CN108892680A - A kind of preparation method of bissiropyran power color group - Google Patents
A kind of preparation method of bissiropyran power color group Download PDFInfo
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- CN108892680A CN108892680A CN201810922159.7A CN201810922159A CN108892680A CN 108892680 A CN108892680 A CN 108892680A CN 201810922159 A CN201810922159 A CN 201810922159A CN 108892680 A CN108892680 A CN 108892680A
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- bissiropyran
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- power color
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- SMQUZDBALVYZAC-UHFFFAOYSA-N ortho-hydroxybenzaldehyde Natural products OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 salicylaldehyde compound Chemical class 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 150000003413 spiro compounds Chemical class 0.000 claims description 2
- ZTRPYTHOEREHEN-UHFFFAOYSA-N piperazine pyridine Chemical group N1CCNCC1.N1=CC=CC=C1.N1=CC=CC=C1 ZTRPYTHOEREHEN-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 12
- 239000008367 deionised water Substances 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 abstract description 5
- 239000004814 polyurethane Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- ZYZWCJWINLGQRL-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)CC=C1C1=CC=CC=C1 ZYZWCJWINLGQRL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000003471 mutagenic agent Substances 0.000 abstract description 4
- 231100000707 mutagenic chemical Toxicity 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract 3
- 239000006184 cosolvent Substances 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QSECPQCFCWVBKM-UHFFFAOYSA-N 2-iodoethanol Chemical compound OCCI QSECPQCFCWVBKM-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- FLHJIAFUWHPJRT-UHFFFAOYSA-N 2,3,3-trimethylindole Chemical class C1=CC=C2C(C)(C)C(C)=NC2=C1 FLHJIAFUWHPJRT-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010011469 Crying Diseases 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3293—Hydroxyamines containing heterocyclic groups
-
- 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
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a kind of preparation methods of bissiropyran power color group.With 4,4- dihydroxybiphenyl, sodium hydroxide, chloroform, deionized water for raw material, using ethylene glycol as cosolvent, synthesized double salicylaldehyde compound, then with benzazolyl compounds condensation reaction, prepared bissiropyran power color group compound.The simple process, reaction condition are mild.Since the bissiropyran has double hydroxyls, it can be very good to be connected among macromolecular chain (such as polyurethane), when macromolecular chain is by mechanical force, power mutagens color occurs for polymer, it can be used as mechanics probing needle, apply to the fields such as stress early warning, detection.
Description
Technical field
The invention discloses a kind of preparation methods of bissiropyran power color group, particularly belong to organic synthesis field.
Background technique
Nearly two during the last ten years, is largely constantly exploited to the functional material system of the stimuli responsives such as heat, light, electricity, mechanical force.
Mechanical force has some unique advantages as a kind of stimulation, and high molecular material is directed to machine in overwhelming majority application
The effect of tool power, therefore develop having a very important significance for force-responsive high molecular material.
Force-responsive polymer is primarily referred to as the various reactions that macromolecular chain participates in when by external force, especially its
Specific reaction introduces specific chemical group or group (also crying power color group) in macromolecular chain, under mechanical force,
Macroscopical external force is passed to the power color group on chain by macromolecular chain, and induction force color group chemically reacts, controllably generates a series of
Important function.
Mechanical force is reported on Nature from Moore seminar in 2007 can activate benzocyclobutene generation open loop, first
It is secondary to prove that mechanical force drive chemical reaction to occur and along the reaction road kinetically prohibited by (heat or light stimulus)
Diameter carries out, and generates the product with high selectivity, macromolecule power chemistry rapidly becomes many multi-disciplinary research hotspots, including changes
, polymer science, material science, bioscience, computer simulation etc..What power color was rolled into a ball is designed to force-responsive polymer
Core content.Power color reported at present rolls into a ball rather limited number, and preparation process is complicated, the application of restraint color group, therefore opens
The power color group for sending out novel, can not only enrich the type of power color group, but also provide more selections for force-responsive polymer.
Spiro-pyrans as power color group with have good power mutagens color, intelligent early-warning, in terms of have it is critically important
Utilization；Bissiropyran is developed double due to having the characteristics that there is better thermal stability, fatigue resistance than spiro-pyrans
Spiro-pyrans power color group, can not only enrich the type of power color group, while can expand the development of force-responsive material.
Summary of the invention
It is an object of the present invention to alleviate the deficiency of existing power color group number, more selections are provided for force-responsive material,
The present invention provides a kind of methods that simplicity prepares bissiropyran power color group, and bissiropyran is introduced into polyurethane system,
Study the force-responsive of its polymer.
In order to realize such purpose, 4,4- dihydroxybiphenyl, sodium hydroxide, chlorine are used in technical solution of the present invention
Imitative, deionized water is that raw material prepares double salicylaldehyde compound, and salicylide and benzazolyl compounds condensation is utilized to obtain bissiropyran
Bissiropyran power color group is finally introduced into polyether polyols by power color group.
The present invention is implemented by the following steps：
Novel bissiropyran power color group, structure involved in the present invention are as follows：
The principle that the present invention prepares bissiropyran power color group compound is as follows：
(1) preparation of double salicylaldehyde
(2) preparation of benzazolyl compounds
(3) preparation of bissiropyran compound
The method of prepare compound of the present invention is as follows：
A:The preparation of double salicylaldehyde compound：
(1) under nitrogen protection, a certain amount of 4,4- dihydroxybiphenyl is weighed, sodium hydroxide, deionized water is in reaction flask
In, 4,4- dihydroxybiphenyls, the molar ratio of sodium hydroxide and deionized water is 1:15:300；
(2) stirring is started, is stirred at reflux, then chloroform and triethylamine mixed solution is added dropwise (mixed liquor volume ratio is 5:1),
Chloroform and 4,4- dihydroxybiphenyl molar ratio are 3.5:1；
(3) back flow reaction 5h, it is cooling, 2mol/L hydrochloric acid solution is added dropwise and is neutralized to neutral (detection of pH test paper), ethyl acetate
Extraction, concentration, column chromatography purifying obtain yellow powder double salicylaldehyde solid.
B:The preparation of benzazolyl compounds：
(1) under nitrogen protection, a certain amount of 2 are weighed, 3,3- tri-methyl indoles are dissolved in anhydrous chloroform, and 2,3,3- tri-
The molar ratio 1 of methyl indol and chloroform：20-1:25；
(2) take a certain amount of ethylene iodohydrin into step 1), the molar ratio of ethylene iodohydrin and 2,3,3- tri-methyl indoles is
1.5:1；
(3) stirring is started, 48h, cooling concentration are reacted under 70 DEG C of constant temperatures, petroleum ether recrystallizes 2 times, obtains purple
Solid；
(4) it weighs a certain amount of step 3) acquisition violet solid and is added to the potassium hydroxide aqueous solution that mass fraction is 20%
In, the molar ratio of violet solid and potassium hydroxide is 1:5-1:In 8；
(5) stirring is started, yellow oil is obtained after 20min, stops stirring, with petroleum ether extraction grease, concentration is obtained
Obtain benzazolyl compounds.
C:The preparation of bissiropyran compound：
1) a certain amount of double salicylaldehyde compound dissolution is weighed in a solvent, the molar ratio of double salicylaldehyde and solvent is 1:
50-1:100；
2) a certain amount of benzazolyl compounds are weighed into solution described in step 1), the benzazolyl compounds and double salicylaldehyde
Molar ratio is 2:1；
3) take a certain amount of catalyst into the 2) solution, the molar ratio of catalyst and benzazolyl compounds is 1:2；
4) stirring is started, reacts 30-36h under 70-85 DEG C of constant temperature, obtains brown liquid, is concentrated, column layer chromatography obtains ink
Green solid powder.
The catalyst is piperidines, triethylene diamine, triethylamine.
The solvent is ethyl alcohol, methanol.
Double spiro-compounds are applied to early warning, context of detection.
Beneficial effects of the present invention
The double salicylaldehyde for the preparation that is easy to get and benzazolyl compounds are carried out condensation reaction by the present invention, obtain a kind of new chemical combination
The compound is introduced into polyurethane system by object, has the discoloration of good mechanical stress, can be used as stress early warning, detection.
Detailed description of the invention
The hydrogen spectrum and carbon spectrum of 1 bissiropyran power color of attached drawing group；
2 hydrogen of polyurethane containing spiro-pyrans of attached drawing spectrum；
3 polyurethane film of attached drawing stretches the color change of front and back.
Specific embodiment
Technical solution in order to preferably explain the present invention is further chatted in detail by specific embodiment work below
It states：
1, the preparation of double salicylaldehyde
A 250mL three-necked flask is taken, 2.98g4,4- dihydroxybiphenyl (0.016mol), 9.98g sodium hydroxide are separately added into
(0.24mol), 90mL deionized water (5mol).A constant pressure funnel is separately taken, chloroform (10mL) is added and triethylamine (2mL) is mixed
Liquid is closed, under nitrogen protection, 65 DEG C of back flow reaction 5h are cooling, and the hydrochloric acid that 2mol/L is added dropwise makes solution be in neutrality (detection of pH test paper),
It is extracted with ethyl acetate, is concentrated, column chromatography separating purification, obtains 0.113g yellow greenish powder i.e. bissiropyran later, and yield is
2.92%, nuclear magnetic data is as follows：
1H NMR(DMSO,400MHz):δ (ppm)=10.85 (s, 2H), 10.33 (s, 2H), 7.90 (s, 2H), 7.84-
7.81 (t, J=8.73Hz, 2H), 7.11-7.09 (t, J=8.60Hz, 2H)13C NMR(DMSO,400MHz):δ (ppm)=
192.11,160.42,134.46,130.77,126.75,122.88,118.44.
2, the preparation of benzazolyl compounds
A 50mL branch mouth bottle is taken, 2,3,3- tri-methyl indole (6.22mmol) of 2mL, 1.46mL ethylene iodohydrin is added
(9.33mmol), and 20mLCHCl is added3As solvent, under nitrogen protection, 70 DEG C of isothermal reaction 48h are cooled to room temperature, dense
Contracting obtains purple grease, then is recrystallized 2 times with petroleum ether and obtain violet solid, and yield 70%, nuclear magnetic data is as follows：
1H NMR(CDCl3,500MHz):δ (ppm)=7.80-7.76 (m, 1H), 7.61-7.55 (m, 3H), 4.88 (t,
2H),4.20(t,2H),3.10(s,3H),1.65(s,6H)。
A 100mL round-bottomed flask is taken, is added 50mL potassium hydroxide solution (mass fraction 20%), adds 1 gram of purple
Solid, solution stir 20min, obtain yellow oil with petroleum ether extraction yellow oil and are concentrated to get benzazolyl compounds,
Yield is 80%, and nuclear magnetic data is as follows：
1H NMR(CDCl3,500MHz):δ (ppm)=7.14 (t, 1H), 7.07 (d, 1H), 6.92 (t, 1H), 6.76 (d,
1H),3.86-3.81(m,2H),3.75-3.70(m,2H),3.61-3.48(m,4H),1.43-1.38(s,6H)。
3, the preparation of bissiropyran
The branch mouth bottle for taking a 100mL, is separately added into double salicylaldehyde (0.43g, 0.00178mol), benzazolyl compounds
(0.72g, 0.00356mol) and piperidines (0.176mL, 0.00178mol) and 50mL dehydrated alcohol, under nitrogen protection, at 85 DEG C
Constant temperature back flow reaction 30h.It is spin-dried for solvent after reaction, with petroleum ether solid, column chromatography separating purification (dichloromethane later
Alkane：Ethyl acetate=20:1) blackish green bissiropyran solid 0.437g, yield 38%, are obtained.Its nuclear magnetic data is following (specific
Nuclear magnetic spectrogram is shown in attached drawing 1).
1H NMR(CDCl3,400MHz):δ (ppm)=7.24 (s, 2H), 7.19-7.18 (d, J=2.10Hz, 2H),
7.17-7.15 (d, J=7.86Hz, 2H), 7.10-7.08 (d, J=7.16Hz, 2H), 6.86 (m, 2H), 6.84 (s, 2H),
6.75-6.72 (d, J=8.41Hz, 2H), 6.65-6.63 (d, J=7.71Hz, 2H), 5.73-5.70 (d, J=10.05Hz,
4H),3.76(s,2H),3.51(m,4H),3.37(m,2H),[1.33&1.18](s,6H).
13C NMR(CDCl3,400MHz):δ (ppm)=153.09,147.35,136.44,133.14,129.59,
128.11,127.63,124.95,121.90,120.07,119.40,118.79,115.35,106.65,104.76,60.87,
52.35,46.17,25.92,20.38.
Embodiment 2
The branch mouth bottle for taking a 100mL, is separately added into double salicylaldehyde (0.43g, 0.00178mol), benzazolyl compounds
(0.72g, 0.00356mol) and triethylamine (0.246mL, 0.00178mol) and 60mL anhydrous methanol, under nitrogen protection, 85
DEG C constant temperature back flow reaction 30h.It is spin-dried for solvent after reaction, with petroleum ether solid, column chromatography separating purification (dichloro later
Methane：Ethyl acetate=20:1) blackish green bissiropyran solid 0.34g, yield 29.7%, are obtained.Specific nuclear magnetic spectrogram is shown in attached
Fig. 1.
Embodiment 3
The branch mouth bottle for taking a 100mL is separately added into double salicylaldehyde (0.43g, 0.00178mol) benzazolyl compounds
(0.72g, 0.00356mol) and triethylene diamine (0.399g, 0.00178mol) and 50mL dehydrated alcohol, under nitrogen protection,
85 DEG C of constant temperature back flow reaction 30h.It is spin-dried for solvent after reaction, with petroleum ether solid, column chromatography separating purification (two later
Chloromethanes：Ethyl acetate=20:1) blackish green bissiropyran solid 0.37g, yield 32.1%, are obtained.Specific nuclear magnetic spectrogram is shown in
Attached drawing 1.
Embodiment 4
The branch mouth bottle for taking a 100mL is separately added into double salicylaldehyde (0.43g, 0.00178mol) benzazolyl compounds
(0.72g, 0.00356mol) and piperidines (0.176mL, 0.00178mol) and 60mL anhydrous methanol, under nitrogen protection, at 70 DEG C
Constant temperature back flow reaction 36h.It is spin-dried for solvent after reaction, with petroleum ether solid, column chromatography separating purification (dichloromethane later
Alkane：Ethyl acetate=20:1) blackish green bissiropyran solid 0.32g, yield 27.6%, are obtained.Specific nuclear magnetic spectrogram is shown in attached drawing
1。
Embodiment 5
1, the preparation of polyurethane
A 25mL branch mouth bottle is taken, is added bissiropyran (0.117g, 0.2451mmol), DBTDL (12uL) adds nothing
Water DMF (2mL) is added HDI (195uL, 1.2118mmol) to dissolved compound, nitrogen protection 5-10min, closed, and 60
Under the conditions of DEG C, reacts one hour, obtain performed polymer 1；Another 100mL branch mouth bottle is taken, the anhydrous polytetrahydrofuran (Mn=of 5g is added
2000g/mol), DBTDL (20uL), nitrogen protection 10min, then performed polymer 1 is gone in branch mouth bottle, it seals, under the conditions of 60 DEG C,
Reaction one hour；It adds HDI (400uL), polymerization reaction, anhydrous DMF dilution is added after reacting sticky (if reaction 2 is small
When it is sticky there is no polymerizeing, can addition HDI appropriate), blocked after about sticky four to five times and precipitated with methanol, obtained white
Pico- yellowing polymer 4.88g, yield 85%, polymer nuclear-magnetism characterization are shown in attached drawing 2, are tested by nucleus magnetic hydrogen spectrum, it is possible to find double
Spiro-pyrans is connected in polyether polyols.
2, polymer film forming
Polymer is dissolved in THF, is added in Teflon mould (long * wide * high=60cm*60cm*1.5cm)
Film forming, after drying to be polymerized, is cut into rectangular-shaped stretching for polymer, sees attached drawing 3.
Research test shows：Polymer containing bissiropyran can occur power mutagens color and (be become by yellow in mechanical force
At green), and with the increase of tensile elongation, color is gradually deepened, and when mechanical force stops, being restored to original face quickly
Color (is less than 10s), it follows that the novel bissiropyran power color group has the function of power mutagens color, while illustrating the power color group
It is expected to be applied to Mechanics of Machinery early warning, detection etc..
Claims (4)
1. a kind of preparation method of bissiropyran power color group, it is characterised in that：The structural formula of the bissiropyran power color group is as follows：
The bissiropyran power color rolls into a ball preparation method：
1) a certain amount of double salicylaldehyde compound dissolution is weighed in a solvent, the molar ratio of double salicylaldehyde and solvent is 1:50-1:
100；
2) a certain amount of benzazolyl compounds are weighed into solution described in step 1), mole of the benzazolyl compounds and double salicylaldehyde
Than being 2:1；
3) take a certain amount of catalyst into the 2) solution, the molar ratio of catalyst and benzazolyl compounds is 1:2；
4) stirring is started, reacts 30-36h under 70-85 DEG C of constant temperature, obtains brown liquid, is concentrated, column layer chromatography obtains blackish green
Solid powder.
2. the preparation method of bissiropyran compound according to claim 1, it is characterised in that：The catalyst is piperazine
Pyridine, triethylene diamine, triethylamine.
3. the preparation method of bissiropyran compound according to claim 1, it is characterised in that：The solvent be ethyl alcohol,
Methanol.
4. the preparation method of bissiropyran compound according to claim 1, it is characterised in that：Double spiro-compounds applications
In early warning, context of detection.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378141A (en) * | 2019-01-01 | 2020-07-07 | 翁秋梅 | Force-induced response supramolecular polymer |
| CN111690131A (en) * | 2020-02-16 | 2020-09-22 | 武汉纺织大学 | Force-induced color-changing high-toughness nylon 6 and preparation method thereof |
| CN114835870A (en) * | 2022-04-27 | 2022-08-02 | 瑞年新材料(广东)有限公司 | Self-repairing color-changing film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3597446A (en) * | 1968-10-03 | 1971-08-03 | Agfa Gevaert Nv | Bifunctional photochromic compounds of the indolino-spiropyran type |
| CN1226267A (en) * | 1996-06-17 | 1999-08-18 | 光学转变公司 | Noval photochromic indeno-fused naphthopyrans |
| CN102850474A (en) * | 2012-09-28 | 2013-01-02 | 江西科技师范大学 | Method for preparing polymethyl methacrylate by single electron transfer living radical emulsion polymerization |
| CN105541855A (en) * | 2015-11-25 | 2016-05-04 | 内蒙古自治区科学技术研究院有限责任公司东部分院 | 1,8-naphthalimide compound bonded with spiro-pyran, preparation method and applications thereof |
-
2018
- 2018-08-14 CN CN201810922159.7A patent/CN108892680A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3597446A (en) * | 1968-10-03 | 1971-08-03 | Agfa Gevaert Nv | Bifunctional photochromic compounds of the indolino-spiropyran type |
| CN1226267A (en) * | 1996-06-17 | 1999-08-18 | 光学转变公司 | Noval photochromic indeno-fused naphthopyrans |
| CN102850474A (en) * | 2012-09-28 | 2013-01-02 | 江西科技师范大学 | Method for preparing polymethyl methacrylate by single electron transfer living radical emulsion polymerization |
| CN105541855A (en) * | 2015-11-25 | 2016-05-04 | 内蒙古自治区科学技术研究院有限责任公司东部分院 | 1,8-naphthalimide compound bonded with spiro-pyran, preparation method and applications thereof |
Non-Patent Citations (4)
| Title |
|---|
| GREGORY I. PETERSON等，: ""3D-Printed Mechanochromic Materials"", 《ACS APPL. MATER. INTERFACES》 * |
| QIUHONG ZHANG等，: ""Light and force dual-responsive waterborne polyurethane in multiple states"及其Electronic supplementary information", 《RSC ADV.》 * |
| 强涛涛主编，: "《合成革化学品》", 31 July 2016, 中国轻工业出版社 * |
| 马世昌主编，: "《基础化学反应》", 31 January 2003, 陕西科学技术出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378141A (en) * | 2019-01-01 | 2020-07-07 | 翁秋梅 | Force-induced response supramolecular polymer |
| CN111690131A (en) * | 2020-02-16 | 2020-09-22 | 武汉纺织大学 | Force-induced color-changing high-toughness nylon 6 and preparation method thereof |
| CN111690131B (en) * | 2020-02-16 | 2022-04-26 | 武汉纺织大学 | Force-induced color-changing high-toughness nylon 6 and preparation method thereof |
| CN114835870A (en) * | 2022-04-27 | 2022-08-02 | 瑞年新材料(广东)有限公司 | Self-repairing color-changing film and preparation method thereof |
| CN114835870B (en) * | 2022-04-27 | 2022-12-06 | 瑞年新材料(广东)有限公司 | Self-repairing color-changing film and preparation method thereof |
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