated for C164H160N22O22[M+H]2+:1395.6111,found1395.6115；It is by testing result it is found that above-mentioned Compound structure is correct.
When chiral amino oxazolyl phenyl is R-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula R-II1 institute The compound stated, yield 51%.The structure detection structure of the compound is as follows:1H NMR(400MHz,CDCl3)δ12.35(s, 2H),12.04(s,2H),11.03(s,2H),10.97(s,2H),10.81(s,2H),8.10(dd,2H),8.09(dd,2H), 8.00(d,2H),7.92(d,2H),7.80(d,2H),7.68(d,1H),7.64(d,1H),7.56(d,1H),7.47(d,1H), 7.47(s,1H),7.42(d,1H),7.33(d,1H),7.04-7.19(m,6H),7.07(dd,2H),6.88(dd,2H),6.58 (d,2H),6.54(s,2H),6.52(d,2H),6.48(d,2H),6.43(s,2H),6.26(s,2H),6.14(s,2H),6.13 (s,2H),6.11(s,2H),6.07(s,2H),3.84-3.91(m,16H),3.73-3.79(m,6H),3.64-3.66(m, 4H),3.09(t,2H),2.74(dd,2H),2.36-2.50(m,10H),2.22-2.29(m,4H),2.12-2.15(m,2H), 1.23-1.33(m,200H).13C NMR(151MHz,CDCl3)δ163.30,163.20,163.13,163.04,162.62, 162.53,162.16,161.77,160.62,153.67,150.53,149.86,149.33,145.52,141.29,139.11, 138.98,138.45,138.23,135.45,133.93,133.92,131.79,129.64,128.73,128.09,127.93, 127.02,126.73,126.50,125.74,125.70,124.19,124.09,122.98,122.59,122.04,121.92, 120.47,117.66,117.09,116.71,116.50,115.26,100.36,99.97,99.00,97.73,75.79, 75.45,75.43,75.20,72.16,69.09,53.68,41.95,32.00,29.76,29.73,29.43,29.39, 28.38,28.36,28.30,28.24,22.76,19.53,19.51,19.46,19.43,19.40,19.34,19.28, 19.26,18.68,17.40,14.18,12.06.MS(ESI)calculated for C164H160N22O22[M+H]2+: 1395.6111,found 1395.6134；By testing result it is found that above compound structure is correct.
Embodiment 5,
Preparation formula S-II2 or R-II2 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
1) by 200mg compound R in 50mL two-mouth bottle, it is dissolved in 3mL anhydrous methylene chloride under argon gas protection, with injection 17 μ L oxalyl chlorides are added in device, and after being stirred at room temperature two hours, after vacuum distillation removes organic solvent, continuation vacuumizes on vacuum pump Two hours, after to be dissolved in 1mL anhydrous methylene chloride under protection of argon gas stand-by；It is the 4-R base -2- (2- of 0.9 equivalent by the amount of substance Aminophenyl) oxazole is dissolved in anhydrous methylene chloride in 50mL two-mouth bottle under argon gas protection, and 35 μ L N, N- diisopropyls are added Base ethamine, after above-mentioned solution of acid chloride is slowly added to syringe, be stirred overnight at room temperature.Column chromatography separation product both obtains chemical combination Object S；Yield is 71%~85%；
2) it is dissolved in 10mL ethyl acetate after mixing 200mg compound S with the palladium carbon solid of 10% content of 20mg, by this Solution air pressure is that heating stirring is stayed overnight in atmosphere of hydrogen；The palladium carbon solid after reaction is filtered out by diatomite, by resulting filter Liquid vacuum distillation removes solvent, and gained yellow solid is compound T；Yield is 91~95%；
3) by 20mg P in 50mL two-mouth bottle, be dissolved in 10mL anhydrous methylene chloride under argon gas protection, with syringe plus Enter 10 μ L oxalyl chlorides, after being stirred at room temperature two hours, after vacuum distillation removes organic solvent, it is small that continuation vacuumizes two on vacuum pump When, after to be dissolved in 3mL anhydrous methylene chloride under protection of argon gas stand-by.By the amount of substance be 2.0 equivalents compound T in 50mL two Anhydrous methylene chloride is dissolved in mouthful bottle under argon gas protection, and 21 μ L n,N-diisopropylethylamine are added, after will be upper with syringe It states solution of acid chloride to be slowly added to, be stirred overnight at room temperature；Column chromatography separation product is up to chemical combination described in formula S-II2 or R-II2 Object；Yield is 28~33%.
When chiral amino oxazolyl phenyl is S-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-II2 institute The compound stated, yield 33%.The structure detection structure of the compound is as follows:1H NMR(600MHz,CDCl3)δ12.41(s, 1H),11.64(s,1H),11.14(s,1H),11.01(s,1H),10.95(s,1H),10.68(s,1H),10.60(s,1H), 10.58(s,1H),10.51(s,1H),8.11(d,1H),8.06(d,1H),8.03(d,1H),7.97(d,1H),7.96(d, 1H),7.92(d,1H),7.90(d,1H),7.87(d,1H),7.82(d,1H),7.80(d,1H),7.76(d,1H),7.74(d, 1H),7.72(d,1H),7.71(d,1H),7.62(d,1H),7.56(d,1H),7.41(d,1H),7.28-7.32(m,6H), 7.19-7.24(m,10H),7.15(dd,1H),7.09-7.12(m,3H),7.03-7.08(m,4H),7.02(s,1H),6.92 (s,1H),6.89(d,1H),6.88(d,1H),6.59(s,1H),6.57(d,1H),6.57(s,1H),6.50(s,1H),6.48 (d,1H),6.47(d,1H),6.28(s,1H),6.28(s,1H),6.15(s,1H),6.12(s,1H),6.11(s,1H),6.10 (s,1H),5.93(s,1H),4.11(m,2H),3.99-4.04(m,2H),3.84-3.92(m,20H),3.68-3.79(m, 20H),3.58(t,1H),3.08(t,1H),2.67(t,1H),2.52(dd,1H),2.33-2.44(m,19H),0.81-1.35 (m,90H).13C NMR(101MHz,CDCl3)δ162.56,162.35,161.99,161.91,161.68,161.21, 161.03,160.93,160.39,159.63,158.99,158.76,158.35,148.90,148.55,148.37,148.31, 148.20,147.57,147.31,146.66,141.81,140.94,138.28,137.73,137.42,137.04,136.91, 136.75,136.23,135.97,133.35,133.19,132.52,132.31,131.32,128.91,127.73,127.20, 126.65,126.30,125.94,125.62,125.41,125.15,122.41,121.95,121.70,121.23,121.09, 120.30,119.99,119.27,118.43,116.61,116.32,115.38,114.62,113.53,99.34,98.48, 98.22,98.07,97.82,97.61,74.88,74.70,72.29,71.71,68.56,32.01,31.52,30.39, 30.28,29.78,29.44,28.87,28.53,28.11,28.01,27.89,27.80,22.78,21.99,21.45, 19.69,19.61,19.56,19.47,19.38,19.34,19.24,19.21,14.21,9.76.MS(MALDI) calculated for C276H274N38O38[M+H]+:4729.0755,found 4729.51；By testing result it is found that above-mentionedization It is correct to close object structure.
When chiral amino oxazolyl phenyl is R-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula R-II2 institute The compound stated, yield 28%.The structure detection structure of the compound is as follows:1H NMR(600MHz,CDCl3)δ12.41(s, 1H),11.64(s,1H),11.14(s,1H),11.01(s,1H),10.95(s,1H),10.68(s,1H),10.60(s,1H), 10.58(s,1H),10.51(s,1H),8.11(d,1H),8.06(d,1H),8.03(d,1H),7.97(d,1H),7.96(d, 1H),7.92(d,1H),7.90(d,1H),7.87(d,1H),7.82(d,1H),7.80(d,1H),7.76(d,1H),7.74(d, 1H),7.72(d,1H),7.71(d,1H),7.62(d,1H),7.56(d,1H),7.41(d,1H),7.28-7.32(m,6H), 7.19-7.24(m,10H),7.15(dd,1H),7.09-7.12(m,3H),7.03-7.08(m,4H),7.02(s,1H),6.92 (s,1H),6.89(d,1H),6.88(d,1H),6.59(s,1H),6.57(d,1H),6.57(s,1H),6.50(s,1H),6.48 (d,1H),6.47(d,1H),6.28(s,1H),6.28(s,1H),6.15(s,1H),6.12(s,1H),6.11(s,1H),6.10 (s,1H),5.93(s,1H),4.11(m,2H),3.99-4.04(m,2H),3.84-3.92(m,20H),3.68-3.79(m, 20H),3.58(t,1H),3.08(t,1H),2.67(t,1H),2.52(dd,1H),2.33-2.44(m,19H),0.81-1.35 (m,90H).13C NMR(101MHz,CDCl3)δ162.56,162.35,161.99,161.91,161.68,161.21, 161.03,160.93,160.39,159.63,158.99,158.76,158.35,148.90,148.55,148.37,148.31, 148.20,147.57,147.31,146.66,141.81,140.94,138.28,137.73,137.42,137.04,136.91, 136.75,136.23,135.97,133.35,133.19,132.52,132.31,131.32,128.91,127.73,127.20, 126.65,126.30,125.94,125.62,125.41,125.15,122.41,121.95,121.70,121.23,121.09, 120.30,119.99,119.27,118.43,116.61,116.32,115.38,114.62,113.53,99.34,98.48, 98.22,98.07,97.82,97.61,74.88,74.70,72.29,71.71,68.56,32.01,31.52,30.39, 30.28,29.78,29.44,28.87,28.53,28.11,28.01,27.89,27.80,22.78,21.99,21.45, 19.69,19.61,19.56,19.47,19.38,19.34,19.24,19.21,14.21,9.76.MS(ESI)calculated for C276H274N38O38[M+Na]+:4751.0574,found 4750.69；By testing result it is found that above compound structure just Really.
Embodiment 6
Preparation formula S-II3 or R-II3 compound represented
Reaction equation is as follows:
Specific preparation process are as follows:
1) by 200mg L in 50mL two-mouth bottle, be dissolved in 3mL anhydrous methylene chloride under argon gas protection, with syringe plus Enter 5 μ L oxalyl chlorides, after being stirred at room temperature two hours, after vacuum distillation removes organic solvent, it is small that continuation vacuumizes two on vacuum pump When, after to be dissolved in 1mL anhydrous methylene chloride under protection of argon gas stand-by；It is 4-R base -2- (the 2- amino of 0.9 equivalent by the amount of substance Phenyl) oxazole is dissolved in anhydrous methylene chloride in 50mL two-mouth bottle under argon gas protection, and 11 μ L N, N- diisopropyl second are added Amine, after above-mentioned solution of acid chloride is slowly added to syringe, be stirred overnight at room temperature.Column chromatography separation product both obtains compound M； Yield is 61%~63%；
2) it is dissolved in 5mL ethyl acetate after mixing 150mg compound M with the palladium carbon solid of 10% content of 15mg, this is molten Liquid gas pressure is that heating stirring is stayed overnight in 1.0 megapascal hydrogen；Preferably, reaction temperature is 60 DEG C；Reaction solution is cooled down afterwards, passes through silicon Diatomaceous earth filters out the palladium carbon solid after reaction, solvent is distilled off in resulting filtrate decompression, gained yellow solid is compound N；Yield is 89~95%；
3) by 10mg P in 50mL two-mouth bottle, be dissolved in 10mL anhydrous methylene chloride under argon gas protection, with syringe plus Enter 5 μ L oxalyl chlorides, after being stirred at room temperature two hours, after vacuum distillation removes organic solvent, it is small that continuation vacuumizes two on vacuum pump When, after to be dissolved in 3mL anhydrous methylene chloride under protection of argon gas stand-by；By the amount of substance be 2.0 equivalents compound N in 50mL two Anhydrous methylene chloride is dissolved in mouthful bottle under argon gas protection, and 10 μ L n,N-diisopropylethylamine are added, after will be upper with syringe It states solution of acid chloride to be slowly added to, be stirred overnight at room temperature；Column chromatography separation product is up to chemical combination described in formula S-II3 or R-II3 Object；Yield is 19~25%.
When chiral amino oxazolyl phenyl is S-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula S-II3 institute The compound stated, yield 25%.The structure detection structure of the compound is as follows:1H NMR(400MHz,CDCl3)δ12.27(s, 1H),10.92(s,1H),10.78(s,1H),10.76(s,1H),10.40(s,1H),10.36(s,1H),10.25(s,1H), 10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s,1H),10.02(s,1H),9.99(s,1H),9.96 (s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H),7.97(d,1H),7.92(d,1H),7.59-7.79(m, 25H),7.55(d,1H),7.49(d,1H),7.39(d,1H),7.30(d,1H),7.17-7.21(m,3H),7.06-7.13(m, 4H),6.93-7.02(m,12H),6.91(s,1H),6.91(s,1H),6.89(d,1H),6.86(s,1H),6.75-6.84(m, 8H),6.70(s,1H),6.65(s,1H),6.51(d,1H),6.48(s,1H),6.45(s,1H),6.42(s,1H),6.40(d, 1H),6.38(d,1H),6.06(s,1H),6.03(s,1H),6.02(s,1H),6.00(s,1H),5.93(s,1H),5.90(s, 1H),5.87(s,1H),5.78(s,1H),5.77(s,1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.72(s, 1H),5.70(s,1H),4.30(m,1H),3.94-3.98(m,2H),3.45-3.88(m,43H),3.37-.42(m,2H), 3.00(dd,1H),2.42(dd,1H),2.16-2.33(m,21H),2.11(dd,1H),1.39-1.49(m,6H),1.00- 1.28(m,222H),0.83-0.89(m,13H).MS(MALDI)calculated for C500H500N70O70[M+H]+: 8604.7795,found 8604.71；By testing result it is found that above compound structure is correct.
When chiral amino oxazolyl phenyl is R-4- phenyl -2- (2- aminophenyl) oxazole, products therefrom is formula R-II3 institute The compound stated, yield 19%.The structure detection structure of the compound is as follows:1H NMR(400MHz,CDCl3)δ12.27(s, 1H),10.92(s,1H),10.78(s,1H),10.76(s,1H),10.40(s,1H),10.36(s,1H),10.25(s,1H), 10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s,1H),10.02(s,1H),9.99(s,1H),9.96 (s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H),7.97(d,1H),7.92(d,1H),7.59-7.79(m, 25H),7.55(d,1H),7.49(d,1H),7.39(d,1H),7.30(d,1H),7.17-7.21(m,3H),7.06-7.13(m, 4H),6.93-7.02(m,12H),6.91(s,1H),6.91(s,1H),6.89(d,1H),6.86(s,1H),6.75-6.84(m, 8H),6.70(s,1H),6.65(s,1H),6.51(d,1H),6.48(s,1H),6.45(s,1H),6.42(s,1H),6.40(d, 1H),6.38(d,1H),6.06(s,1H),6.03(s,1H),6.02(s,1H),6.00(s,1H),5.93(s,1H),5.90(s, 1H),5.87(s,1H),5.78(s,1H),5.77(s,1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.72(s, 1H),5.70(s,1H),4.30(m,1H),3.94-3.98(m,2H),3.45-3.88(m,43H),3.37-.42(m,2H), 3.00(dd,1H),2.42(dd,1H),2.16-2.33(m,21H),2.11(dd,1H),1.39-1.49(m,6H),1.00- 1.28(m,222H),0.83-0.89(m,13H).MS(MALDI)calculated for C500H500N70O70[M+H]+: 8604.7795,found 8604.63；By testing result it is found that above compound structure is correct.
Embodiment 7,
Compound prepared by embodiment 1-6 carries out uv-visible absorption spectra, fluorescence spectrum, circular dichroism and circle The measurement of polarized luminescence spectrum, using methylene chloride as solvent, UV absorption wavelength, launch wavelength are as shown in table 1, circular dichroism Spectrum and circular polarised luminescence spectrum are as shown in Fig. 1-Figure 18.
As table 1 and Figure 13-15, Figure 16-18 it is found that the g value of the circular polarised luminescence of compound prepared by the present invention and Quantum yield increases with the increase of the chain length of compound.
The optical property of the compound of 1 embodiment 1-6 of table preparation
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is all to belong to this hair The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.

Claims (10)

1. a kind of chiral fluorescent chemicals based on quinoline amides folded formation, it is characterised in that: the general structure of the compound As shown in following Formulas I or Formula II,
In Formulas I or Formula II, R1Alkyl, carbazyl, aromatic radical or substituted aromatic base, carbazole independently selected from carbon atom number 1-15 Oxygroup；R2Alkyl, carbazyl, aromatic radical or substituted aromatic base, carbazole oxygroup, fragrant oxygen independently selected from carbon atom number 1-15 Base or substituted aroma oxygroup, the substituent group of the substituted aromatic base are the alkene of the alkyl of carbon atom number 1-15, carbon atom number 2-15 Base；R3Alkoxy, carbazyl, aromatic radical or the substitution virtue of alkyl, carbon atom number 1-15 independently selected from carbon atom number 1-15 Perfume base, carbazole oxygroup, fragrant oxygroup or substituted aroma oxygroup, one or more substituent groups of the substituted aromatic base are carbon atom number 1- 15 alkyl, the alkenyl of carbon atom number 2-15, the alkynyl of carbon atom number 2-15, carbon atom number 1-10 alkoxy, R1、R2And R3 It is same or different to each other, n is the integer greater than 1.
2. the chiral fluorescent chemicals according to claim 1 based on quinoline amides folded formation, it is characterised in that:
The compound includes S type enantiomer and R type enantiomer；Wherein,
The structural formula of S type enantiomer be following formula S-I or formula S-II shown in,
The structural formula of R type enantiomer be following formula R-I or formula R-II shown in,
In formula S-I, formula S-II, formula R-I or formula R-II, R1Alkyl, carbazyl, aromatic radical independently selected from carbon atom number 1-15 Or substituted aromatic base, carbazole oxygroup, R2Alkyl, carbazyl, aromatic radical, substituted aroma independently selected from carbon atom number 1-15 Base, carbazole oxygroup, fragrant oxygroup or substituted aroma oxygroup, the substituent group of the substituted aromatic base are the alkane of carbon atom number 1-15 The alkenyl of base, carbon atom number 2-15；R3Alkoxy, the click of alkyl, carbon atom number 1-15 independently selected from carbon atom number 1-15 Oxazolyl, aromatic radical, substituted aromatic base, carbazole oxygroup, fragrant oxygroup or substituted aroma oxygroup, a substitution of the substituted aromatic base Or multi-substituent is the alkyl of carbon atom number 1-15, the alkenyl of carbon atom number 2-15, the alkynyl of carbon atom number 2-15, carbon atom number The alkoxy of 1-10, R1、R2And R3It is same or different to each other, n is the integer greater than 1.
3. the chiral fluorescent chemicals according to claim 1 or 2 based on quinoline amides folded formation, it is characterised in that: institute Stating n is 4,8 or 16, the R1For isobutyl group, the R2For methyl, the R3For tert-butyl.
4. a kind of preparation method of the chiral fluorescent chemicals based on quinoline amides folded formation, which is characterized in that the compound For as shown in Formulas I in claim 1, the preparation method includes the following steps:
1) chiral 2- (2- aminophenyl) oxazole that 4 replace under protection of argon gas, is dissolved in anhydrous methylene chloride, N, N- bis- is added Wopropyl ethyl amine makees alkali, obtains solution a；The acyl chlorides of 4- isobutoxy -8- amino -2- carboxyl quinoline amide polymer is dissolved in nothing Water methylene chloride obtains solution b；The quinoline amides polymer to get single chiral is stirred after solution a, b are mixed；
2) under an atmosphere of hydrogen, the palladium carbon of the quinoline amides polymer for the single chiral that step 1) obtains and 10% content is dissolved in Ethyl acetate, heating stirring to get the quinoline amides polymer of single chiral amine；
3) under protection of argon gas, anhydrous methylene chloride makees solvent, and n,N-diisopropylethylamine makees alkali, step 2) is obtained single The amine and pivalyl chloride of chiral quinoline amides polymer are stirred at room temperature 2~4 hours to get Formulas I compound represented is arrived.
5. the preparation method of the chiral fluorescent chemicals according to claim 4 based on quinoline amides folded formation, feature It is,
In the step 1), the carboxylic of n,N-diisopropylethylamine, 4- isobutoxy -8- amino -2- carboxyl quinoline amide polymer The ratio of the amount of the substance of chiral 2- (2- aminophenyl) oxazole that acid replaces with 4 is 2~100:1:0.85~10；
In the step 2), the pressure of hydrogen is 0.8~1.5 megapascal, and the temperature of heating is 40~60 degrees Celsius, heating stirring Time is 6-15 hours, and the mass ratio of the palladium carbon of the quinoline amides polymer and 10% content of single chiral is 10:1~3；
In the step 3), the ratio between amount of substance of amine of quinoline amides polymer of valeryl chlorine and single chiral be 1~ 500:1。
6. a kind of preparation method of the chiral fluorescent chemicals based on quinoline amides folded formation, which is characterized in that the compound For as shown in Formulas I in claim 1, the preparation method includes the following steps:
1) under protection of argon gas, anhydrous methylene chloride makees solvent, and n,N-diisopropylethylamine makees alkali, by 4- isobutoxy -8- ammonia The amine and pivalyl chloride of base -2- carboxyl quinoline amide polymer, which are stirred at room temperature 2~4 hours, obtains fluorescence-causing substance valeryl Quinoline amides polymer；
2) the valeryl quinoline amides polymer that step 1) obtains is dissolved in the mixed solvent of tetrahydrofuran and methanol, by NaOH It is added after being dissolved in deionized water, obtains the carboxylic acid of valeryl quinoline amides polymer after 1~4h of heating stirring；
3) carboxylic acid for the valeryl quinoline amides polymer that step 2) obtains under protection of argon gas, is dissolved in anhydrous dichloromethane Alkane is added oxalyl chloride, is stirred at room temperature to obtain the acyl chlorides of valeryl quinoline amides polymer；
4) chiral 2- (2- aminophenyl) oxazole that 4 replace under protection of argon gas, is dissolved in anhydrous methylene chloride, N, N- bis- is added Wopropyl ethyl amine obtains solution c；The acyl chlorides for the valeryl quinoline amides polymer that step 3) obtains is dissolved in anhydrous dichloromethane Alkane obtains solution d, and solution c, d are mixed to get Formulas I compound represented.
7. the preparation method of the chiral fluorescent chemicals according to claim 6 based on quinoline amides folded formation, feature It is,
In the step 1), the amine of n,N-diisopropylethylamine, 4- isobutoxy -8- amino -2- carboxyl quinoline amide polymer Ratio with the amount of the substance of pivalyl chloride is 2~100:1:0.85~10；
In the step 2), the ratio between tetrahydrofuran, amount of substance of methanol and water are 5~100:1~100:0.1~50；New penta The ratio between amount of substance of acyl group quinoline amides polymer and sodium hydroxide is 1:10~1:20；
In the step 3), the ratio between amount of substance of the carboxylic acid of valeryl quinoline amides polymer and oxalyl chloride for 1:2~ 100；
In the step 4), chiral 2- (2- aminophenyl) oxazole of the acyl chlorides of valeryl quinoline amides polymer and 4 substitutions The ratio between the amount of substance be 1:0.85~1.2.
8. a kind of preparation method of the chiral fluorescent chemicals based on quinoline amides folded formation, which is characterized in that the compound For as shown in Formula II in claim 1, the preparation method includes the following steps:
1) 4,7- diisobutyl -1,10- Phen -2,9- carboxylic acid under protection of argon gas, is dissolved in anhydrous methylene chloride, is added Oxalyl chloride is stirred at room temperature to obtain 4,7- diisobutyl -1,10- Phen -2,9- carboxylic acid chloride；
2) amine of chiral quinoline amides polymer under protection of argon gas, is dissolved in anhydrous methylene chloride, N, N- diisopropyl is added Ethamine obtains solution e；4,7- diisobutyl -1,10- Phen -2,9- the carboxylic acid chloride that step 1) obtains is dissolved in anhydrous Methylene chloride obtains solution f；Stirring is after solution e, f are mixed to get Formula II compound represented.
9. the preparation method of the chiral fluorescent chemicals according to claim 8 based on quinoline amides folded formation, feature It is,
In the step 1), the ratio between 4,7- diisobutyl -1,10- Phen -2,9- carboxylic acids and the amount of substance of oxalyl chloride are 1:5~1000；
In the step 2), 4,7- diisobutyl -1,10- Phen -2,9- carboxylic acid chlorides, n,N-diisopropylethylamine and 4 The ratio between substituted amount of substance of chiral 2- (2- aminophenyl) oxazole is 1:5~1000:2~10.
10. it is a method according to any one of claims 1-3 based on the chiral fluorescent chemicals of quinoline amides folded formation in chiral organic hair The preparation of luminescent material, the preparation of chiral fluorescence probe and the application in fluorescence identifying field.
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CN110357880A (en) * 2019-05-31 2019-10-22 北京师范大学 The chiral fluorescent chemicals and the preparation method and application thereof with circular polarised luminescence property based on folded formation
CN110407764A (en) * 2019-08-08 2019-11-05 南京大学 Chiral fluorescent chemicals and the preparation method and application thereof based on the luxuriant alkane skeleton of ring

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