CN111004146A - Liquid azophenyl molecular solar thermal fuel and synthesis method and application thereof - Google Patents
Liquid azophenyl molecular solar thermal fuel and synthesis method and application thereof Download PDFInfo
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- CN111004146A CN111004146A CN201911298516.8A CN201911298516A CN111004146A CN 111004146 A CN111004146 A CN 111004146A CN 201911298516 A CN201911298516 A CN 201911298516A CN 111004146 A CN111004146 A CN 111004146A
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- 239000007788 liquid Substances 0.000 title claims abstract description 27
- 239000000446 fuel Substances 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title claims abstract description 15
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004146 energy storage Methods 0.000 claims abstract description 13
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011232 storage material Substances 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 11
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002535 acidifier Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000012954 diazonium Substances 0.000 claims description 8
- 150000001989 diazonium salts Chemical class 0.000 claims description 8
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- NUOQYOOGFASBIB-UHFFFAOYSA-N 2-[(1,5-diethyl-6-hydroxycyclohexa-2,4-dien-1-yl)diazenyl]benzene-1,4-diol Chemical compound C(C)C1(C(C(=CC=C1)CC)O)N=NC1=C(C=CC(=C1)O)O NUOQYOOGFASBIB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 abstract 1
- KHLUGJCHPXSQOJ-UHFFFAOYSA-N [3-(4-bromobutoxy)-2,6-diethylphenyl]-phenyldiazene Chemical compound BrCCCCOC=1C(=C(C(=CC=1)CC)N=NC1=CC=CC=C1)CC KHLUGJCHPXSQOJ-UHFFFAOYSA-N 0.000 description 18
- 238000006317 isomerization reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 bromobutoxy group Chemical group 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
-
- 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
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
Abstract
The invention relates to a liquid azophenyl 'molecular solar thermal fuel' and a synthesis method and application thereof. The technical scheme is as follows: the diazo salt of 2, 6-diethylaniline and phenol are subjected to coupling reaction at 0-5 ℃ to generate 2, 6-diethyl-4' -hydroxy azophenol. Through nucleophilic substitution reaction with 1, 4-dibromobutane, a liquid azophenyl 'molecular solar thermal fuel', namely 4-bromobutoxy-2 ', 6' -diethyl azobenzene, is synthesized. The invention has the characteristics of simple synthesis method, liquid product at normal temperature, high stability, quick photoresponse, long half-life period and large energy storage capacity, and has potential application prospect in the field of solvent-free molecular solar energy storage materials.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to an azobenzene molecular solar thermal fuel 4-bromobutoxy-2 ', 6' -diethylazobenzene which is liquid at normal temperature.
Background
"molecular solar thermal fuel" is a stable photochromic molecular absorption of photon energy (E)hv) Then, the configuration transformation is carried out, and the structure is changed into a high-energy metastable state structure, so that the energy is stored in a strained chemical bond (enthalpy difference delta H between two isomers); overcoming a certain activation energy barrier (E) under an external stimulus (light, heat or catalyst)a) Thereafter, the metastable structure reverts to the steady-state structure and the stored energy is released in the form of heat. The energy storage-discharge process is a closed cycle, and does not generate any discharge and waste in the process, so the energy storage-discharge process is an ideal molecular energy supply system.
Azobenzene is simple to synthesize, has good stability, can generate reversible trans-cis isomerization through ultraviolet-visible light induction, and is often used as molecular solar thermal fuel. However, trans-cis isomerization is remarkably inhibited in a solid state, a solvent must be added, and dilution of the solvent inevitably causes reduction of the energy density of the system volume.
Therefore, the research and development of the liquid azobenzene derivative which has simple synthesis method, quick response to light and high stability and can realize trans-cis isomerization without a solvent have very important significance when being applied to the field of solar energy storage.
Disclosure of Invention
The invention aims to synthesize an azophenyl 'molecular solar thermal fuel' which is liquid at normal temperature, namely 4-bromobutoxy-2 ', 6' -diethyl azobenzene, and the azophenyl 'molecular solar thermal fuel' has the advantages of high stability, quick photoresponse, long half-life period and large energy storage capacity.
In order to achieve the purpose, the invention adopts the technical scheme that: a liquid azophenyl 'molecular solar thermal fuel' is 4-bromobutoxy-2 ', 6' -diethyl azobenzene, is a compound consisting of an azobenzene group substituted by ortho-position diethyl and a butoxy chain substituted by bromine at the tail end, and has a structural formula shown as (I):
further, the liquid azophenyl molecular solar thermal fuel is liquid at normal temperature.
A synthesis method of liquid azophenyl 'molecular solar thermal fuel' comprises the following synthesis steps:
1) dripping an acidifying agent into an aqueous solution of 2, 6-diethylaniline to obtain a hydrochloride turbid solution of the 2, 6-diethylaniline; slowly dripping the ice water solution of sodium nitrite into the hydrochloride turbid solution of the 2, 6-diethylaniline at the temperature of 0-5 ℃ to obtain the diazonium salt solution of the 2, 6-diethylaniline;
2) preparing phenol and sodium hydroxide into a sodium phenolate aqueous solution, dripping a diazonium salt solution of 2, 6-diethylaniline into the sodium phenolate aqueous solution at 0-5 ℃, and adjusting the pH to 8-9; after the dropwise addition is finished, reacting for 4 hours in an ice-water bath; after the reaction is finished, dripping an acidifying agent into the reaction system, stirring at room temperature for 30min, then carrying out suction filtration, washing the obtained solid with water and n-ethane in sequence, and then recrystallizing with dichloromethane/n-hexane to obtain 2, 6-diethyl-4' -hydroxy azophenol crystals;
3) 2, 6-diethyl-4 ' -hydroxy azophenol crystal, 1, 4-dibromobutane, potassium carbonate and potassium iodide are subjected to reflux reaction in an ethanol solution at 80 ℃ for 24 hours, after the reaction is finished, the reaction solution is filtered, the obtained filtrate is put into ice water, after standing for 12 hours, dichloromethane is added for extraction, the obtained extract liquid is dried, dichloromethane is evaporated under reduced pressure, and column chromatography is carried out by taking dichloromethane/n-hexane as a developing agent to obtain 4-bromobutoxy-2 ', 6 ' -diethyl azobenzene.
The synthetic route of the invention is as follows:
further, the acidifying agent is prepared by mixing concentrated hydrochloric acid with the concentration of 12mol/L and water according to the volume ratio of 1:1, mixing to obtain the product.
Further, in the synthesis method, in the step 1), the molar ratio of the 2, 6-diethylaniline, the sodium nitrite and the 12mol/L concentrated hydrochloric acid is 1:1: 4-4.1.
Further, in the synthesis method, step 2), the molar ratio of the phenol to the sodium hydroxide to the 12mol/L concentrated hydrochloric acid is 1:1: 4-4.1.
Further, in the above synthesis method, in step 3), the molar ratio of the 2, 6-diethyl-4' -hydroxyazo phenol crystals, 1, 4-dibromobutane, and potassium carbonate is 1:10: 3.
Further, the above synthesis method is characterized in that, in the step 3), K2CO3The molar ratio of the compound to KI is 38-40: 1.
The liquid azophenyl 'molecular solar thermal fuel' is applied to solvent-free molecular solar energy storage materials.
The invention has the beneficial effects that:
1. the invention firstly synthesizes 2, 6-diethyl-4 '-hydroxy azophenol, and then directly synthesizes 4-bromobutoxy-2', 6 '-diethyl azobenzene by nucleophilic substitution of the 2, 6-diethyl-4' -hydroxy azophenol and 1, 4-dibromobutane. The synthesized liquid azophenyl 'molecular solar thermal fuel', namely 4-bromobutoxy-2 ', 6' -diethyl azobenzene, contains azo groups, and has potential application prospects in the field of molecular solar energy storage.
2. The invention has simple preparation process. The product is liquid at normal temperature, and provides a foundation for the product to be used as a solvent-free energy storage material.
3. According to the invention, the target product not only has large energy storage capacity, but also has longer half-life period than the traditional azobenzene.
Drawings
FIG. 1 is an infrared spectrum of 4-bromobutoxy-2 ', 6' -diethylazobenzene synthesized in example 1.
FIG. 2 is a diagram showing a process for preparing 4-bromobutoxy-2 ', 6' -diethylazobenzene as synthesized in example 11H NMR spectrum.
FIG. 3a is a Differential Scanning Calorimetry (DSC) plot of 4-bromobutoxy-2 ', 6' -diethylazobenzene synthesized in example 1.
Fig. 3b is a partial enlarged view of fig. 3 a.
FIG. 4 is a UV-Vis spectrum of 4-bromobutoxy-2 ', 6' -diethylazobenzene synthesized in example 1.
FIG. 5 is a Differential Scanning Calorimetry (DSC) plot of the maximum isomerization rate of the 4-bromobutoxy-2 ', 6' -diethylazobenzene synthesized in example 1 after exposure to ultraviolet light (365 nm).
Detailed Description
Example 1
Synthesis of diazonium salt of 1, 2, 6-diethylaniline from 4-bromobutoxy-2 ', 6 ' -diethylazobenzene (I) liquid azophenyl ' molecular solar thermal fuel
In a 50mL beaker, 1.0mL (6.08mmol) of 2, 6-diethylaniline and 8mL of deionized water were added. 2.05mL (24.6mmol) of 12mol/L concentrated hydrochloric acid was put into another 50mL beaker, and 2.05mL of deionized water was added to prepare an acidifying agent. And (3) dripping an acidifying agent into the aqueous solution of the 2, 6-diethylaniline at normal temperature, stirring at room temperature, and carrying out acidification reaction for 30min to obtain the hydrochloride turbid solution of the 2, 6-diethylaniline.
In a 20mL beaker, 420mg (6.08mmol) of sodium nitrite and 8mL of deionized water were taken to prepare NaNO2An aqueous solution.
Mixing the turbid solution of hydrochloride of 2, 6-diethylaniline with NaNO2And transferring the aqueous solution into an ice-water bath, cooling the aqueous solution to 0-5 ℃, and slowly dripping the cooled sodium nitrite aqueous solution into the hydrochloride turbid solution of the 2, 6-diethylaniline at the temperature to obtain the diazonium salt solution of the 2, 6-diethylaniline.
2. Synthesis of 2, 6-diethyl-4' -hydroxy azophenol
In a 100mL beaker, 572mg (6.07mmol) of phenol, 243mg (6.07mmol) of sodium hydroxide and 10mL of deionized water were added, and the mixture was stirred at room temperature until the phenol was completely dissolved to obtain an aqueous solution of sodium phenolate.
Placing the obtained sodium phenolate aqueous solution in an ice water bath, and keeping the temperature of the system at 0-5 ℃. At the temperature, the diazonium salt solution of 2, 6-diethylaniline is slowly dripped into the above sodium phenate aqueous solution, and the pH value is 8-9 during the process of dripping the diazonium salt is controlled by NaOH aqueous solution. After the dropwise addition is finished, the system is placed in an ice-water bath environment and reacts for 4 hours.
After the reaction, 2.05mL (24.6mmol) of 12mol/L concentrated hydrochloric acid was put into another 50mL beaker, and 2.05mL of deionized water was added to prepare an acidulant. At normal temperature, the acidifier is dropped into the reaction system, and stirred for 30min at room temperature. And (3) carrying out suction filtration, washing the obtained solid with water until the pH value of the supernatant is neutral, washing with n-ethane to obtain yellow powder, and recrystallizing the yellow powder with dichloromethane/n-hexane (the volume ratio is 1:2) to obtain 900mg of 2, 6-diethyl-4' -hydroxy azophenol crystals with the yield of 53%.
3. Synthesis of 4-bromobutoxy-2 ', 6' -diethylazobenzene
In a 50mL round-bottomed flask, 255mg (1.00mmol) of 2, 6-diethyl-4' -hydroxyazo phenol crystals were dissolved in 20mL of ethanol, and then 1.20mL (10.05mmol) of 1, 4-dibromobutane, 415mg (3.00mmol) of potassium carbonate, 13mg (0.078mmol) of potassium iodide were added with stirring, and the reaction was refluxed at 80 ℃ for 24 hours. And after the reaction is finished, filtering the reaction solution, putting the obtained filtrate into ice water, standing for 12 hours, adding dichloromethane for extraction, collecting the extract after three times of extraction, adding a certain amount of anhydrous magnesium sulfate into the extract, and drying for 24 hours. The magnesium sulfate was removed by filtration, and the resulting dichloromethane extract was subjected to reduced pressure to distill off the solvent. After column chromatography (developing solvent dichloromethane/n-hexane ═ 1:2(v: v)), the solvent was removed from the red layer obtained by column chromatography, and 303mg of the target product 4-bromobutoxy-2 ', 6' -diethylazobenzene was obtained in a liquid state at ordinary temperature in a yield of 78%.
(II) detection
FIG. 1 shows the IR spectrum of 4-bromobutoxy-2 ', 6' -diethylazobenzene as a product. Wherein 1250cm-1And 1141cm-1The characteristic peak of ether appears, indicating the presence of ether linkage in the product.
FIG. 2 is a NMR spectrum of 4-bromobutoxy-2 ', 6' -diethylazobenzene as a product. In FIG. 2, chemical shifts 7.92-7.86 (m,2H), 7.22-7.11 (m,3H), 7.05-6.98 (m,2H) are respectively assigned to proton peaks on the benzene ring; the triplet at chemical shift 4.09(t, J ═ 5.9Hz,2H) is the proton peak on the oxygen-linked methylene group; the triplet at chemical shift 3.51(t, J ═ 6.4Hz,2H) is the proton peak on the methylene group attached to the bromine; the multiple peaks at chemical shifts 2.16-1.94 (m,4H) are proton peaks on the other two methylene groups on the bromobutoxy group; the quartet at chemical shift 2.64(q, J ═ 7.5Hz,4H) is the proton peak on the methylene group in the two ethyl groups on the phenyl ring; the triplet at chemical shift 1.14(t, J ═ 7.5Hz,6H) is the proton peak on the methyl group of the two ethyl groups on the phenyl ring.
FIGS. 3a and 3b are Differential Scanning Calorimetry (DSC) plots of the product 4-bromobutoxy-2 ', 6' -diethylazobenzene. Fig. 3b is a partial enlarged view of fig. 3 a. In FIGS. 3a and 3b, it can be seen that the product, 4-bromobutoxy-2 ', 6' -diethylazobenzene, has a melting point of-18.73 ℃ and is liquid at ordinary temperature. Based on the method, the product can respond to ultraviolet light in a normal-temperature liquid state, and therefore, the product can be used as a solvent-free solar energy storage material.
FIG. 4 is a UV-Vis spectrum of the product 4-bromobutoxy-2 ', 6' -diethylazobenzene. It can be seen that the peak values of the transition peaks of pi-pi and n-pi are blue shifted and the absorbance is changed correspondingly when the product 4-bromobutoxy-2 ', 6' -diethylazobenzene is irradiated by ultraviolet light (365nm) for different time. The longer the ultraviolet light irradiation time, the greater the degree of blue shift of the peak value, and the greater the absorbance change value. The change of the absorbance at 373nm is taken to monitor the isomerization rate of the product 4-bromobutoxy-2 ', 6' -diethylazobenzene under different ultraviolet irradiation time, and it can be seen that when the isomerization rate of the product reaches the maximum (the isomerization rate is 88%), namely the absorbance at 373nm is reduced to no longer change, and only the time is about 15s, which proves that the product has rapid response to the ultraviolet light.
FIG. 5 is a Differential Scanning Calorimetry (DSC) plot of the product 4-bromobutoxy-2 ', 6' -diethylazobenzene at its maximum isomerization after exposure to ultraviolet light (365 nm). As can be seen from the graph, the energy storage capacity was 96.65J/g at a product isomerization rate of 88%, i.e., the complete energy storage capacity of the product was calculated to be 42.8 KJ/mol. Therefore, the 4-bromobutoxy-2 ', 6' -diethylazobenzene can be used in the field of solvent-free molecular solar energy storage materials and has potential application.
Claims (9)
1. The liquid azophenyl 'molecular solar thermal fuel' is characterized in that the liquid azophenyl 'molecular solar thermal fuel' is 4-bromobutoxy-2 ', 6' -diethyl azobenzene, and has a structural formula shown as (I):
2. the liquid azophenyl molecular solar thermal fuel according to claim 1, wherein the liquid azophenyl molecular solar thermal fuel is liquid at room temperature.
3. The synthesis method of liquid azophenyl "molecular solar thermal fuel" as claimed in claim 1 or 2, characterized by comprising the following synthesis steps:
1) dripping an acidifying agent into an aqueous solution of 2, 6-diethylaniline to obtain a hydrochloride turbid solution of the 2, 6-diethylaniline; slowly dripping the ice water solution of sodium nitrite into the hydrochloride turbid solution of the 2, 6-diethylaniline at the temperature of 0-5 ℃ to obtain the diazonium salt solution of the 2, 6-diethylaniline;
2) preparing phenol and sodium hydroxide into a sodium phenolate aqueous solution, dripping a diazonium salt solution of 2, 6-diethylaniline into the sodium phenolate aqueous solution at 0-5 ℃, and adjusting the pH to 8-9; after the dropwise addition is finished, reacting for 4 hours in an ice-water bath; after the reaction is finished, dripping an acidifying agent into the reaction system, stirring at room temperature for 30min, then carrying out suction filtration, washing the obtained solid with water and n-ethane in sequence, and then recrystallizing with dichloromethane/n-hexane to obtain 2, 6-diethyl-4' -hydroxy azophenol crystals;
3) 2, 6-diethyl-4 ' -hydroxy azophenol crystal, 1, 4-dibromobutane, potassium carbonate and potassium iodide are subjected to reflux reaction in an ethanol solution at 80 ℃ for 24 hours, after the reaction is finished, the reaction solution is filtered, the obtained filtrate is put into ice water, after standing for 12 hours, dichloromethane is added for extraction, the obtained extract liquid is dried, dichloromethane is evaporated under reduced pressure, and column chromatography is carried out by taking dichloromethane/n-hexane as a developing agent to obtain 4-bromobutoxy-2 ', 6 ' -diethyl azobenzene.
4. The synthesis method according to claim 3, wherein the acidifying agent is concentrated hydrochloric acid with a concentration of 12mol/L and water in a volume ratio of 1:1, mixing to obtain the product.
5. The synthesis method according to claim 4, wherein in the step 1), the molar ratio of the 2, 6-diethylaniline to the sodium nitrite to the 12mol/L concentrated hydrochloric acid is 1:1: 4-4.1.
6. The synthesis method of claim 4, wherein in the step 2), the molar ratio of the phenol to the sodium hydroxide to the 12mol/L concentrated hydrochloric acid is 1:1: 4-4.1.
7. The synthesis method according to claim 4, wherein in the step 3), the molar ratio of the 2, 6-diethyl-4' -hydroxyazo phenol crystals, 1, 4-dibromobutane and potassium carbonate is 1:10: 3.
8. The method of claim 4, wherein in step 3), K is2CO3The molar ratio of the compound to KI is 38-40: 1.
9. Use of the liquid azophenyl "molecular solar thermal fuel" according to claim 1 in solvent-free molecular solar energy storage materials.
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