CN108976242A - Synthesis a kind of while that there is photochromic and ion detection function Indoline spiropyran derivative - Google Patents
Synthesis a kind of while that there is photochromic and ion detection function Indoline spiropyran derivative Download PDFInfo
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- CN108976242A CN108976242A CN201810870159.7A CN201810870159A CN108976242A CN 108976242 A CN108976242 A CN 108976242A CN 201810870159 A CN201810870159 A CN 201810870159A CN 108976242 A CN108976242 A CN 108976242A
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- bromo
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- indoline
- ethyl
- dehydrated alcohol
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- UKXKGTGQIITIAB-UHFFFAOYSA-N spiro[1,3-dihydroindole-2,2'-pyran] Chemical class C1C2=CC=CC=C2NC11OC=CC=C1 UKXKGTGQIITIAB-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000001514 detection method Methods 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 241001141101 Nitrospirales Species 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 10
- -1 bromo- 1- ethyl -2,3,3- trimethyl -3H- indoles bromide Chemical class 0.000 claims description 7
- UMGFKFJUOSQNKK-UHFFFAOYSA-N C1=CC(Br)=C2C(C)(C)C(C)=NC2=C1 Chemical class C1=CC(Br)=C2C(C)(C)C(C)=NC2=C1 UMGFKFJUOSQNKK-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 claims description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 3
- MOIQBKKDRVMNMF-UHFFFAOYSA-N Cl.NN.BrC1=CC=CC=C1 Chemical compound Cl.NN.BrC1=CC=CC=C1 MOIQBKKDRVMNMF-UHFFFAOYSA-N 0.000 claims description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 230000003292 diminished effect Effects 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000004885 piperazines Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000005336 safety glass Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical group CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- FLHJIAFUWHPJRT-UHFFFAOYSA-N 2,3,3-trimethylindole Chemical compound C1=CC=C2C(C)(C)C(C)=NC2=C1 FLHJIAFUWHPJRT-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- 0 CCN(C(C1(C)C)(C=C2)Oc3c2cc(*)cc3)c(cc2)c1cc2Br Chemical compound CCN(C(C1(C)C)(C=C2)Oc3c2cc(*)cc3)c(cc2)c1cc2Br 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WINNISSSXBRWMA-UHFFFAOYSA-N dinitromethane Chemical compound [O-][N+](=O)C[N+]([O-])=O WINNISSSXBRWMA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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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
-
- 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
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- 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
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- 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
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- Immunology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Have the function of the Indoline spiropyran derivative of photochromic property, ion detection and heat, photochemical stable performance simultaneously the present invention relates to a kind of, it has following chemical structural formula:
Description
Technical field
Has the function of the Yin of photochromic property, ion detection and heat, photochemical stable simultaneously the present invention relates to a kind of
Diindyl quinoline spiropyran derivatives.
Background technique
The discovery of photochromism has more than 100 years history so far.Report is Meer earliest, he sent out in 1876
The sylvite for having showed dinitromethane has coloured reversible change under light action.Markward in 1899 has found l, 4- bis- again
Hydrogen -2,3,4,4- Tetrachloronaphthalene -1- ketone also have reversible color change under light action, and this phenomenon are called photochromic mutual
Become.
Indoline spiropyran is the most extensive the most in-depth one kind studied at present, nineteen fifty-two as photochromic compound
Fisher and Hirsthberg has found its photochromism again, and it is photochemical that Hirstberg in 1956 proposes that it can be used as
A possibility that recalling the optical shutter with a kind of variable density is learnt, the extensive concern of whole world scientist is caused.1994,
It is former to be put forward for the first time double photon three dimension storage using spiro-pyrans photochromic material as model compound by Rentzepis et al.
It manages and develops principle device.Heterolytic fission of the Indoline spiropyran class compound photochromic mechanism based on key, when with ultraviolet light
It when exciting colourless spiro-pyrans, that is, can lead to the heterolytic fission of spiral shell carbon-oxygen bond, generate absorption peak in the open loop portion of Long wavelength region and spend cyanines class
Compound.Indoline spiropyran class compound is under open loop situations, and optionally with certain complexing of metal ion, showing can
Detect the characteristic of ion.In storage application, hot unstability can be such that the information of record loses.Currently, most indoles
Quinoline spiro-pyrans class compound has that heat and photochemical stability are poor as optical storage media, changes colour recovery time
It is shorter, it is unable to the information that long-term preservation is recorded.Has the function of photochromic property, ion detection and heat, photochemistry simultaneously
There is not been reported for the Indoline spiropyran derivative of stability.The purpose of the present invention is design a kind of while having photochromic
Property, ion detection function and heat, the Indoline spiropyran derivative of photochemical stable and its synthetic method.It is visited in biology
The fields such as needle, photoswitch, the Indoline spiropyran derivative of this type can be used as very promising multi-functional, multi-use optical
Material.
Summary of the invention
The purpose of the present invention is design a kind of while having the function of photochromic property, ion detection and heat, photochemistry
The Indoline spiropyran derivative and its synthetic method of stability.
Technical scheme is as follows:
Indoline spiral shell that is a kind of while having the function of photochromic property, ion detection and heat, photochemical stable performance
Pyran derivate, it has following chemical structural formula:
A kind of preparation method of above-mentioned Indoline spiropyran derivative, it the following steps are included:
4- bromobenzene hydrazine hydrochloride and 3- methyl -2- butanone are added in flask by step 1, under stiring, acetic acid are added, are returned
Stream reaction 8h steams acetic acid, remaining liq saturation NaHCO after the reaction was completed3Solution adjusts pH value to 9, is extracted with ethyl acetate
It takes, obtained organic phase is spin-dried for solvent and obtains bromo- 2,3,3- trimethyl -3H- indoles crude product of 5-；
Step 2 is by the bromo- 2,3,3- tri-methyl indole of 5- and bromoethane CH3CH2- Br and dehydrated alcohol are added in flask, add
Thermal agitation has a large amount of solids to occur, and liquid reddens at this time to flowing back, and flow back 6h, and natural cooling stands overnight, is filtered under diminished pressure,
It is washed with methylene chloride, dry the bromo- 1- ethyl -2,3 of target product 5-, 3- trimethyl -3H- indoles bromide；
The bromo- 1- ethyl -2,3,3- trimethyl -3H- indoles bromide of 5- and 5- nitrosalicylaldehyde are added to burning by step 3
In bottle, dehydrated alcohol is added, heating stirring, when dehydrated alcohol reflux, a few drop piperazines are added dropwise from condenser pipe upper end in solid dissolution
Pyridine flows back after 6h, and natural cooling has solid appearance, and filtering is washed with cold dehydrated alcohol, dry, and it is bromo- to obtain pink solid 5'-
1'- ethyl -3', 3'- dimethyl -6- nitro spiral shell [chromene -2,2'- indoline]；
The present invention has the advantage that
1. the experimental program post-processing that the present invention is announced is simple, intermediate product can direct plunge into next step without further purification
Reaction.
2. the experimental program suitable substrates range that the present invention is announced is very wide, functional group compatibility is high, and yield is very high.
3. Indoline spiropyran derivative of the invention have the function of simultaneously photochromic property, ion detection and heat,
Photochemical stable performance.
Detailed description of the invention
Fig. 1 is that the hydrogen of bromo- 1'- ethyl -3', 3'- dimethyl -6- the nitro spiral shell [chromene -2,2'- indoline] of 5'- is composed.
Fig. 2 is that the carbon of bromo- 1'- ethyl -3', 3'- dimethyl -6- the nitro spiral shell [chromene -2,2'- indoline] of 5'- is composed.
Fig. 3 is that bromo- 1'- ethyl -3', 3'- dimethyl -6- nitro spiral shell [chromene -2,2'- the indoline]-ethyl alcohol of 5'- is molten
Liquid (1 × 10-4Mol/L ultra-violet absorption spectrum (365nm ultraviolet light, testing time 1-8s, maximum absorption wavelength λ)maxFor
553nm)。
Fig. 4 is bromo- 1'- ethyl -3', 3'- dimethyl -6- the nitro spiral shell [chromene -2,2'- indoles of 5'- containing compound
Quinoline] photochromism of the composite intermediate layer safety glass under the ultraviolet light irradiation of 360nm.
Fig. 5 is bromo- 1'- ethyl -3', 3'- dimethyl -6- the nitro spiral shell [chromene -2,2'- indoles of 5'- containing compound
Quinoline] composite intermediate layer safety glass color change cycle-index.
Fig. 6 is in bromo- 1'- ethyl -3', 3'- dimethyl -6- nitro spiral shell [chromene -2,2'- the indoline]-ethyl alcohol of 5'-
The ultra-violet absorption spectrum that different metal ions measure is added in solution.
Fig. 7 is the thermogravimetric of bromo- 1'- ethyl -3', 3'- dimethyl -6- the nitro spiral shell [chromene -2,2'- indoline] of 5'-
Analysis graph.
Specific embodiment
Prepare bromo- 1'- ethyl -3', 3'- dimethyl -6- the nitro spiral shell [chromene -2,2'- indoline] of 5'-
The first step, the synthesis of bromo- 2,3,3- trimethyl -3H- indoles of 5-
6.5g (29.5mmol) 4- bromobenzene hydrazine hydrochloride and 2.5g (29.5mmol) 3- methyl -2- butanone are added to
In 100mL three-neck flask, under magnetic agitation effect, 50mL acetic acid, back flow reaction 8h are added.After the reaction was completed, second is steamed
Acid, remaining liq saturation NaHCO3Solution adjusts pH value to 9 or so.It is extracted by several times with ethyl acetate, obtained organic phase is used
Anhydrous MgSO4It is dry, filter out MgSO4And it is spin-dried for solvent and obtains the bromo- 2,3,3- trimethyl -3H- indoles crude product of 5-；
Second step, the bromo- 1- ethyl -2,3 of 5-, the synthesis of 3- trimethyl -3H- indoles bromide
By 3.4g (14.4mmol) 2,3,3- tri-methyl indole and 1.6g (14.9mmol) bromoethane and 15mL dehydrated alcohol
It is added into 150mL round-bottomed flask, heating stirring has a large amount of solids to occur at this time to flowing back.Flow back 6h, and natural cooling is stood
Overnight, it is filtered under diminished pressure, is washed with methylene chloride, dry target product.
Third step, the conjunction of bromo- 1'- ethyl -3', 3'- dimethyl -6- the nitro spiral shell [chromene -2,2'- indoline] of 5'-
At
The bromo- 1- ethyl -2,3,3- trimethyl -3H- indoles bromide of 0.72g (2.1mmol) 5- and 0.35g (2.1mmol)
5- nitrosalicylaldehyde is added in 50mL round-bottomed flask, adds 20mL dehydrated alcohol, heating stirring.It flows back to dehydrated alcohol
When, solid dissolution is added dropwise a few drop piperidines from condenser pipe upper end, flows back after 6h, and natural cooling has solid appearance, filtering, with cold nothing
Water-ethanol washing, it is dry, obtain bromo- 1'- ethyl -3', 3'- dimethyl -6- the nitro spiral shell of target product 5'- [chromene -2,
2'- indoline].Its hydrogen spectrogram and carbon spectrogram are shown in Fig. 1 and Fig. 2.Its ultra-violet absorption spectrum is shown in Fig. 3.By micro Indoline spiropyran
Derivative be uniformly mixed with the tertiary butyraldehyde of appropriate polyvinyl alcohol, dibutyl phthalate and ethyl acetate institute at film, be placed in two
30 minutes obtained composite intermediate layer safety glasses are dried in pressurization at 140 DEG C between the unorganic glass of block 2mm thickness, in 360nm ultraviolet lamp
Irradiating its lower color becomes purple from colorless and transparent after irradiation 10 seconds；Dark place 48 hours or more its purple is placed in restore gradually
It is extremely colourless, see Fig. 4, cycle-index is shown in Fig. 5.Fig. 6 is shown in bromo- 1'- ethyl -3', 3'- the dimethyl -6- nitro spiral shell [benzene of 5'-
And pyrans -2,2'- indoline] that the ultra-violet absorption spectrum that different metal ions measure is added in-ethanol solution is different, therefore it has
There is ion detection function.Fig. 7 shows that the 5% weightless decomposition temperature of BNI is 268 DEG C, and total weight loss is not before temperature is lower than 597 DEG C
More than 40%, this shows that BNI molecule possesses very outstanding hot property, is a kind of photochromic material with potential application foreground
Material.
Claims (2)
1. a kind of have the function of the indoline spiral shell pyrrole of photochromic property, ion detection and heat, photochemical stable performance simultaneously
It mutters derivative, it is characterized in that it has following chemical structural formula:
2. the preparation method of Indoline spiropyran derivative described in a kind of claim 1, it is characterized in that it the following steps are included:
4- bromobenzene hydrazine hydrochloride and 3- methyl -2- butanone are added in flask by step 1, under stiring, acetic acid are added, reflux is anti-
8h is answered, after the reaction was completed, steams acetic acid, remaining liq saturation NaHCO3Solution adjusts pH value to 9, is extracted with ethyl acetate,
Obtained organic phase is spin-dried for solvent and obtains the bromo- 2,3,3- trimethyl -3H- indoles crude product of 5-；
Step 2 is by the bromo- 2,3,3- tri-methyl indole of 5- and bromoethane CH3CH2- Br and dehydrated alcohol are added in flask, and heating is stirred
It mixes to reflux, there are a large amount of solids to occur at this time, and liquid reddens, flow back 6h, and natural cooling stands overnight, is filtered under diminished pressure, with two
Chloromethanes washing, dry bromo- 2,3,3- trimethyl -1- alkyl -3H- indoles bromide of target product 5-；
The bromo- 1- ethyl -2,3,3- trimethyl -3H- indoles bromide of 5- and 5- nitrosalicylaldehyde are added to flask by step 3
In, dehydrated alcohol is added, heating stirring, when dehydrated alcohol reflux, a few drop piperazines are added dropwise from condenser pipe upper end in solid dissolution
Pyridine flows back after 6h, and natural cooling has solid appearance, and filtering is washed with cold dehydrated alcohol, dry, and it is bromo- to obtain pink solid 5'-
1'- ethyl -3', 3'- dimethyl -6- nitro spiral shell [chromene -2,2'- indoline].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810870159.7A CN108976242A (en) | 2018-08-02 | 2018-08-02 | Synthesis a kind of while that there is photochromic and ion detection function Indoline spiropyran derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810870159.7A CN108976242A (en) | 2018-08-02 | 2018-08-02 | Synthesis a kind of while that there is photochromic and ion detection function Indoline spiropyran derivative |
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| Publication Number | Publication Date |
|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590794A (en) * | 2019-10-08 | 2019-12-20 | 湖南大学 | Novel dicarboxy spiropyran derivative and preparation method thereof |
| CN113024571A (en) * | 2021-03-24 | 2021-06-25 | 北京大学 | Spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and preparation method and application thereof |
| CN113046093A (en) * | 2021-03-24 | 2021-06-29 | 北京大学 | Patterned liquid crystal film based on spiropyran derivative molecular switch and preparation method and application thereof |
| CN113372484A (en) * | 2021-06-11 | 2021-09-10 | 南京大学 | Cationic hydrogel for in-situ catalytic crosslinking of spiropyran and preparation method thereof |
| CN113637020A (en) * | 2021-08-18 | 2021-11-12 | 江南大学 | Water-soluble photochromic compound and preparation method and application thereof |
| CN113666939A (en) * | 2021-08-17 | 2021-11-19 | 康赛妮集团有限公司 | Photochromic compound and preparation method and application thereof |
| CN113736282A (en) * | 2021-09-07 | 2021-12-03 | 三峡大学 | Synthesis and application of indole hemicyanine structure photochromic dye |
| CN115209869A (en) * | 2020-02-17 | 2022-10-18 | 因特科股份有限公司 | Transparent colored cosmetic composition capable of automatically changing color under ultraviolet irradiation |
| CN116814149A (en) * | 2023-05-23 | 2023-09-29 | 厦门卓施特新材料科技有限公司 | High-stability aerogel temperature change control Wen Gaoliao and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6167848A (en) * | 1984-09-11 | 1986-04-08 | Mitsubishi Chem Ind Ltd | Recording material |
| CN105820171A (en) * | 2016-04-21 | 2016-08-03 | 常州大学 | Benzoindoline spiropyran colorimetric probe as well as preparation method and application |
| WO2016199173A1 (en) * | 2015-06-10 | 2016-12-15 | Council Of Scientific & Industrial Research | Novel spiropyran based composition and application thereof as security tag |
-
2018
- 2018-08-02 CN CN201810870159.7A patent/CN108976242A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6167848A (en) * | 1984-09-11 | 1986-04-08 | Mitsubishi Chem Ind Ltd | Recording material |
| WO2016199173A1 (en) * | 2015-06-10 | 2016-12-15 | Council Of Scientific & Industrial Research | Novel spiropyran based composition and application thereof as security tag |
| CN105820171A (en) * | 2016-04-21 | 2016-08-03 | 常州大学 | Benzoindoline spiropyran colorimetric probe as well as preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| BAOZHONG LV等: "Spiropyran-induced one-dimensional cyclodextrin microcrystals with light-driven fluorescence change", 《J. MATER. CHEM. C》 * |
| 严韩: "新型光功能有机分子的结构设计、合成及其性质研究", 《南京大学研究生毕业论文》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590794A (en) * | 2019-10-08 | 2019-12-20 | 湖南大学 | Novel dicarboxy spiropyran derivative and preparation method thereof |
| CN115209869A (en) * | 2020-02-17 | 2022-10-18 | 因特科股份有限公司 | Transparent colored cosmetic composition capable of automatically changing color under ultraviolet irradiation |
| CN113024571A (en) * | 2021-03-24 | 2021-06-25 | 北京大学 | Spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and preparation method and application thereof |
| CN113046093A (en) * | 2021-03-24 | 2021-06-29 | 北京大学 | Patterned liquid crystal film based on spiropyran derivative molecular switch and preparation method and application thereof |
| CN113372484A (en) * | 2021-06-11 | 2021-09-10 | 南京大学 | Cationic hydrogel for in-situ catalytic crosslinking of spiropyran and preparation method thereof |
| CN113666939A (en) * | 2021-08-17 | 2021-11-19 | 康赛妮集团有限公司 | Photochromic compound and preparation method and application thereof |
| CN113637020A (en) * | 2021-08-18 | 2021-11-12 | 江南大学 | Water-soluble photochromic compound and preparation method and application thereof |
| CN113736282A (en) * | 2021-09-07 | 2021-12-03 | 三峡大学 | Synthesis and application of indole hemicyanine structure photochromic dye |
| CN113736282B (en) * | 2021-09-07 | 2023-08-01 | 三峡大学 | Synthesis and application of indole hemicyanine structure photochromic dye |
| CN116814149A (en) * | 2023-05-23 | 2023-09-29 | 厦门卓施特新材料科技有限公司 | High-stability aerogel temperature change control Wen Gaoliao and preparation method thereof |
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