CN102994073A - Benzoxazole-based fluorescent-identified RAFT reagent, synthesis method and application - Google Patents
Benzoxazole-based fluorescent-identified RAFT reagent, synthesis method and application Download PDFInfo
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Abstract
The invention relates to a benzoxazole-based fluorescent-identified RAFT reagent, a synthesis method and an application. The synthesis method comprises the following steps of: under the action of a base catalyst, stirring dithio formate, amino-dithio formate or trithio carbonate and p-halogenatedalkyl phenyl benzoxazole for 4-24 hours in an organic solvent; and after the reaction is finished, decompressing to remove a great amount of organic solvent, then cleaning with distilled water, filtering, obtaining petroleum ether recrystal for solid, carrying out vacuum drying and obtaining the benzoxazole-based fluorescent-identified RAFT reagent. The invention has the advantages that the reaction condition is moderate, the process is simple, the yield is high and the separation and purification of products are easy; and the related benzoxazole-based fluorescent-identified RAFT reagent can be used for preparing fluorescent-identified polymer, the chain end of the obtained polymer and the fluorophore are coupled by stable C-C bonds, and the physicochemical property is very stable; and the application prospect in the aspect of preparing functional polymers with specific structures, molecular weight and fluorescent identifying function is very good.
Description
Technical field
The present invention relates to a kind of benzoxazolyl fluorescence labelling RAFT reagent and synthetic method and application, such RAFT reagent can be used to prepare the functional polymer of the controlled benzoxazolyl chain end fluorescence labelling of structure and molecular weight, belongs to the technical field of the synthetic preparation of living radical polymerization technique functional high molecule material.
Background technology
The functional polymer of chain end fluorescence labelling is widely used and studies (Sinkeldam RW in fields such as chemical analysis, biological medicine, medical diagnosis, food engineering and environmental sciences, Greco NJ, Tor Y.Chem Rev 2010,110,2579-2619;
MST, Chem Rev 2009,109,190 – 212).Novel process or the method for the functional polymer of the synthetic chain end fluorescence labelling that development technology is simple, with low cost are significant.
RAFT (RAFT) polymerization utilize the dithio carbonyl compound (Z-C (=S)-S-R) as chain transfer agents (RAFT reagent), can design very simply and easily and prepare ad hoc structure and functional high molecule material (the Chiefari J that specifies molecular weight and molecualr weight distribution, Chong YK, Ercole F, et a1.Macromolecules 1998,31,5559-5562; Le TP, Moad G, Rizzardo E, et a1.WO9801478.1998-01.).The polymkeric substance of RAFT polymerization technique preparation, general structure be Z-C (=S)-S-[M]
n-R, the end of its chain have kept Z and R group.Therefore, utilize Z and R group with the RAFT reagent of fluorescence property, can prepare very easily structure and molecular weight functional polymer controlled, the chain end fluorescence labelling.At present, the RAFT reagent of fluorescence labelling has become one of most popular method (Boutevin B, David G, Boyer C.Adv Polym Sci 2007,206, the 31-135 of preparation fluorescence labelling functional polymer; Beija M, Charreyre M-T, Martinho JMG.Prog Polym Sci 2011,36,568-602.).
The RAFT reagent of fluorescence labelling is synthetic to be the key that the RAFT polymerization technique prepares the fluorescence labelling functional polymer.The material that much has the fluorescence labelling function is such as carbazole (Zhang JH, Dong AJ, Cao TY, et a1.EurPolym J 2008,44,1071-1080; Guo Ruiwei, Qi Gui village, Fang Daobin. Chinese patent, CN200410072592,2005-07; Zhou D, Zhu X, Zhu J, et a1.J Polym Sci Part A Polym Chem 2008,46,6198-6205.), naphthalene (Fu J, Cheng ZP, Zhou N, et a1.Polymer 2008,49,5431-5438.), anthracene (Zhou NC, Lu LD, Zhu XL, et a1.Polym Bull 2006,57,491-498), luxuriant and rich with fragrance (Zhu J, Zhu XL, Zhou D, et a1.Eur Polym J 2004,40,743-749.), pyrene (Zhou N, Lu L, Zhu J, et a1.Polymer 2007,48,1255-1260.) etc., as Z group or R group, be used to the RAFT reagent of synthetic fluorescence labelling function.Wherein, because the chain end C-S key with the synthetic polymkeric substance of the fluorescence labelling RAFT reagent place of Z radical functino is very unstable, lose easily the fluorescence labelling of chain end, so the application of the fluorescence labelling RAFT reagent of Z radical functino has been subject to serious restriction.The synthetic polymer ends of the fluorescence labelling RAFT reagent place of R radical functino generally all is to connect with fluorophor by the C-C key, chemical property is highly stable, has higher using value (Beija M, Charreyre M-T, Martinho JMG.Prog Polym Sci 2011,36,568-602.).But the synthetic relatively difficulty of the fluorescence labelling RAFT reagent of R radical functino.At present, bibliographical information is arranged, utilize fluorescent substance and the phenylformic acid such as anthracene with hydroxyl, pyrene, by polystep reactions such as esterification and sulfurations, fluorescence labelling RAFT reagent (Zhou NC, Lu LD, the Zhu XL of preparation R radical functino, et a1.PolymBull 2006,57,491-498; Zhou N, Lu L, Zhu J, et a1.Polymer 2007,48,1255-1260.).Severe reaction conditions, the yield of the method are low.Also has bibliographical information, utilization is with the fluorescent substance of carboxyl or hydroxyl, prepare fluorescence labelling RAFT reagent (the Thang SH of R radical functino with the RAFT reagent react of amino, hydroxyl or carboxyl with the R group, Chong YK, Mayadunne RTA, et a1.Tetrahedron Lett 1999,40,2435-2438; Chen M, Ghiggino KP, Mau AWH, et a1.Chem Commun 2002,22,2276-2277; Prazeres TJV, Beija M, Charreyre M-T, et a1.Polymer 2010,51,355-367).But the synthesis step of this technique is numerous and diverse, yield is very low; In addition, this technique often needs with excessive fluorescent substance for improving yield, cause purification of products difficult, also increased preparation cost; And, between the polymer chain and fluorophor that the RAFT reagent place of this technique preparation synthesizes, be to connect by ester bond or amido linkage, hydrolysis loses fluorophor (Beija M, Charreyre M-T, Martinho JMG.Prog Polym Sci2011 easily, 36,568-602.).In addition, it is worth mentioning that, the fluorescence labelling RAFT reagent of synthetic R radical functino generally need to be used the fluorescent substance with the special reaction group, this class material often is not commercial product, be difficult to obtain or combine very difficultly, it is high that this causes finally synthesizing this class fluorescence labelling RAFT reagent cost.Present this present situation needs exploitation a kind of easier, economical, efficiently, and to hold facile commercialization fluorescent substance as main raw material, the synthetic method of the fluorescence labelling RAFT reagent of R radical functino.
The fluorescence of Benzooxazole kind fluorescent substance is bright, and fluorescence quantum yield is high, and stoke shift is large, is a kind of fluorescence dye that has a extensive future (Ohshima A, Momotake A, Arai T.Tetrahedron Lett 2004,45,9377-9381; 34.Taki M, Wolford JL, O ' Halloran TV.J Am Chem Soc 2004,126,712-713.).But, also do not have at present the bibliographical information about benzoxazolyl fluorescence labelling RAFT reagent.The present invention utilizes the nucleophilic substitution reaction between haloalkyl Ben base benzoxazole and dithio formate, Aminodithioformate or the trithiocarbonate, very simple and effective ground preparation benzoxazolyl fluorescence labelling RAFT reagent.The reaction conditions of considering again nucleophilic substitution reaction is gentle, and yield is higher, and benzoxazolyl fluorescence labelling RAFT reagent involved in the present invention and preparation method thereof has good application prospect.
Summary of the invention
The object of the present invention is to provide a kind of easy, economic, efficient fluorescence labelling RAFT reagent of R radical functino, and based on being synthetic method and the application of fluorescent substance to haloalkyl Ben base benzoxazole.
The synthetic method that the purpose of this invention is to provide a class benzoxazolyl fluorescence labelling RAFT reagent.
The benzoxazolyl fluorescence labelling RAFT reagent that the present invention synthesizes has following structure:
The general formula of benzoxazolyl RAFT reagent
Z is:
Y is: C
1～C
3Alkyl
In the Z group, especially recommend phenyl and carbazyl;
Synthetic method among the present invention is to utilize fluorescent substance: to haloalkyl Ben base benzoxazole, and the nucleophilic substitution reaction between excessive dithio formate, Aminodithioformate or the trithiocarbonate.Mainly comprise following two processes:
(1), according to the conventional method, utilize dithiocarbonic anhydride to be main raw material, preparation dithio formate, Aminodithioformate or trithiocarbonate.
(2), the dithio formate with above-mentioned preparation, Aminodithioformate or trithiocarbonate, in the presence of alkaline catalysts, under 40 ~ 80 ° of C, and to haloalkyl Ben base benzoxazole, stirring reaction 4 ~ 24h in organic solvent; A large amount of organic solvents are removed in decompression after reacting end, use subsequently a large amount of distilled water washs, after filtration gained solid sherwood oil recrystallization, the vacuum-drying, namely obtain target product---benzoxazolyl fluorescence labelling RAFT reagent.The reaction equation of preparation method among the present invention is:
Z is:
Y is: C
1～C
3Alkyl
M is: Na, K, MgCl or MgBr
X is: Cl, Br or I
Employed among the present invention haloalkyl Ben base benzoxazole is referred to that mainly its structural formula is as follows to the chloromethyl phenyl benzoxazole, to the 2-bromomethylphenyl benzoxazole with to iodomethyl Ben base benzoxazole:
Employed dithio formate, Aminodithioformate or trithiocarbonate among the present invention, mainly refer to their sodium salt, sylvite or magnesium salts, general formula be Z-C (=S)-S-M, wherein M is: Na, K, MgCl or MgBr.Especially recommend dithiobenzoic acid magnesium bromide and N-carbazole dithio sodium formiate.
The formate of dithio carbonyl described in the preparation method of the present invention, dithiocar-bamate or trithio carbonyl formate generally have certain water-soluble, and therefore excessive salt is removed by washing easily.Byproduct of reaction is that halogeno salt also is water miscible, and washing is removed easily.
Dithio formate among the present invention, Aminodithioformate or trithiocarbonate and the mol ratio of haloalkyl Ben base benzoxazole is recommended as: 1:(15 ~ 2.0); Alkaline catalysts is recommended as with mol ratio to haloalkyl Ben base benzoxazole: (0.05 ~ 0.2): 1.
Organic solvent mainly refers to tetrahydrofuran (THF), tetracol phenixin, chloroform, methylene dichloride, toluene, benzene, normal hexane, hexanaphthene, ethyl acetate, DMSO, dioxane or pyrrolidinone compounds among the preparation method of the present invention.Especially recommend tetrahydrofuran (THF).
Alkaline catalysts mainly refers to sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, dipotassium hydrogen phosphate, sodium-acetate, Potassium ethanoate, sodium hydride, potassium hydride KH or triethylamine among the preparation method of the present invention.
Preparation method's of the present invention benzoxazolyl fluorescence labelling RAFT reagent is solid, can be by the Methods For Purification of recrystallization, product can keep stable for a long time, it is active that the RAFT polymerization of vinylbenzene, acrylamide, vinylformic acid and acrylic ester monomer is had better control, can be used for the functional polymer of the controlled chain end fluorescence labelling of synthetic molecules structure, molecular weight distribution.
RAFT reagent involved in the present invention applicable to different monomers and solvent, is applicable to solution polymerization, letex polymerization, mass polymerization and diffuse-aggregate different polymerization processs.
The invention has the advantages that: the used benzoxazolyl fluorescent substance of (1) the present invention is commercial prod, obtains easily.(2) the used excessive dithio carbonyl formate of the present invention, dithiocar-bamate or trithio carbonyl formate, above-mentioned excessive salt can improve the utilization ratio of benzoxazolyl fluorescent substance in reaction on the one hand.Simultaneously, because above-mentioned salt is water miscible, excessive salt is removed by washing easily, can not increase the difficulty of separating-purifying.Byproduct of reaction is that halogeno salt also is water miscible, also removes by washing easily.(3) preparation technology's reaction conditions of the present invention is gentle, and process is simple, and yield is high, and product separation is purified and also is easier to.(4) the fluorescence labelling polymkeric substance that the benzoxazolyl fluorescence labelling RAFT reagent that the present invention relates to can be used for preparing, and be that physico-chemical property is highly stable by stable C-C key connecting between resulting polymers chain end and the fluorophor.(5) have in preparation and have good application prospect aspect functional high molecule material ad hoc structure and molecular weight, the fluorescence labelling function.
Description of drawings
Fig. 1: the fluorogram of the polymkeric substance of dithiobenzoic acid 4-(2-benzoxazole) benzyl ester preparation;
Fig. 2: the fluorogram of the polymkeric substance of N-carbazole dithio formic acid 4-(2-benzoxazole) benzyl ester preparation.
Embodiment
Help to understand the present invention by following embodiment, but do not limit the summary of the invention of this patent.
Embodiment 1: the preparation of dithiobenzoic acid 4-(2-benzoxazole) benzyl ester
With the bromobenzene of (31.4g, 0.20mol), the tetrahydrofuran (THF) of (6.1g, 0.25mol) magnesium chips and 200mL drying joins in the there-necked flask of the 500mL that prolong is housed, in the presence of nitrogen, stirs 4h in 40 ° of C lower magnetic forces.Remove by filter unreacted excessive magnesium chips, with slowly adding (19.0g, 0.25mol) dithiocarbonic anhydride in the backward filtrate.Under 40 ° of C, slowly stir 2h.After finishing, reaction namely obtained the tetrahydrofuran solution of dithiobenzoic acid magnesium bromide.With add in the tetrahydrofuran solution of backward dithiobenzoic acid magnesium bromide (24.4g, 0.10mol) to the sodium hydroxide of chloromethyl phenyl benzoxazole and (0.4g, 0.01mol) as catalyzer, 60 ° of C lower magnetic forces stir lower reaction 4h.After reaction finished, a large amount of tetrahydrofuran solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of red dithiobenzoic acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain dithiobenzoic acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 82% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=4.65ppm (s, 2H), δ=7.96ppm (d, 2H), δ=7.35 ~ 7.68ppm (m, 11H); The Theoretical Calculation molecular weight is: 361.4799, and high resolution mass spec actual measurement values for molecular weight is: 361.0567; Ultimate analysis: C=69.82%, H=4.21%, N=3.78%, S=17.67%.
Embodiment 2: the preparation of dithiobenzoic acid 4-(2-benzoxazole) benzyl ester
With the bromobenzene of (31.4g, 0.20mol), the tetrahydrofuran (THF) of (6.1g, 0.25mol) magnesium chips and 200mL drying joins in the there-necked flask of the 500mL that prolong is housed, in the presence of nitrogen, stirs 4h in 40 ° of C lower magnetic forces.Remove by filter unreacted excessive magnesium chips, with slowly adding (19.0g, 0.25mol) dithiocarbonic anhydride in the backward filtrate.Under 40 ° of C, slowly stir 2h.After finishing, reaction namely obtained the tetrahydrofuran solution of dithiobenzoic acid magnesium bromide.With adding (28.8g in the tetrahydrofuran solution of backward dithiobenzoic acid magnesium bromide, 0.10mol) to 2-bromomethylphenyl benzoxazole and (0.4g, 0.02mol) sodium hydroxide or (0.56g, 0.02mol) potassium hydroxide as catalyzer, 60 ° of C lower magnetic forces stir lower reaction 12h.After reaction finished, a large amount of tetrahydrofuran solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of red dithiobenzoic acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain dithiobenzoic acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 80% based on the product yield to the chloromethyl phenyl benzoxazole.Consistent among the characterization data of dithiobenzoic acid 4-(2-benzoxazole) benzyl ester of present embodiment preparation and the embodiment 1.
Embodiment 3: the preparation of dithiobenzoic acid 4-(2-benzoxazole) benzyl ester
With the bromobenzene of (31.4g, 0.20mol), the tetrahydrofuran (THF) of (6.1g, 0.25mol) magnesium chips and 200mL drying joins in the there-necked flask of the 500mL that prolong is housed, in the presence of nitrogen, stirs 4h in 40 ° of C lower magnetic forces.Remove by filter unreacted excessive magnesium chips, with slowly adding (19.0g, 0.25mol) dithiocarbonic anhydride in the backward filtrate.Under 40 ° of C, slowly stir 2h.After finishing, reaction namely obtained the tetrahydrofuran solution of dithiobenzoic acid magnesium bromide.With adding (33.5g in the tetrahydrofuran solution of backward dithiobenzoic acid magnesium bromide, 0.10mol) to iodomethyl Ben base benzoxazole and (0.4g, 0.005mol) sodium hydroxide or (0.56g, 0.005mol) potassium hydroxide as catalyzer, 80 ° of C lower magnetic forces stir lower reaction 24h.After reaction finished, a large amount of tetrahydrofuran solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of red dithiobenzoic acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain dithiobenzoic acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 79% based on the product yield to the chloromethyl phenyl benzoxazole.Consistent among the characterization data of dithiobenzoic acid 4-(2-benzoxazole) benzyl ester of present embodiment preparation and the embodiment 1.
Embodiment 4: the preparation of dithio naphthoic acid 4-(2-benzoxazole) benzyl ester
With the 1-bromonaphthalene of (41.5g, 0.20mol), the tetrahydrofuran (THF) of (6.1g, 0.25mol) magnesium chips and 200mL drying joins in the there-necked flask of the 500mL that prolong is housed, in the presence of nitrogen, stirs 4h in 40 ° of C lower magnetic forces.Remove by filter unreacted excessive magnesium chips, with slowly adding (19.0g, 0.25mol) dithiocarbonic anhydride in the backward filtrate.Under 40 ° of C, slowly stir 2h.After finishing, reaction namely obtained the tetrahydrofuran solution of dithio naphthoic acid magnesium bromide.Add in the tetrahydrofuran solution of above-mentioned dithio naphthoic acid magnesium bromide subsequently (24.4g, 0.10mol) to the sodium hydroxide of chloromethyl phenyl benzoxazole and (0.4g, 0.01mol) as catalyzer, stir lower reaction 5h in 60 ° of C lower magnetic forces.After reaction finished, a large amount of tetrahydrofuran solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of dithio naphthoic acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain dithio naphthoic acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 74% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=4.63ppm (s, 2H), δ=7.31 ~ 7.75ppm (m, 10H), δ=7.95ppm (d, 2H), δ=7.85-7.94, (d, 1H), δ=8.01 ~ 8.10ppm (m, 2H); The Theoretical Calculation molecular weight is: 411.5386, and high resolution mass spec actual measurement values for molecular weight is: 411.0756; Ultimate analysis: C=73.11%, H=4.18%, N=3.38%, S=15.56%.
The preparation of embodiment 5:N-carbazole dithio formic acid 4-(2-benzoxazole) benzyl ester
With the carbazole of (33.4g, 0.20mol), the tetrahydrofuran (THF) of (5.1g, 0.22mol) sodium and 200mL drying joins in the there-necked flask of the 500mL that prolong is housed, in the presence of nitrogen, stirs 4h in 40 ° of C lower magnetic forces.Drip lentamente a small amount of water with the utmost point in the backward reaction system, by reaction excessive sodium is removed, subsequent filtration, and in filtrate, slowly add (19.0g, 0.25mol) dithiocarbonic anhydride.Under 40 ° of C, slowly stir 2h.After finishing, reaction namely obtained the tetrahydrofuran solution of N-carbazole dithio sodium formiate.Add in the tetrahydrofuran solution of above-mentioned N-carbazole dithio sodium formiate subsequently (24.4g, 0.10mol) to the sodium hydroxide of chloromethyl phenyl benzoxazole and (0.4g, 0.01mol) as catalyzer, stir lower reaction 5h in 60 ° of C lower magnetic forces.After reaction finished, a large amount of tetrahydrofuran solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of luteotestaceous N-carbazole dithio formic acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain N-carbazole dithio formic acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 78% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=4.62ppm (s, 2H), δ=7.96ppm (d, 2H), δ=8.24ppm (d, 2H), δ=8.47ppm (d, 2H), δ=7.35 ~ 7.81ppm (m, 10H); The Theoretical Calculation molecular weight is: 450.5746, and high resolution mass spec actual measurement values for molecular weight is: 450.0564; Ultimate analysis: C=71.96%, H=4.03%, N=6.21%, S=14.44%.
The preparation of embodiment 6:N-pyrroles dithio formic acid 4-(2-benzoxazole) benzyl ester
With the pyrroles of (13.4g, 0.20mol), the tetrahydrofuran (THF) of (5.1g, 0.22mol) sodium and 100mL drying joins in the there-necked flask of the 250mL that prolong is housed, in the presence of nitrogen, stirs 4h in 40 ° of C lower magnetic forces.Drip lentamente a small amount of water with the utmost point in the backward reaction system, by reaction excessive sodium is removed, filter, and in filtrate, slowly add (19.0g, 0.25mol) dithiocarbonic anhydride.Under 40 ° of C, slowly stir 2h.After finishing, reaction namely obtained the tetrahydrofuran solution of N-pyrroles's dithio sodium formiate.Add in the tetrahydrofuran solution of above-mentioned N-pyrroles's dithio sodium formiate subsequently (24.4g, 0.10mol) to the sodium hydroxide of chloromethyl phenyl benzoxazole and (0.4g, 0.01mol) as catalyzer, stir lower reaction 5h in 60 ° of C lower magnetic forces.After reaction finished, a large amount of tetrahydrofuran solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of yellow N-pyrroles's dithio formic acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain N-pyrroles's dithio formic acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 80% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=4.58 (s, 2H), δ=7.95 (d, 2H), δ=7.31 ~ 7.47 (m, 6H), δ=6.31 (m, 2H), δ=7.39 (m, 2H); The Theoretical Calculation molecular weight is: 350.4573, and high resolution mass spec actual measurement values for molecular weight is: 350.0544; Ultimate analysis: C=65.14%, H=4.05%, N=8.11%, S=18.47%.
The preparation of embodiment 7:N-imidazoles dithio formic acid 4-(2-benzoxazole) benzyl ester
With the imidazoles of (13.6g, 0.20mol), the tetrahydrofuran (THF) of (5.1g, 0.22mol) sodium and 100mL drying joins in the there-necked flask of the 250mL that prolong is housed, in the presence of nitrogen, stirs 4h in 40 ° of C lower magnetic forces.Drip lentamente a small amount of water with the utmost point in the backward reaction system, by reaction excessive sodium is removed, filter, and in filtrate, slowly add (19.0g, 0.25mol) dithiocarbonic anhydride.Under 40 ° of C, slowly stir 2h.After finishing, reaction namely obtained the tetrahydrofuran solution of TMSIM N imidazole dithio sodium formiate.Add in the tetrahydrofuran solution of above-mentioned TMSIM N imidazole dithio sodium formiate subsequently (24.4g, 0.10mol) to the sodium hydroxide of chloromethyl phenyl benzoxazole and (0.4g, 0.01mol) as catalyzer, stir lower reaction 5h in 60 ° of C lower magnetic forces.After reaction finished, a large amount of tetrahydrofuran solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of TMSIM N imidazole dithio formic acid 4-(2-benzoxazole) benzyl ester of brown color after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain TMSIM N imidazole dithio formic acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 71% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=4.58 (s, 2H), δ=7.95 (d, 2H), δ=7.31 ~ 7.47 (m, 7H), δ=7.24 (d, 1H), δ=8.03 (s, 1H); The Theoretical Calculation molecular weight is: 351.4453, and high resolution mass spec actual measurement values for molecular weight is: 351.0512; Ultimate analysis: C=61.53%, H=3.75%, N=12.01%, S=18.25%.
The preparation of embodiment 8:O-methyl sulphur ortho acid 4-(2-benzoxazole) benzyl ester
In the there-necked flask of a 250mL that magnetic agitation, prolong and dropping funnel be housed, under nitrogen protection, add (11.4g, 0.10mol) methyl sodium xanthonate in 0 ° of C.The dehydrated alcohol that adds subsequently 50mL by dropping funnel is after the stirring and dissolving.Under magnetic agitation, slowly add (12.2g, 0.05mol) to the tetrahydrofuran solution of chloromethyl phenyl benzoxazole, and the sodium hydroxide of (0.2g, 0.005mol) slowly is warmed up to 60 ° of C subsequently as catalyzer, react 5h under the magnetic agitation.After reaction finished, a large amount of solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of yellow O-methyl sulphur ortho acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain O-methyl sulphur ortho acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 74% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=3.61 (s, 3H), δ=4.62 (s, 2H), δ=7.96 (d, 2H), δ=7.31 ~ 7.57 (m, 6H); The Theoretical Calculation molecular weight is: 315.4099, and high resolution mass spec actual measurement values for molecular weight is: 315.0372; Ultimate analysis: C=60.92%, H=4.11%, N=4.44%, S=20.36%.
The preparation of embodiment 9:O-ethyl sulphur ortho acid 4-(2-benzoxazole) benzyl ester
In the there-necked flask of a 250mL that magnetic agitation, prolong and dropping funnel be housed, under nitrogen protection, add (11.4g, 0.10mol) sodium ethyl-xanthogenate in 0 ° of C.The dehydrated alcohol that adds subsequently 50mL by dropping funnel is after the stirring and dissolving.Under magnetic agitation, slowly add (12.2g, 0.05mol) to the tetrahydrofuran solution of chloromethyl phenyl benzoxazole, and the sodium hydroxide of (0.2g, 0.005mol) slowly is warmed up to 60 ° of C subsequently as catalyzer, react 5h under the magnetic agitation.After reaction finished, a large amount of solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of yellow O-ethyl sulphur ortho acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain O-ethyl sulphur ortho acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 77% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=1.18 (t, 3H), δ=3.62 (q, 2H), δ=4.61 (s, 2H), δ=7.95 (d, 2H), δ=7.32 ~ 7.58 (m, 6H); The Theoretical Calculation molecular weight is: 329.4365, and high resolution mass spec actual measurement values for molecular weight is: 329.0502; Ultimate analysis: C=61.96%, H=4.61%, N=4.24%, S=19.46%.
The preparation of embodiment 10:O-propyl group sulphur ortho acid 4-(2-benzoxazole) benzyl ester
In the there-necked flask of a 250mL that magnetic agitation, prolong and dropping funnel be housed, under nitrogen protection, add (11.4g, 0.10mol) sodium ethyl-xanthogenate in 0 ° of C.The dehydrated alcohol that adds subsequently 50mL by dropping funnel is after the stirring and dissolving.Under magnetic agitation, slowly add (12.2g, 0.05mol) to the tetrahydrofuran solution of chloromethyl phenyl benzoxazole, and the sodium hydroxide of (0.2g, 0.005mol) slowly is warmed up to 60 ° of C subsequently as catalyzer, react 5h under the magnetic agitation.After reaction finished, a large amount of solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of yellow O-propyl group sulphur ortho acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain O-propyl group sulphur ortho acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 75% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=1.01 (t, 3H), δ=1.51 (m, 2H), δ=3.63 (t, 2H), δ=4.60 (s, 2H), δ=7.94 (d, 2H), δ=7.33 ~ 7.60 (m, 6H); The Theoretical Calculation molecular weight is: 343.4631, and high resolution mass spec actual measurement values for molecular weight is: 343.0703; Ultimate analysis: C=62.93%, H=5.01%, N=4.04%, S=18.64%.
The preparation of embodiment 11:S-methyl-S '-4-(2-benzoxazole) benzyl trithiocarbonate
In the there-necked flask of a 250mL that magnetic agitation, prolong and dropping funnel be housed, under nitrogen protection, add (16.0g, 0.10mol) S-methyl trisulfide for yellow soda ash in 0 ° of C.The dehydrated alcohol that adds subsequently 50mL by dropping funnel is after the stirring and dissolving.Under magnetic agitation, slowly add (12.2g, 0.05mol) to the tetrahydrofuran solution of chloromethyl phenyl benzoxazole, and the sodium hydroxide of (0.2g, 0.005mol) slowly is warmed up to 60 ° of C subsequently as catalyzer, react 5h under the magnetic agitation.After reaction finished, a large amount of solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of yellow S-methyl-S '-4-(2-benzoxazole) benzyl trithiocarbonate after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain S-methyl-S '-4-(2-benzoxazole) benzyl trithiocarbonate.Reaction equation is as follows:
Be about 81% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=3.54 (s, 3H), δ=4.61 (s, 2H), δ=7.97 (d, 2H), δ=7.34 ~ 7.59 (m, 6H); The Theoretical Calculation molecular weight is: 331.4755, and high resolution mass spec actual measurement values for molecular weight is: 331.0181; Ultimate analysis: C=58.02%, H=3.91%, N=4.24%, S=28.96%.
The preparation of embodiment 12:S-ethyl-S '-4-(2-benzoxazole) benzyl trithiocarbonate
In the there-necked flask of a 250mL that magnetic agitation, prolong and dropping funnel be housed, under nitrogen protection, add (16.0g, 0.10mol) S-ethyl trithiocarbonic acid sodium in 0 ° of C.The dehydrated alcohol that adds subsequently 50mL by dropping funnel is after the stirring and dissolving.Under magnetic agitation, slowly add (12.2g, 0.05mol) to the tetrahydrofuran solution of chloromethyl phenyl benzoxazole, and the sodium hydroxide of (0.2g, 0.005mol) slowly is warmed up to 60 ° of C subsequently as catalyzer, react 5h under the magnetic agitation.After reaction finished, a large amount of solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of yellow S-ethyl-S '-4-(2-benzoxazole) benzyl trithiocarbonate after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain S-ethyl-S '-4-(2-benzoxazole) benzyl trithiocarbonate.Reaction equation is as follows:
Be about 83% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=0.98 (t, 3H), δ=1.52 (q, 2H), δ=4.60 (s, 2H), δ=7.95 (d, 2H), δ=7.32 ~ 7.58 (m, 6H); The Theoretical Calculation molecular weight is: 345.5021, and high resolution mass spec actual measurement values for molecular weight is: 345.0401; Ultimate analysis: C=59.06%, H=4.41%, N=4.04%, S=27.86%.
The preparation of embodiment 13:S-propyl group-S '-4-(2-benzoxazole) benzyl trithiocarbonate
In the there-necked flask of a 250mL that magnetic agitation, prolong and dropping funnel be housed, under nitrogen protection, add (16.0g, 0.10mol) S-propyl trisulfide for yellow soda ash in 0 ° of C.The dehydrated alcohol that adds subsequently 50mL by dropping funnel is after the stirring and dissolving.Under magnetic agitation, slowly add (12.2g, 0.05mol) to the tetrahydrofuran solution of chloromethyl phenyl benzoxazole, and the sodium hydroxide of (0.2g, 0.005mol) slowly is warmed up to 60 ° of C subsequently as catalyzer, react 5h under the magnetic agitation.After reaction finished, a large amount of solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the crude product of yellow S-propyl group-S '-4-(2-benzoxazole) benzyl trithiocarbonate after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain S-propyl group-S '-4-(2-benzoxazole) benzyl trithiocarbonate.Reaction equation is as follows:
Be about 83% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=1.18 (t, 3H), δ=1.18 (m, 2H), δ=3.52 (t, 2H), δ=4.60 (s, 2H), δ=7.95 (d, 2H), δ=7.32 ~ 7.58 (m, 6H); The Theoretical Calculation molecular weight is: 359.5287, and high resolution mass spec actual measurement values for molecular weight is: 359.0471; Ultimate analysis: C=60.09%, H=4.81%, N=3.94%, S=26.80%.
Embodiment 14:N, the preparation of N-dimethylamino dithio formic acid 4-(2-benzoxazole) benzyl ester
In the there-necked flask of a 250mL that magnetic agitation, prolong and dropping funnel be housed, under nitrogen protection, add the trihydrate of (22.5g, 0.10mol) Sodium dimethyldithiocarbamate 40min in 0 ° of C.The dehydrated alcohol that adds subsequently 50mL by dropping funnel.Under magnetic agitation, slowly add (12.2g, 0.05mol) to the tetrahydrofuran solution of chloromethyl phenyl benzoxazole subsequently, and (0.2g, 0.005mol) sodium hydroxide as catalyzer, slowly be warmed up to subsequently 60 ° of C, react 5h under the magnetic agitation.After reaction finished, a large amount of solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain yellow N, the crude product of N-dimethylamino dithio formic acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain N, N-dimethylamino dithio formic acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 81% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=3.62 (s, 6H), δ=4.62 (s, 2H), δ=7.96 (d, 2H), δ=7.31 ~ 7.59 (m, 6H); The Theoretical Calculation molecular weight is: 328.4517, and high resolution mass spec actual measurement values for molecular weight is: 328.0702; Ultimate analysis: C=62.16%, H=4.92%, N=8.54%, S=19.56%.
Embodiment 15:N, the preparation of N-diethylamino dithio formic acid 4-(2-benzoxazole) benzyl ester
In the there-necked flask of a 250mL that magnetic agitation, prolong and dropping funnel be housed, under nitrogen protection, add the trihydrate of (22.5g, 0.10mol) Thiocarb in 0 ° of C.The dehydrated alcohol that adds subsequently 50mL by dropping funnel.Under magnetic agitation, slowly add (12.2g, 0.05mol) to the tetrahydrofuran solution of chloromethyl phenyl benzoxazole subsequently, and (0.2g, 0.005mol) sodium hydroxide as catalyzer, slowly be warmed up to subsequently 60 ° of C, react 5h under the magnetic agitation.After reaction finished, a large amount of solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain yellow N, the crude product of N-diethylamino dithio formic acid 4-(2-benzoxazole) benzyl ester after filtration, the drying.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain N, N-diethylamino dithio formic acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 87% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=1.29 (t, 6H), δ=3.72 (q, 2H), δ=3.94 (q, 2H), δ=4.60 (s, 2H), δ=7.95 (d, 2H), δ=7.32 ~ 7.58 (m, 6H); The Theoretical Calculation molecular weight is: 356.5049, and high resolution mass spec actual measurement values for molecular weight is: 356.0992; Ultimate analysis: C=63.96%, H=5.62%, N=7.84%, S=18.06%.
Embodiment 16:N, the preparation of N-dipropyl aminodithioformic acid 4-(2-benzoxazole) benzyl ester
With the dipropyl amine of (20.1g, 0.20mol), the tetrahydrofuran (THF) of (5.1g, 0.22mol) sodium and 100mL drying joins in the there-necked flask of the 250mL that prolong is housed, in the presence of nitrogen, stirs 4h in 40 ° of C lower magnetic forces.Drip lentamente a small amount of water with the utmost point in the backward reaction system, by reaction excessive sodium is removed, filter, and in filtrate, slowly add (19.0g, 0.25mol) dithiocarbonic anhydride.Under 40 ° of C, slowly stir 2h.Reaction has namely obtained N, the tetrahydrofuran solution of N-dipropyl aminodithioformic acid sodium after finishing.Subsequently to above-mentioned N, add (24.4g in the tetrahydrofuran solution of N-dipropyl aminodithioformic acid sodium, 0.10mol) to the sodium hydroxide of chloromethyl phenyl benzoxazole and (0.4g, 0.01mol) as catalyzer, stir lower reaction 5h in 60 ° of C lower magnetic forces.After reaction finished, a large amount of tetrahydrofuran solvents was removed in decompression, washs resulting oily dope with a large amount of distilled water immersions subsequently.Obtain the N of brown color after filtration, the drying, the crude product of N-dipropyl aminodithioformic acid 4-(2-benzoxazole) benzyl ester.Separate through sherwood oil recrystallization or silica gel column chromatography, can obtain N, N-dipropyl aminodithioformic acid 4-(2-benzoxazole) benzyl ester.Reaction equation is as follows:
Be about 87% based on the product yield to the chloromethyl phenyl benzoxazole.Nuclear-magnetism
1H-NMR (300M, CDCl
3): δ=1.09 (m, 6H), δ=1.39 (m, 4H), δ=3.68 (m, 4H), δ=4.60 (s, 2H), δ=7.95 (d, 2H), δ=7.32 ~ 7.58 (m, 6H); The Theoretical Calculation molecular weight is: 384.5581, and high resolution mass spec actual measurement values for molecular weight is: 384.1936; Ultimate analysis: C=65.56%, H=6.42%, N=7.24%, S=16.66%.
Embodiment 17: in the there-necked flask of a 150mL that magnetic agitation is housed; add methyl acrylate (17.2g; 0.2mol); RAFT reagent dithiobenzoic acid 4-(2-benzoxazole) benzyl ester (0.72g; 0.002mol) initiator A IBN (0.066g; 0.0004mol); with an amount of tetrahydrofuran (THF) as solvent, under nitrogen protection, in 60 ° of C; stirring reaction 10h; after reaction finished, resulting polymers solution precipitated with a large amount of ethanol, and precipitation is through obtaining the polymethyl acrylate of benzoxazolyl chain end fluorescence labelling after the vacuum-drying; molecular weight is 8500g/mol, and molecular weight distribution PDI is 1.26.Resulting polymers fluorescence is as shown below, under the emission wavelength of 375nm, a very strong excitation peak is arranged in the 324nm place, under the 324nm wavelength excites, a very strong emission peak is arranged at the 375nm place.As shown in Figure 1.
Embodiment 18: in the there-necked flask of a 150mL that magnetic agitation is housed; add vinylbenzene (20.8g; 0.2mol); RAFT reagent dithiobenzoic acid 4-(2-benzoxazole) benzyl ester (0.72g; 0.002mol) initiator A IBN (0.066g; 0.0004mol); with an amount of tetrahydrofuran (THF) as solvent, under nitrogen protection, in 60 ° of C; stirring reaction 10h; after reaction finished, resulting polymers solution precipitated with a large amount of ethanol, and precipitation is through obtaining the polystyrene of benzoxazolyl chain end fluorescence labelling after the vacuum-drying; molecular weight is 8300g/mol, and molecular weight distribution PDI is 1.21.The fluorescence of resulting polymers and embodiment 17 polymethyl acrylates are similar, under the emission wavelength of 375nm, a very strong excitation peak are arranged in the 324nm place, under the 324nm wavelength excites, a very strong emission peak are arranged at the 375nm place.
Embodiment 19: in the there-necked flask of a 150mL that magnetic agitation is housed; add N; N-DMAA (19.8g; 0.2mol); RAFT reagent dithiobenzoic acid 4-(2-benzoxazole) benzyl ester (0.72g, 0.002mol) initiator A IBN (0.066g, 0.0004mol); with an amount of tetrahydrofuran (THF) as solvent; under nitrogen protection, in 60 ° of C, stirring reaction 10h; after reaction finishes; resulting polymers solution precipitates with a large amount of ethanol, and precipitation is through obtaining the poly-N,N-DMAA of benzoxazolyl chain end fluorescence labelling after the vacuum-drying; molecular weight is 9350g/mol, and molecular weight distribution PDI is 1.32.The fluorescence of resulting polymers and embodiment 17 polymethyl acrylates are similar, under the emission wavelength of 375nm, a very strong excitation peak are arranged in the 324nm place, under the 324nm wavelength excites, a very strong emission peak are arranged at the 375nm place.
Embodiment 20: in the there-necked flask of a 150mL that magnetic agitation is housed; add methyl acrylate (17.2g; 0.2mol); RAFT reagent N-carbazole dithio formic acid 4-(2-benzoxazole) benzyl ester (0.90g; 0.002mol) initiator A IBN (0.066g; 0.0004mol); with an amount of tetrahydrofuran (THF) as solvent, under nitrogen protection, in 60 ° of C; stirring reaction 10h; after reaction finished, resulting polymers solution precipitated with a large amount of ethanol, and precipitation is through obtaining the polymethyl acrylate of benzoxazolyl chain end fluorescence labelling after the vacuum-drying; molecular weight is 10350g/mol, and molecular weight distribution PDI is 1.29.Resulting polymers fluorescence such as figure below under the emission wavelength of 356nm, have a excitation peak the strongest in the 257nm place, under the 257nm wavelength excites, a emission peak the strongest is arranged at the 356nm place.As shown in Figure 2.
Embodiment 21: in the there-necked flask of a 150mL that magnetic agitation is housed; add vinylbenzene (20.8g; 0.2mol); RAFT reagent N-carbazole dithio formic acid 4-(2-benzoxazole) benzyl ester (0.90g; 0.002mol) initiator A IBN (0.066g; 0.0004mol); with an amount of tetrahydrofuran (THF) as solvent, under nitrogen protection, in 60 ° of C; stirring reaction 10h; after reaction finished, resulting polymers solution precipitated with a large amount of ethanol, and precipitation is through obtaining the polystyrene of benzoxazolyl chain end fluorescence labelling after the vacuum-drying; molecular weight is 11500g/mol, and molecular weight distribution PDI is 1.27.The fluorescence of resulting polymers and embodiment 20 polymethyl acrylates are similar, under the emission wavelength of 375nm, a very strong excitation peak are arranged in the 324nm place, under the 324nm wavelength excites, a very strong emission peak are arranged at the 375nm place.
Embodiment 22: in the there-necked flask of a 150mL that magnetic agitation is housed; add N; N-DMAA (19.8g; 0.2mol); RAFT reagent N-carbazole dithio formic acid 4-(2-benzoxazole) benzyl ester (0.90g, 0.002mol) initiator A IBN (0.066g, 0.0004mol); with an amount of tetrahydrofuran (THF) as solvent; under nitrogen protection, in 60 ° of C, stirring reaction 10h; after reaction finishes; resulting polymers solution precipitates with a large amount of ethanol, and precipitation is through obtaining the poly-N,N-DMAA of benzoxazolyl chain end fluorescence labelling after the vacuum-drying; molecular weight is 10050g/mol, and molecular weight distribution PDI is 1.28.The fluorescence of resulting polymers and embodiment 20 polymethyl acrylates are similar, under the emission wavelength of 375nm, a very strong excitation peak are arranged in the 324nm place, under the 324nm wavelength excites, a very strong emission peak are arranged at the 375nm place.
Embodiment 23: by the prepared benzoxazolyl RAFT reagent of embodiment 6 to embodiment 16, according to embodiment 17 described methods, may be used to prepare the polymkeric substance of benzoxazolyl chain end fluorescence labelling, the fluorescence property of the fluorescence property of resulting polymers and embodiment 17 resulting polymers is similar.
Claims (10)
1. a class benzoxazolyl fluorescence labelling RAFT reagent, the R group that it is characterized in that this RAFT reagent is the phenmethyl benzoxazole, its structure is:
Z is:
Y is: C
1～C
3Alkyl.
2. the preparation method of the described benzoxazolyl fluorescence labelling of claim 1 a RAFT reagent, it is characterized in that: in organic solvent, under the effect of alkaline catalysts, use carrying out nucleophilic substitution reaction between haloalkyl Ben base benzoxazole and water miscible dithio formate, Aminodithioformate or the trithiocarbonate reagent.
3. the preparation method of the described benzoxazolyl fluorescence labelling of claim 2 a RAFT reagent is characterized in that used to haloalkyl benzene base benzoxazole being: to the chloromethyl phenyl benzoxazole, to the 2-bromomethylphenyl benzoxazole or to iodomethyl benzene base benzoxazole.
4. the preparation method of the described benzoxazolyl fluorescence labelling of claim 2 a RAFT reagent, it is characterized in that used reagent is for having water miscible dithio formate, Aminodithioformate or trithiocarbonate, its structure be Z-C (=S)-S-M, structural formula is as follows:
Z is:
Y is: C
1～C
3Alkyl
M is: Na, K, MgCl or MgBr.
5. the preparation method of the described benzoxazolyl fluorescence labelling of claim 2 a RAFT reagent is characterized in that used reagent is dithiobenzoic acid magnesium bromide or N-carbazole dithio sodium formiate.
6. the preparation method of the described benzoxazolyl fluorescence labelling of claim 2 a RAFT reagent is characterized in that alkaline catalysts is sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, yellow soda ash, salt of wormwood, sodium phosphate, potassiumphosphate, dipotassium hydrogen phosphate, sodium-acetate, Potassium ethanoate, sodium hydride, potassium hydride KH or triethylamine.
7. the preparation method of the described benzoxazolyl fluorescence labelling of claim 2 a RAFT reagent is characterized in that used alkaline catalysts refers to sodium hydroxide or potassium hydroxide.
8. the preparation method of the described benzoxazolyl fluorescence labelling of claim 2 a RAFT reagent is characterized in that dithio formate, Aminodithioformate or trithiocarbonate and the mol ratio of haloalkyl benzene base benzoxazole is recommended as 1:1.5 ~ 2.0; Alkaline catalysts is recommended as 0.05 ~ 0.2:1 with mol ratio to haloalkyl Ben base benzoxazole.
9. the preparation method of the described benzoxazolyl fluorescence labelling of claim 2 a RAFT reagent is characterized in that solvent used in the nucleophilic substitution reaction process refers to tetrahydrofuran (THF), tetracol phenixin, chloroform, methylene dichloride, toluene, benzene, normal hexane, hexanaphthene, ethyl acetate, DMSO, dioxane or pyrrolidone.
10. with the fluorescence labelling functional polymer of the described benzoxazolyl fluorescence labelling of claim 1 RAFT reagent preparation, it is characterized in that monomer is selected from one or more in esters of acrylic acid, vinylbenzene and the acrylic amide.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897013A (en) * | 2019-03-31 | 2019-06-18 | 白银乐天园化学有限责任公司 | A kind of preparation method of selective PPAR delta agonists GW501516 |
| CN114599613A (en) * | 2019-11-07 | 2022-06-07 | 陶氏环球技术有限责任公司 | Fluorescently-labeled water treatment polymers |
-
2012
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| Title |
|---|
| RUIWEI GUO等: "Facile and Efficient Synthesis of Fluorescence-Labeled RAFT Agents and Their Application inthe Preparation of α -, ω - and α , ω -End-Fluorescence-Labeled Polymers", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897013A (en) * | 2019-03-31 | 2019-06-18 | 白银乐天园化学有限责任公司 | A kind of preparation method of selective PPAR delta agonists GW501516 |
| CN109897013B (en) * | 2019-03-31 | 2023-04-07 | 无锡科华生物科技有限公司 | Preparation method of selective PPAR delta agonist GW501516 |
| CN114599613A (en) * | 2019-11-07 | 2022-06-07 | 陶氏环球技术有限责任公司 | Fluorescently-labeled water treatment polymers |
| CN114599613B (en) * | 2019-11-07 | 2024-04-02 | 陶氏环球技术有限责任公司 | Fluorescent-labeled water treatment polymers |
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