CN109320519A - A kind of synthetic method of double hydroxyls or trihydroxy Rhodamine Derivatives - Google Patents

A kind of synthetic method of double hydroxyls or trihydroxy Rhodamine Derivatives Download PDF

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CN109320519A
CN109320519A CN201810981655.XA CN201810981655A CN109320519A CN 109320519 A CN109320519 A CN 109320519A CN 201810981655 A CN201810981655 A CN 201810981655A CN 109320519 A CN109320519 A CN 109320519A
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rh6g
trihydroxy
acetic acid
glacial acetic
synthetic method
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马志勇
杨扬
胡欢
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom

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Abstract

The synthetic method of a kind of double hydroxyls or trihydroxy Rhodamine Derivatives belongs to methodology of organic synthesis.Rh6G-OH and ethylene oxide are added under the condition of ice salt bath in the tetrahydrofuran solution of glacial acetic acid, wherein the molar ratio of Rh6G-OH and ethylene oxide is 1:5~20, and the molar ratio of Rh6G-OH and glacial acetic acid is 1:300；After reaction 48h or more is stirred at room temperature, revolving removes solvent and obtains crude product；White solid is obtained after crude product pillar layer separation；Synthetic route of the present invention is simple and efficient, and reaction substrate is simple and easy to get, and reaction condition as mild as a dove (normal temperature and pressure), and can control obtained product by changing the reaction time.Double hydroxyls, trihydroxy Rhodamine Derivatives in the present invention, which are easy to be introduced directly into polyurethane (perhaps polyureas) chain, to be also easy to connect double bond or initiator is linked into the more polyolefin chains of type, there is boundless application prospect.

Description

A kind of synthetic method of double hydroxyls or trihydroxy Rhodamine Derivatives
Technical field
The invention belongs to methodology of organic synthesis field, summary of the invention is a kind of double hydroxyls, trihydroxy Rhodamine Derivatives Synthetic method and application.
Background technique
Intelligent response fluorescence off-color material is increasingly becoming research hotspot, effect of this kind of material in environmental stimuli in recent years Reversible variation can occur for its lower fluorescence property (such as luminous color and intensity).Rhodamine is a kind of common iridescent Group, rhodamine have good photophysical property, such as high extinction coefficient, high quantum production rate, photostability and long transmitted wave It is long.In addition, rhodamine molecule can be designed by structure, synthesis obtains the derivative with different functional groups, this is conducive to Adjust its luminosity.It is before us research shows that rhodamine lactams is the quick group of the very excellent power of a kind of performance.Mesh Preceding that Rhodamine Derivatives are introduced into polymeric system is actually rare to prepare the report of force-responsive material, and main cause is sieve The external functional group of red light colour group is few, it is difficult to be introduced into polymer chain.The present invention provides one kind to be efficiently synthesized double hydroxyls The method of base, trihydroxy Rhodamine Derivatives, our 70% or more method yield, the rhodamine of this kind of polyhydroxy is easy to Be introduced directly into the chain of polyurethane (perhaps polyureas) be also easy to connect double bond or initiator to be linked into type more Polyolefin chain in, have boundless application prospect preparing force-responsive fluorescence intelligent color-changing Material Field.In the present invention Rhodamine Derivatives retain the original structure of rhodamine as completely as possible, it is contemplated that its excellent photoluminescent property will obtain To reservation.The access site (number of hydroxyl) for increasing Rhodamine Derivatives makes rhodamine color group multidigit point be incorporated into polymer Structure, limited degree is higher, is then expected to the response of external force sensitiveer.
Summary of the invention
The purpose of the present invention is to provide the synthetic methods and application of a kind of double hydroxyls, trihydroxy Rhodamine Derivatives.
Advantages of the present invention and its application prospect:
Synthetic route provided by the present invention is simple and efficient, and reaction substrate is simple and easy to get, and reaction condition is (normal as mild as a dove Normal temperature and pressure), and obtained product can be controlled by changing the reaction time.
Double hydroxyls, trihydroxy Rhodamine Derivatives in the present invention are easy to be introduced directly into polyurethane (or polyureas) In chain, also it is easy to connect double bond or initiator is linked into the more polyolefin chains of type, preparing force-responsive fluorescence There is boundless application prospect in intelligent color-changing polymer material field.
A kind of synthetic method of double hydroxyls or trihydroxy Rhodamine Derivatives, it is characterised in that:
Rh6G-OH and ethylene oxide are added under the condition of ice salt bath in the tetrahydrofuran solution of glacial acetic acid, wherein The molar ratio of Rh6G-OH and ethylene oxide is 1:5~20, and the molar ratio of Rh6G-OH and glacial acetic acid is 1:300；It is stirred at room temperature anti- After answering 48h or more, revolving removes solvent and obtains crude product；White solid is obtained after crude product pillar layer separation；
Wherein react 72h or more, all trihydroxy product Rh6G-3OH:
It reacts 48-72h and is free of 72h, for the mixing of double hydroxy product Rh6G-2OH and trihydroxy product Rh6G-3OH Object.
Further, pillar layer separation eluant, eluent is methylene chloride: ethyl alcohol volume ratio is the mixed liquor of 35:1.
Further, glacial acetic acid and tetrahydrofuran volume ratio are 1:1 in the tetrahydrofuran solution of glacial acetic acid.
The molecular structure of four kinds of dihydroxy, trihydroxy Rhodamine Derivatives.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum of compound R h6G-2OH.Abscissa is chemical shift, unit: ppm；Ordinate is strong Degree.
The nuclear-magnetism carbon that Fig. 2 is compound R h6G-2OH is composed.Abscissa is chemical shift, unit: ppm；Ordinate is strong Degree.
Fig. 3 is the nucleus magnetic hydrogen spectrum of compound R h6G-3OH.Abscissa is chemical shift, unit: ppm；Ordinate is strong Degree.
The nuclear-magnetism carbon that Fig. 4 is compound R h6G-3OH is composed.Abscissa is chemical shift, unit: ppm；Ordinate is strong Degree.
Specific embodiment
Synthetic route and specific synthesis step
Synthesis step example:
The synthesis of Rh6G-2OH/3OH
Rh6G is a kind of very cheap raw material, and Rh6G and ethanol amine flow back 12 hours in ethanol, and precipitating is precipitated and is Rh6G-OH, yield are more than 90%.
The round-bottomed flask for taking a 150mL, by Rh6G-OH (1.00g, 2.1mmol) and ethylene oxide (0.96g, It 21.0mmol) is added under the condition of ice salt bath in the tetrahydrofuran solution (1/1, v/v) of 70mL glacial acetic acid, reaction is stirred at room temperature After 48h or 72h, revolving removes solvent and obtains crude product.Crude product with pillar layer separation (methylene chloride: ethyl alcohol volume ratio= 35:1, v/v) after obtain white solid.48h is reacted, yield: 72% (double hydroxy products: 0.40g, 36%, trihydroxy product: 0.43g, 36%).72h is reacted, all trihydroxy products: 0.95g, 80%.
Rh6G-OH and ethylene oxide are added under the condition of ice salt bath in the tetrahydrofuran solution of glacial acetic acid, wherein The molar ratio of Rh6G-OH and ethylene oxide is 1:5~20, and the molar ratio of Rh6G-OH and glacial acetic acid is 1mmol:300mmol；Room After temperature is stirred to react 48h-72h, revolving removes solvent and obtains crude product.White solid is obtained after crude product pillar layer separation.
React 72h or more, all trihydroxy product Rh6G-3OH:
48-72h is reacted, 72h is free of, for the mixture of double hydroxy product Rh6G-2OH and trihydroxy product Rh6G-3OH
Further, Rh6G-2OH is respectively obtained after pillar layer separation (eluant, eluent is methylene chloride: ethyl alcohol=35:1, v/v) (white solid) and Rh6G-3OH (pink solid).
Example 1
The round-bottomed flask for taking a 150mL, by Rh6G-OH (1.00g, 2.1mmol) and ethylene oxide (0.96g, It 21.0mmol) is added under the condition of ice salt bath in the tetrahydrofuran solution (1/1, v/v) of 70mL glacial acetic acid, reaction is stirred at room temperature After 48h, revolving removes solvent and obtains crude product.Crude product is obtained with after pillar layer separation (methylene chloride: ethyl alcohol=35:1, v/v) To Rh6G-2OH (white solid) and Rh6G-3OH (pink solid).Gross production rate: 72% (double hydroxy products: 0.40g, 36%, Trihydroxy product: 0.43g, 36%).
Example 2
The round-bottomed flask for taking a 150mL, by Rh6G-OH (1.00g, 2.1mmol) and ethylene oxide (0.96g, It 21.0mmol) is added under the condition of ice salt bath in the tetrahydrofuran solution (1/1, v/v) of 70mL glacial acetic acid, reaction is stirred at room temperature After 60h, revolving removes solvent and obtains crude product.Crude product is obtained with after pillar layer separation (methylene chloride: ethyl alcohol=35:1, v/v) To Rh6G-2OH (white solid) and Rh6G-3OH (pink solid).Gross production rate: 75% (double hydroxy products: 0.17g, 15%, Trihydroxy product: 0.72g, 60%).
Example 3
The round-bottomed flask for taking a 150mL, by Rh6G-OH (1.00g, 2.1mmol) and ethylene oxide (0.96g, It 21.0mmol) is added under the condition of ice salt bath in the tetrahydrofuran solution (1/1, v/v) of 70mL glacial acetic acid, reaction is stirred at room temperature After 72h, revolving removes solvent and obtains crude product.Crude product is obtained with after pillar layer separation (methylene chloride: ethyl alcohol=35:1, v/v) To Rh6G-3OH (pink solid).All trihydroxy products: 0.95g, 80%.
Rh6G-2OH
Nucleus magnetic hydrogen spectrum1H NMR(400MHz,CDCl3)δ/ppm:8.07–7.83(m,1H), 7.57–7.40(m,2H), 7.13-6.99 (m, 1H), 6.91 (s, 2H), 6.48 (d, J=10.4 Hz, 2H), 3.62 (t, J=5.3Hz, 4H), 3.41 (d, J =25.5Hz, 2H), 3.28 (dd, J=9.4,4.7Hz, 2H), 3.25-3.14 (m, 4H), 3.08-2.96 (m, 4H), 2.09 (d, J=9.1Hz, 6H), 1.03 (t, J=7.1Hz, 6H)
Nuclear-magnetism carbon spectrum13C NMR(101MHz,CDCl3)δ/ppm:170.14,153.52, 151.46,150.56, 150.44,147.74,132.92,130.25,130.00,129.49,128.44, 128.01,123.82,123.13, 118.51,113.83,110.44,104.85,96.49,65.70, 62.40,59.07,53.76,48.32,44.81,38.35, 17.85,16.75,14.69,11.66.
Rh6G-3OH
Nucleus magnetic hydrogen spectrum1H NMR(400MHz,CDCl3), δ/ppm:8.68 (s, 1H ,-CH=N), 8.46 (s, 1H, Ar-H), 8.42 (s, 1H, Ar-H), 8.16 (s, 1H, Ar-H), 8.06~7.99 (m, 4H, Ar-H), 7.72~7.69 (d, 5H, Ar-H), 7.51~7.45 (m, 4H, Ar-H), 7.15~7.13 (m, H, Ar-H), 6.57 (s, 1H, Ar-H), 6.54 (s, 1H, Ar-H), 6.47~6.46 (d, 2H, Ar-H), 6.27~6.24 (m, 2H, Ar-H), 3.35~3.32 (m, 8H, CH3CH2), 1.18~ 1.14(t,12H,CH3CH2-).
Nuclear-magnetism carbon spectrum13C NMR(101MHz,CDCl3)δ/ppm:170.20,153.13, 150.85,150.18, 133.08,130.36,130.03,129.49,128.70,123.81,123.32, 113.45,110.41,65.37,62.18, 59.08,53.73,48.25,44.94,17.89,11.62.
RhBRh6G-2OH and RhB-3OH can refer to above method and synthesize to obtain, using ethylene oxide as reactant, vinegar Acid and tetrahydrofuran are as solvent.

Claims (3)

1. the synthetic method of a kind of double hydroxyls or trihydroxy Rhodamine Derivatives, it is characterised in that:
Rh6G-OH and ethylene oxide are added under the condition of ice salt bath in the tetrahydrofuran solution of glacial acetic acid, wherein Rh6G-OH and The molar ratio of ethylene oxide is 1:5~20, and the molar ratio of Rh6G-OH and glacial acetic acid is 1:300；Reaction 48h or more is stirred at room temperature Afterwards, revolving removes solvent and obtains crude product；White solid is obtained after crude product pillar layer separation；
Wherein react 72h or more, all trihydroxy product Rh6G-3OH:
It reacts 48-72h and is free of 72h, for the mixture of double hydroxy product Rh6G-2OH and trihydroxy product Rh6G-3OH.
2. synthetic method according to claim 1, it is characterised in that:
Pillar layer separation eluant, eluent is methylene chloride: ethyl alcohol volume ratio is the mixed liquor of 35:1.
3. synthetic method according to claim 1, it is characterised in that: glacial acetic acid and four in the tetrahydrofuran solution of glacial acetic acid Hydrogen furans volume ratio is 1:1.
CN201810981655.XA 2018-08-27 2018-08-27 A kind of synthetic method of double hydroxyls or trihydroxy Rhodamine Derivatives Pending CN109320519A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113354789A (en) * 2021-07-21 2021-09-07 江南大学 Force-induced color-changing polyurethane elastomer material, and preparation method and application thereof

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113354789A (en) * 2021-07-21 2021-09-07 江南大学 Force-induced color-changing polyurethane elastomer material, and preparation method and application thereof

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Application publication date: 20190212