CN109456341A - Sulfonamide rhodamine compound and preparation method and application of the one kind with alkynyl or the derivative site of azido - Google Patents

Sulfonamide rhodamine compound and preparation method and application of the one kind with alkynyl or the derivative site of azido Download PDF

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CN109456341A
CN109456341A CN201811218269.1A CN201811218269A CN109456341A CN 109456341 A CN109456341 A CN 109456341A CN 201811218269 A CN201811218269 A CN 201811218269A CN 109456341 A CN109456341 A CN 109456341A
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azido
rhodamine
alkynyl
sulfonamide
compound
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CN109456341B (en
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肖义
郑莹
张新富
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Dalian University of Technology
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Abstract

Sulfonamide rhodamine compound and preparation method and application of the one kind with alkynyl or the derivative site of azido, belong to field of fine chemical.A kind of sulfonamide rhodamine compound with alkynyl or the derivative site of azido is prepared by the amidation process of common sulfonic acid rhodamine, overcomes the shortcomings that common sulfonic acid rhodamine can not be applied because not having derivative site.In a mild condition can be by the characteristic of Click reaction forming using alkynyl and azido, sulfonamide rhodamine compound in the present invention with alkynyl or azido group can carry out Click with large biological molecules, Medicine small molecule or the bioactive molecule such as nucleic acid, polypeptide, phosphatide etc. and react to synthesize the novel molecular with specific function that can be applicable to life science.

Description

One kind has the sulfonamide rhodamine compound and system of alkynyl or the derivative site of azido Preparation Method and application
Technical field
The present invention relates to a kind of sulfonamide rhodamine compounds and preparation method with alkynyl or the derivative site of azido With application, belong to field of fine chemical.
Background technique
Imaging-PAM is widely applied to every field, has especially obtained significant hair in life science Exhibition, wherein super-resolution fluorescence micro-imaging obtains Nobel chemistry Prize repeatly.The development of fluorescence probe has promoted Imaging-PAM It improves.Fluorescence probe is regarded as jewellery by scientists always due to the features such as its distinctive high sensitivity.Wherein, rhodamine is glimmering Photoinitiator dye is due to its preferable photostability, high-fluorescence quantum yield, the excellent optical physics such as longer absorption, launch wavelength and Photochemical properties have become one of the fluorescence probe being most widely used.Scientists have carried out largely by parent of rhodamine Structure of modification, wherein it is the most successful (oxygen atom in rhodamine is changed to silicon atom) with silicon substrate rhodamine, rhodamine is contaminated The wavelength of material extends near infrared region and successfully applies in cell micro-imaging.Sulfonic acid rhodamine and common oxygen bridge rhodamine Spectral property it is similar, equally have excellent photophysical property, but due to sulfonic acid rhodamine shortage can carry out derivative derivative Site, therefore widely do not paid close attention to and applied.
Click chemistry (click reaction) with its reaction condition it is mild and the advantages that reaction rate is fast in 2001 by Barry Sharpless just causes great concern in the field of chemical synthesis after proposing.Click reaction passes through alkynyl group and azido Group is generating the connection between triazole structure realization chemical molecular under the catalysis of metallic copper, for increasing the variable of chemical structure Property.
Summary of the invention
In order to solve the technical issues of sulfonic acid rhodamine lacks derivative site, the present invention provides a kind of with alkynyl or nitrine The sulfonamide rhodamine compound in the derivative site of base, is connected to sulfonic acid rhodamine for alkynyl or azido group by amidation process On, allow alkynyl or azido group to become the derivative site of sulfonic acid rhodamine.It can be with azido group relatively mild using alkynyl Under the conditions of the advantages of carrying out Click reaction, which applies having in life science by the way that Click reaction is producible The novel molecular of specific function.
One kind has the sulfonamide rhodamine compound of alkynyl or the derivative site of azido, which has the following structure General formula:
In general formula, R1With Wherein: the integer of n=0-18, the integer of m=0-18, X-For anion, institute Stating anion is BF4 -、Cl-、Br-、I-、NO3 -、SO4 2-、ClO4 -、CH3COO-、CH3SO3 -Or CF3SO3 -。
It is describedThe positively charged sum of institute is equal to the negatively charged sum of anion institute, R1And R2It can be different bases Group.
R3WithWherein: R3And R4It can be different groups.
Wherein: n1=0-11 Integer, n2The integer of=0-5, m1The integer of=0-11, n3The integer of=0-11, m2The integer of=0-11, n4=0-5's is whole Number, m3The integer of=0-11.
A=C or N.
One kind has the preparation method of alkynyl or the sulfonamide rhodamine compound in the derivative site of azido, the sulfonamide The preparation method of rhodamine compound includes the following steps:
It synthesizes firstIt is alkynylamine when A=CIt is azido amine when A=N The sulfonamide rhodamine with alkynyl or the derivative site of azido is obtained by amidation process with sulfonic acid rhodamine Compound, the preparation method is as follows:
Wherein: R1, R2, R3, R4, R5, X-, n, m, n1, n2, n3, n4, m1, m2, m3, the definition of A determines in general structure Justice.
One kind has the application of alkynyl or the sulfonamide rhodamine compound in the derivative site of azido, the alkynyl of the compound Derivative with azidoOr the azido derivative of the compound with alkynylIt is reacted and is connected by Click Deliver a child into the new compound with specific function, it is described with azidoFor with azido large biological molecule, Medicine small molecule or bioactive molecule, it is described with alkynylFor with alkynyl large biological molecule, Medicine small molecule or Bioactive molecule, reaction formula are as follows:
Wherein, R1, R2, R3, R4, R5, X-, n, m, n1, n2, n3, n4, m1, m2, m3Definition with the definition in general structure.
The beneficial effects of the present invention are: preparing one kind by common sulfonic acid rhodamine has alkynyl or the derivative position of azido The sulfonamide rhodamine compound of point.Preparation method is simple, while overcoming common sulfonic acid rhodamine due to not having derivative site The shortcomings that can not being applied.The characteristic of click reaction forming, this hair can be passed through in a mild condition using alkynyl and azido Sulfonamide rhodamine compound in bright with alkynyl or azido group can with the large biological molecules such as nucleic acid, polypeptide, phosphatide into Row specificity fluorescent label, additionally it is possible to which reacting synthesis with progress click such as Medicine small molecule, bioactive molecules can be applicable to life Order the novel molecular with specific function of scientific domain.
Specific embodiment
The present invention is illustrated with following embodiment but not limited to this, wherein unless otherwise indicated, all numbers and Percentage is by weight.
Specific embodiments of the present invention are described in detail below in conjunction with technical solution.
Embodiment 1
3- chlorine propylamine (10.69mmol) is weighed in reaction flask, solvent DMSO is added, sodium azide is added after being sufficiently stirred NaOH aqueous solution is added into reaction solution to fully reacting, is extracted 3-5 times, is associated with ether for (32mmol), room temperature reaction Machine phase is washed 3-5 times with saturated salt solution, and organic phase decompression is spin-dried for obtaining product.Product structure is identified by HRMS.
Embodiment 2
The 3 of Boc radical protection, 3 '-diaminodipropylamines of one Amino End Group are dissolved in DMF solvent, K is added2CO3It stirs It mixes uniformly, nitrine chloropropane is added, room temperature reaction is extracted 3-5 times with ether after complete reaction, merges organic phase, with saturation Salt is washed 3-5 times, and organic phase decompression is spin-dried for.It will be spin-dried for reacting at room temperature 12h, water in the solution of products therefrom addition DCM and TFA It washes three times, decompression is spin-dried for organic phase and obtains target product.Product structure is identified by HRMS.
Embodiment 3
Synthetic method replaces 3,3 '-diaminodipropylamines referring to embodiment 2, (3- aminopropyl) ether of spent glycol two.
Embodiment 4
2,2'- oxygen bis- (ethamine) is dissolved in DMF solvent, K is added2CO3It stirs evenly, propargyl bromide is added, react at room temperature, It is extracted 3-5 times with ether after complete reaction, merges organic phase, washed 3-5 times with saturated common salt, merged organic subtract each other and press rotation It is dry.It will be spin-dried for reacting at room temperature 12h in the solution of products therefrom addition DCM and TFA, three times, decompression is spin-dried for organic phase and obtains mesh for washing Mark product.Product structure is identified by HRMS.
Embodiment 5
Synthetic method is bis- (ethamine) with 3,3 '-diaminodipropylamines substitution 2,2'- oxygen referring to embodiment 4.
Embodiment 6
Sulfonic acid rhodamine (1.83mmol) is weighed in reaction flask, 1,2- dichloroethanes is added and is sufficiently stirred, is slowly added dropwise Phosphorus oxychloride, 95 DEG C of back flow reactions, thin-layer chromatography detects extent of reaction, and after sulfonic acid rhodamine fully reacting, cooling, decompression is steamed It is spare to obtain rhodamine sulfonic acid chloride for solvent out；Azido amine (3.66mmol), triethylamine and acetonitrile addition reaction flask are stirred at room temperature, Rhodamine sulfonic acid chloride is dissolved in acetonitrile and is slowly added to reaction solution, is reacted at room temperature, thin-layer chromatography detects extent of reaction.Product washing Extraction, decompression steam solvent, purify through pillar layer separation, and product structure is identified by HRMS.
Embodiment 7
Synthetic method is referring to embodiment 6.
Embodiment 8
Synthetic method is referring to embodiment 6.
Embodiment 9
Synthetic method is referring to embodiment 6.
Embodiment 10
Synthetic method is referring to embodiment 6.
Embodiment 11
Synthetic method is referring to embodiment 6.
Embodiment 12
Synthetic method is referring to embodiment 6.
Embodiment 13
Sulfonic acid rhodamine (1.83mmol) is weighed in reaction flask, 1,2- dichloroethanes is added and is sufficiently stirred, trichlorine is added Oxygen phosphorus, 95 DEG C of back flow reactions, thin-layer chromatography detect extent of reaction, to sulfonic acid rhodamine fully reacting, by the cooling decompression of reaction solution Steaming solvent, to obtain rhodamine sulfonic acid chloride spare；Azido amine (3.66mmol), triethylamine, acetonitrile are added reaction flask room temperature and stirred It mixes, rhodamine sulfonic acid chloride is dissolved in acetonitrile and is slowly added in reaction solution, react at room temperature, thin-layer chromatography detects extent of reaction.It produces Object washing extraction, decompression steam solvent, purify through pillar layer separation, and product structure is identified by HRMS.
Embodiment 14
Synthetic method is referring to embodiment 13.
Embodiment 15
Synthetic method is referring to embodiment 13.
Embodiment 16
Synthetic method is referring to embodiment 13.
Embodiment 17
Synthetic method is referring to embodiment 13.
Embodiment 18
Synthetic method is referring to embodiment 13.
Embodiment 19
Synthetic method is referring to embodiment 13.
Embodiment 20
Sulfonic acid rhodamine (1.83mmol) is weighed in reaction flask, 1,2- dichloroethanes is added and is sufficiently stirred, trichlorine is added Oxygen phosphorus, 95 DEG C of back flow reactions, thin-layer chromatography detect extent of reaction, to sulfonic acid rhodamine fully reacting, by the cooling decompression of reaction solution Steaming solvent, to obtain rhodamine sulfonic acid chloride spare；Azido amine (3.66mmol), triethylamine, acetonitrile are added reaction flask room temperature and stirred It mixes, rhodamine sulfonic acid chloride is dissolved in acetonitrile and is slowly added in reaction solution, react at room temperature, thin-layer chromatography detects extent of reaction.Product Washing extraction, decompression steam solvent, purify through pillar layer separation, and product structure is identified by HRMS.
Embodiment 21
Synthetic method is referring to embodiment 20.
Embodiment 22
Synthetic method is referring to embodiment 20.
Embodiment 23
Synthetic method is referring to embodiment 20.
Embodiment 24
Synthetic method is referring to embodiment 20.
Embodiment 25
Synthetic method is referring to embodiment 20.
Embodiment 26
Synthetic method is referring to embodiment 20.
Embodiment 27
Sulfonic acid rhodamine (1.83mmol) is weighed in reaction flask, 1,2- dichloroethanes is added and is sufficiently stirred, trichlorine is added Oxygen phosphorus, 95 DEG C of back flow reactions, thin-layer chromatography detect extent of reaction, to sulfonic acid rhodamine fully reacting, by the cooling decompression of reaction solution Steaming solvent, to obtain rhodamine sulfonic acid chloride spare；Azido amine (3.66mmol), triethylamine, acetonitrile are added reaction flask room temperature and stirred It mixes, rhodamine sulfonic acid chloride is dissolved in acetonitrile and is slowly added in reaction solution, react at room temperature, thin-layer chromatography detects extent of reaction.Product Washing extraction, decompression steam solvent, purify through pillar layer separation, and product structure is identified by HRMS.
Embodiment 28
Synthetic method is referring to embodiment 27.
Embodiment 29
Synthetic method is referring to embodiment 27.
Embodiment 30
Synthetic method is referring to embodiment 27.
Embodiment 31
Synthetic method is referring to embodiment 27.
Embodiment 32
Synthetic method is referring to embodiment 27.
Embodiment 33
Synthetic method is referring to embodiment 27.
Embodiment 34
Sulfonic acid rhodamine (1.83mmol) is weighed in reaction flask, 1,2- dichloroethanes is added and is sufficiently stirred, trichlorine is added Oxygen phosphorus, 95 DEG C of back flow reactions, thin-layer chromatography detect extent of reaction, to sulfonic acid rhodamine fully reacting, by the cooling decompression of reaction solution Steaming solvent, to obtain rhodamine sulfonic acid chloride spare；Alkynylamine (3.66mmol), triethylamine, acetonitrile are added reaction flask and are stirred at room temperature, Rhodamine sulfonic acid chloride is dissolved in acetonitrile and is slowly added to reaction solution, is reacted at room temperature, thin-layer chromatography detects extent of reaction.Product washing extraction It takes, decompression steams solvent, and product structure is identified by HRMS.
Embodiment 35
Synthetic method is referring to embodiment 34.
Embodiment 36
Sulfonic acid rhodamine (1.83mmol) is weighed in reaction flask, 1,2- dichloroethanes is added and is sufficiently stirred, trichlorine is added Oxygen phosphorus, 95 DEG C of back flow reactions, thin-layer chromatography detect extent of reaction, to sulfonic acid rhodamine fully reacting, by the cooling decompression of reaction solution Steaming solvent, to obtain rhodamine sulfonic acid chloride spare；Alkynylamine (3.66mmol), triethylamine, acetonitrile are added reaction flask and are stirred at room temperature, Rhodamine sulfonic acid chloride is dissolved in acetonitrile and is slowly added to reaction solution, is reacted at room temperature, thin-layer chromatography detects extent of reaction.Product washing extraction It takes, decompression steams solvent, and product structure is identified by HRMS.
Embodiment 37
Synthetic method is referring to embodiment 36.
Embodiment 38
Synthetic method is referring to embodiment 36.
Embodiment 39
Synthetic method is referring to embodiment 36.
Embodiment 40
Synthetic method is referring to embodiment 36.
Embodiment 41
Synthetic method is referring to embodiment 36.
Embodiment 42
Sulfonic acid rhodamine (1.83mmol) is weighed in reaction flask, 1,2- dichloroethanes is added and is sufficiently stirred, trichlorine is added Oxygen phosphorus, 95 DEG C of back flow reactions, thin-layer chromatography detect extent of reaction, to sulfonic acid rhodamine fully reacting, by the cooling decompression of reaction solution Steaming solvent, to obtain rhodamine sulfonic acid chloride spare；Alkynylamine (3.66mmol), triethylamine, acetonitrile are added reaction flask and are stirred at room temperature, Rhodamine sulfonic acid chloride is dissolved in acetonitrile and is slowly added to reaction solution, is reacted at room temperature, thin-layer chromatography detects extent of reaction.Product washing extraction It takes, decompression steams solvent, and product structure is identified by HRMS.
Embodiment 43
Synthetic method is referring to embodiment 42.
Embodiment 44
Synthetic method is referring to embodiment 42.
Embodiment 45
Synthetic method is referring to embodiment 42.
Embodiment 46
Sulfonic acid rhodamine (1.83mmol) is weighed in reaction flask, 1,2- dichloroethanes is added and is sufficiently stirred, trichlorine is added Oxygen phosphorus, 95 DEG C of back flow reactions, thin-layer chromatography detect extent of reaction, to sulfonic acid rhodamine fully reacting, by the cooling decompression of reaction solution Steaming solvent, to obtain rhodamine sulfonic acid chloride spare；Alkynylamine (3.66mmol), triethylamine, acetonitrile are added reaction flask and are stirred at room temperature, Rhodamine sulfonic acid chloride is dissolved in acetonitrile and is slowly added to reaction solution, is reacted at room temperature, thin-layer chromatography detects extent of reaction.Product washing extraction It takes, decompression steams solvent, and product structure is identified by HRMS.
Embodiment 47
Synthetic method is referring to embodiment 46.
Embodiment 48
Synthetic method is referring to embodiment 46.
Embodiment 49
Azido sulfonamide rhodamine compound is added in reaction flask, argon gas protection is lower to be added DMF, stir thoroughly at room temperature After being completely dissolved, butine is added, is sufficiently stirred.Cupric sulfate pentahydrate and sodium ascorbate difference is soluble in water, it sequentially adds anti- Bottle is answered, is reacted at room temperature, chromatographic sheet detects extent of reaction.Product washing extraction, organic phase is dry with anhydrous sodium sulfate, decompression Remove solvent.Product is purified through pillar layer separation, and product structure is identified by HRMS.
Embodiment 50
Synthetic method is referring to embodiment 49.
Embodiment 51
Synthetic method is referring to embodiment 49.
Embodiment 52
Acetylenic sulfonamide rhodamine compound is added in reaction flask, argon gas protection is lower to be added DMF, and stir thoroughly at room temperature is complete After fully dissolved, reaction flask is added in nitrine propane, is sufficiently stirred.Cupric sulfate pentahydrate and sodium ascorbate difference is soluble in water, Reaction flask is sequentially added, is reacted at room temperature, thin-layer chromatography detects extent of reaction.Product washing extraction, organic phase anhydrous sodium sulfate It is dry, solvent is removed under reduced pressure.Product is purified through pillar layer separation, and product structure is identified by HRMS.
Embodiment 53
Synthetic method is referring to embodiment 52.
Embodiment 54
Synthetic method is referring to embodiment 52.
Embodiment 55
Acetylenic sulfonamide rhodamine compound is added in reaction flask, argon gas protection is lower to be added DMF, and stir thoroughly at room temperature is complete After fully dissolved, reaction flask is added in nitrine polypeptide chain, is sufficiently stirred.Cupric sulfate pentahydrate and sodium ascorbate are dissolved in water respectively In, reaction flask is sequentially added, is reacted at room temperature, thin-layer chromatography detects extent of reaction.Product washing extraction, organic phase anhydrous slufuric acid Sodium is dry, and solvent is removed under reduced pressure.Product is purified through pillar layer separation, and product structure is identified by HRMS.
Embodiment 56
Synthetic method is referring to embodiment 55.
Embodiment 57
Synthetic method is referring to embodiment 55.
Embodiment 58
Acetylenic sulfonamide rhodamine compound is added in reaction flask, argon gas protection is lower to be added DMF, and stir thoroughly at room temperature is complete After fully dissolved, reaction flask is added in nitrine nucleic acid chains, is sufficiently stirred.Cupric sulfate pentahydrate and sodium ascorbate are dissolved in water respectively In, reaction flask is sequentially added, is reacted at room temperature, thin-layer chromatography detects extent of reaction.Product washing extraction, organic phase anhydrous slufuric acid Sodium is dry, and solvent is removed under reduced pressure.Product is purified through pillar layer separation, and product structure is identified by HRMS.
Embodiment 59
Synthetic method is referring to embodiment 58.
Embodiment 60
Azido sulfonamide rhodamine compound is added in reaction flask, argon gas protection is lower to be added DMF, stir thoroughly at room temperature After being completely dissolved, reaction flask is added in alkynyl nucleic acid chains, is sufficiently stirred.Cupric sulfate pentahydrate and sodium ascorbate are dissolved in water respectively In, reaction flask is sequentially added, is reacted at room temperature, thin-layer chromatography detects extent of reaction.Product washing extraction, organic phase anhydrous slufuric acid Sodium is dry, and solvent is removed under reduced pressure.Product is purified through pillar layer separation, and product structure is identified by HRMS.
Embodiment 61
Acetylenic sulfonamide rhodamine compound is added in reaction flask, argon gas protection is lower to be added DMF, and stir thoroughly at room temperature is complete After fully dissolved, reaction flask is added in azide, is sufficiently stirred.Cupric sulfate pentahydrate and sodium ascorbate difference is soluble in water, Reaction flask is sequentially added, is reacted at room temperature, thin-layer chromatography detects extent of reaction.Product washing extraction, organic phase anhydrous sodium sulfate It is dry, solvent is removed under reduced pressure.Product is purified through pillar layer separation, and product structure is identified by HRMS.

Claims (3)

1. the sulfonamide rhodamine compound that one kind has alkynyl or the derivative site of azido, which is characterized in that compound tool Just like flowering structure general formula:
In general formula, R1With R2= Wherein: the integer of n=0-18, the integer of m=0-18, X-For anion, the yin from Son is BF4 -、Cl-、Br-、I-、NO3 -、SO4 2-、ClO4 -、CH3COO-、CH3SO3 -Or CF3SO3 -, describedInstitute is positively charged Lotus sum is equal to the negatively charged sum of anion institute, R1And R2It can be different groups；
R3With R4=Wherein: R3And R4It can be different groups；
R5=Wherein: n1The integer of=0-11, n2The integer of=0-5, m1The integer of=0-11, n3The integer of=0-11, m2The integer of=0-11, n4The integer of=0-5, m3=0- 11 integer；
A=C or N.
2. a kind of system with alkynyl or the sulfonamide rhodamine compound in the derivative site of azido according to claim 1 Preparation Method, which is characterized in that the preparation method of the sulfonamide rhodamine includes the following steps:
It synthesizes firstIt is alkynylamine when A=CIt is azido amine when A=N The sulfonamide rhodamine with alkynyl or the derivative site of azido is obtained by amidation process with sulfonic acid rhodamine Compound, the preparation method is as follows:
Wherein: R1, R2, R3, R4, R5, X-, n, m, n1, n2, n3, n4, m1, m2, m3, the definition of A determines in claim 1 general formula Justice.
3. a kind of sulfonamide rhodamine compound that there is alkynyl or azido to derive site according to claim 1 is answered With, which is characterized in that alkynyl derivatives of the compound with azidoOr the azido derivative of the compound with With alkynylThe compound with specific function is generated by Click reaction forming；It is described with azidoFor Large biological molecule, Medicine small molecule or bioactive molecule with azido, it is described with alkynylFor with alkynyl Large biological molecule, Medicine small molecule or bioactive molecule.
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