CN117820159A - Synthesis method of 3,3' -dihydroxyazobenzene and hyperbranched azobenzene derived from same - Google Patents
Synthesis method of 3,3' -dihydroxyazobenzene and hyperbranched azobenzene derived from same Download PDFInfo
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- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- KONUTRXTUUBGKS-UHFFFAOYSA-N 3-[(3-hydroxyphenyl)diazenyl]phenol Chemical compound OC1=CC=CC(N=NC=2C=C(O)C=CC=2)=C1 KONUTRXTUUBGKS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- -1 tert-butyldimethylsilyloxy Chemical group 0.000 claims description 12
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 229940018563 3-aminophenol Drugs 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 229940125782 compound 2 Drugs 0.000 claims description 10
- 229940126214 compound 3 Drugs 0.000 claims description 10
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- HHSARRMUXPDGJD-UHFFFAOYSA-N butyl(dimethyl)silicon Chemical group CCCC[Si](C)C HHSARRMUXPDGJD-UHFFFAOYSA-N 0.000 claims description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- TZRQZPMQUXEZMC-UHFFFAOYSA-N tert-butyl n-(2-bromoethyl)carbamate Chemical compound CC(C)(C)OC(=O)NCCBr TZRQZPMQUXEZMC-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229940125898 compound 5 Drugs 0.000 claims description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 150000005172 methylbenzenes Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical compound C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- UTXIKCCNBUIWPT-UHFFFAOYSA-N 1,2,4,5-tetrakis(bromomethyl)benzene Chemical compound BrCC1=CC(CBr)=C(CBr)C=C1CBr UTXIKCCNBUIWPT-UHFFFAOYSA-N 0.000 claims description 2
- RBZMSGOBSOCYHR-UHFFFAOYSA-N 1,4-bis(bromomethyl)benzene Chemical compound BrCC1=CC=C(CBr)C=C1 RBZMSGOBSOCYHR-UHFFFAOYSA-N 0.000 claims description 2
- BWZHKRSSCFRVIE-UHFFFAOYSA-N 1-n,4-n-dimethyl-2h-pyridine-1,4-diamine Chemical compound CNN1CC=C(NC)C=C1 BWZHKRSSCFRVIE-UHFFFAOYSA-N 0.000 claims description 2
- BXVSAYBZSGIURM-UHFFFAOYSA-N 2-phenoxy-4h-1,3,2$l^{5}-benzodioxaphosphinine 2-oxide Chemical compound O1CC2=CC=CC=C2OP1(=O)OC1=CC=CC=C1 BXVSAYBZSGIURM-UHFFFAOYSA-N 0.000 claims description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 2
- 229940125904 compound 1 Drugs 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 15
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- PEXGTUZWTLMFID-UHFFFAOYSA-N 2-phenyldiazenylphenol Chemical compound OC1=CC=CC=C1N=NC1=CC=CC=C1 PEXGTUZWTLMFID-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- GHITVUOBZBZMND-UHFFFAOYSA-N 1,3,5-tris(bromomethyl)benzene Chemical compound BrCC1=CC(CBr)=CC(CBr)=C1 GHITVUOBZBZMND-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- XBZVPWIDTDAKDL-UHFFFAOYSA-N 3-[tert-butyl(dimethyl)silyl]oxyaniline Chemical compound CC(C)(C)[Si](C)(C)OC1=CC=CC(N)=C1 XBZVPWIDTDAKDL-UHFFFAOYSA-N 0.000 description 1
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- LHHCSNFAOIFYRV-DOVBMPENSA-N boceprevir Chemical compound O=C([C@@H]1[C@@H]2[C@@H](C2(C)C)CN1C(=O)[C@@H](NC(=O)NC(C)(C)C)C(C)(C)C)NC(C(=O)C(N)=O)CC1CCC1 LHHCSNFAOIFYRV-DOVBMPENSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis and polymer synthesis, and particularly relates to a synthesis method of 3,3' -dihydroxyazobenzene and hyperbranched azobenzene derived from the same.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and polymer synthesis, and particularly relates to a synthesis method of 3,3' -dihydroxyazobenzene and hyperbranched azobenzene derived from the same.
Background
Aromatic azo compounds are important compounds formed by connecting aromatic rings through nitrogen-nitrogen double bonds (-N=N-), and are widely applied to dyes, food additives, free radical reaction initiators and the like. Azobenzene and derivatives thereof have two isomers of cis (cis) and trans (trans), and when external conditions such as illumination, temperature and the like are changed, reversible structural isomerization transformation occurs, and color and three-dimensional structures are changed, so that the azobenzene and derivatives thereof can be applied to various aspects such as molecular motors, molecular switches, energy storage and the like. Furthermore, azo compounds show good prospects in terms of electronics and pharmaceuticals. And can be used as an optical trigger for designing and synthesizing various optical response systems. Compared with a small-molecule azobenzene compound, the azobenzene polymer has excellent thermal stability, film forming property and processability, is an ideal matrix material, has an aromatic azobenzene structure introduced into a high molecular chain, and has important application value as a light functional material in the fields of light control materials, light orientation materials, surface relief gratings and the like.
The hydroxyazobenzene is an important intermediate for synthesizing functional aromatic azobenzene compounds, 3 '-dihydroxyazobenzene is taken as a member of the intermediate compounds, and the conventional method for synthesizing the hydroxyazobenzene is difficult to work because the hydroxyl is in the meta position of azo group, so that the commercial 3,3' -dihydroxyazobenzene is expensive. The method for synthesizing 3,3' -dihydroxyazobenzene by taking 3-nitrophenol as a starting material reported in the literature (J.Mater.chem., 1999,9,673-681) needs steps of protection of tetrahydropyran on hydroxy, reduction and nitridation of lithium aluminum hydride, protection of detetrahydropyran and the like, but the method has higher cost, and complex reaction control and post-treatment purification, and is difficult to realize industrial production. Direct oxidation of 3-aminophenol using different oxidants results in low product yields (Chemical Paper,2019, 73 (2), 375-385) or difficulties in obtaining the product (Australian Journal ofChemistry (1984), 37 (4), 845-55). The azobenzene polymer is mainly divided into a side chain type polymer, a main chain type polymer and other polymers with special structures, and the synthesis method mainly comprises a free radical polymerization method, a condensation polymerization method, a post-modification method and the like. According to the invention, the 3,3' -dihydroxyazobenzene is derivatized to introduce flexible alkyl and high-activity amino, and then substitution reaction is carried out with high-activity polybrominated toluene to synthesize the novel azobenzene polymer with multiple functional groups.
Disclosure of Invention
The invention aims to provide a method for synthesizing 3,3' -dihydroxyazobenzene and hyperbranched azobenzene derived from the same, which takes 3-aminophenol as a starting material, uses dimethyl tertiary butyl silicon base to protect hydroxyl to obtain 3- (tertiary butyl dimethyl silicon base) aniline firstly because phenol is unstable under an oxidation condition, takes air as an oxidant under the catalysis of cuprous bromide secondly, synthesizes 3,3' -di (tertiary butyl dimethyl silicon base) azobenzene efficiently, and finally protects the silicon base of 3,3' -di (tertiary butyl dimethyl silicon base) azobenzene, and obtains a target product with high purity through recrystallization and purification.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a synthetic method of 3,3' -dihydroxyazobenzene is shown in a formula I:
the synthesis method comprises the following steps: 3-aminophenol is used as a starting material, dimethyl tertiary butyl silicon base is firstly used for protecting hydroxyl groups to obtain 3- (tertiary butyl dimethyl silicon base) aniline, then under the catalysis of cuprous bromide, air is used as an oxidant to synthesize 3,3' -di (tertiary butyl dimethyl silicon base) azobenzene, and finally the 3,3' -di (tertiary butyl dimethyl silicon base) azobenzene is subjected to silicon base protection removal, and the target product 3,3' -dihydroxyazobenzene with high purity is obtained through recrystallization and purification.
Further, the synthesis of the compound 2 in the formula I comprises the following steps: reacting 3-aminophenol, namely a compound 1, 4-dimethylaminopyridine, dimethyl tertiary butyl chlorosilane and triethylamine at room temperature, detecting the reaction by TLC until the reaction is complete, and distilling under reduced pressure to obtain 3- (tertiary butyl dimethyl siloxy) aniline, namely a compound 2; the mass ratio of the 3-aminophenol to the 4-dimethylaminopyridine to the dimethyl tertiary butyl chlorosilane to the triethylamine is 10:1:30:30.
Further, the synthesis procedure of the compound 3 is as follows: exposing the compound 2, pyridine and CuBr in toluene to air for reaction at 60 ℃, and distilling under reduced pressure to obtain a compound 3, namely 3,3' -di (tert-butyldimethylsilyloxy) azobenzene; the mass ratio of the compound 2 to the pyridine to the CuBr is 100:3:9.
Further, the synthesis of the compound 4 in the formula I comprises the following steps: adding the compound 3, tetrabutylammonium fluoride and tetrahydrofuran into a flask to react at room temperature, adding hydrochloric acid to make a reaction system acidic, distilling under reduced pressure to remove tetrahydrofuran and water, adding DMF to fully dissolve solids in the flask, adding 100ml of saturated saline solution to separate out solid substances, filtering, and drying in vacuum to obtain the compound 4, namely 3,3' -dihydroxyazobenzene; the mass ratio of the compound 3 to the tetrabutylammonium fluoride is 2:3.
The preparation method of the hyperbranched azobenzene polymer derived from 3,3' -dihydroxyazobenzene comprises the following synthetic route:
the synthesis method comprises the following steps: 3,3' -dihydroxyazobenzene, N-Boc-bromoethylamine, K 2 CO 3 Sequentially adding DMF into a round bottom flask, reacting at 80deg.C for 12 hr, pouring the reaction solution into saturated saline solution to precipitate the product, filtering, washing with water, and vacuumAir drying to obtain a product 3,3' -di (N-Boc-ethoxy) azobenzene, namely a compound 5; sequentially adding 3,3 '-di (N-Boc-ethoxy) azobenzene, methylene dichloride and trifluoroacetic acid into a round bottom flask, reacting for 2 hours at room temperature, removing methylene dichloride and trifluoroacetic acid by reduced pressure distillation, adding a NaOH solution to adjust Ph to alkalinity, adding ethyl acetate for extraction, drying by anhydrous sodium sulfate, distilling under reduced pressure, and recrystallizing acetonitrile to obtain a product 3,3' -di (beta-amino-ethoxy) azobenzene, namely a compound 6; dissolving compound 6 and polybrominated methylbenzene in ethanol, stirring at room temperature for 2h, adding distilled water, and separating out target compound (branched polymeric azobenzene) with structural formula of
The azo-containing compound contains azo groups, various amino groups (including quaternary amines) and active bromine atoms, can participate in various reactions, and can be used as a light response functional compound and a reaction intermediate for introducing functional azo phenyl groups and amino groups. The synthesis steps mainly comprise the substitution reaction of 3,3' -dihydroxyazobenzene and N-Boc-bromoethylamine, BOC protection of amino, and substitution reaction of amino and active polybrominated substances.
Further, the mass ratio of the 3,3' -dihydroxyazobenzene to the N-Boc-bromoethylamine to the potassium carbonate is 2:7:20.
Further, the polybasic bromomethylbenzene is one of 1, 4-dibromomethylbenzene, 1, 35-tribromomethylbenzene and 1,3,4, 6-tetrabromomethylbenzene, and the type or the amount of substances can be regulated, so that the microstructure of the branched azobenzene can be changed, and the type of functional groups can be regulated.
The invention has the advantages that: the synthesis method of the 3,3' -dihydroxyazobenzene provided by the invention has the advantages of low synthesis cost, few synthesis steps and simple post-treatment, and takes the low-cost 3-aminophenol as the initial raw material, so that the total reaction yield is 53.9%. The 3-aminophenol has a phenol structure, so that other oxidation byproducts are easily generated in the oxidative coupling process, the reaction efficiency is low, and the purification is difficult. The invention protects phenolic hydroxyl group by dimethyl tertiary butyl silicon group which is easy to protect and easy to deprotect, so that aniline oxidative diazotization can be efficiently carried out, in addition, oxygen in air is used as an oxidant, the reaction condition is mild and clean, and the final target product can be purified by a recrystallization mode, thus being suitable for large-scale synthesis. The novel azobenzene polymer is synthesized by introducing aminoethyl based on 3,3' -dihydroxyazobenzene, so that the flexibility and the reactivity of molecules are improved, and polybrominated methylbenzenes are quickly and efficiently synthesized at room temperature, wherein the hydroxyl groups are in the meta positions of azo groups, in the conversion constitution of cis-trans isomerism, the increased space transformation range is brought to increase the photosensitivity, the introduction of alkyl groups increases the flexibility of the molecules, and in addition, the structure and the functionality of the polymer can be regulated by the type and the addition amount of polybrominated methylbenzenes, so that the polymer has different functionalities according to the needs of practical application and research, and the polymer (active bromine atoms or primary amino groups) can be further modified.
Drawings
FIG. 1 is 1H NMR (CDCl) of 3,3' -di (t-butyldimethylsilyloxy) azobenzene 3 ，400MHz)。
FIG. 2 is 1H NMR (DMSO-D6, 400 MHz) of 3,3' -dihydroxyazobenzene.
FIG. 3 is 13C NMR (DMSO-D6, 100 MHz) of 3,3' -dihydroxyazobenzene.
FIG. 4 is 1H NMR (CDCl) of 3,3' -bis (N-Boc-ethoxy) azobenzene 3 ，400MHz)。
FIG. 5 is 1H NMR (CDCl) of 3,3' -bis (. Beta. -amino-ethoxy) azobenzene 3 ，400MHz)。
FIG. 6 is an infrared spectrum of branched polymeric azobenzene.
Detailed Description
A method for synthesizing 3,3' -dihydroxyazobenzene comprises the following steps: .
Synthesis of 3- (t-butyldimethylsilyloxy) aniline Compound 2: 5.00g of m-hydroxyaniline, 0.55g of 4-dimethylaminopyridine (DMAP, 0.1 equiv), 20.70g of dimethyl tert-butylchlorosilane (3 equiv) and 18.3ml of triethylamine (3 equiv) are sequentially added into a 500ml round bottom flask, 150ml of dichloromethane is then added as a reaction solvent, stirring is carried out at room temperature, the reaction is carried out by TLC detection until the reaction is complete, the dichloromethane is removed by distillation under reduced pressure to obtain a crude product, and the crude product is purified by recrystallization to obtain 9.22g (yield 90%).
Synthesis of 3,3' -di (t-butyldimethylsilyloxy) azobenzene Compound 3: 9.22g of Compound 2, 0.344g of cuprous bromide (0.06 equiv), 0.713g of pyridine (0.18 equiv) and 150ml of toluene are sequentially added into a 500ml round-bottomed flask, the mixture is stirred and reacted for 20 hours at the temperature of 60 ℃ with an opening, the toluene is removed by distillation under reduced pressure, 150ml of water is added into a reaction flask, ethyl acetate is used for extracting an aqueous phase, anhydrous sodium sulfate is used for drying an organic phase, the crude product is obtained by distillation under reduced pressure, and the product is obtained by recrystallization and purification (yield 73%).
Synthesis of 3,3' -dihydroxyazobenzene Compound 4 6.67g of Compound 3, 14.26g of tetrabutylammonium fluoride (3 equiv) and 100ml of tetrahydrofuran were sequentially added to a 250ml round bottom flask, reacted at room temperature for 1 hour, then hydrochloric acid was added to make the reaction system acidic, tetrahydrofuran and water were distilled off under reduced pressure, then 10ml of DMF was added to sufficiently dissolve the solids in the flask, then 100ml of saturated brine was added to precipitate a solid matter, and the resultant was filtered and dried under vacuum to give 2.65g of a product (yield 82%).
Synthesis of 3,3' -bis (N-Boc-ethoxy) azobenzene Compound 5: 2.65g of Compound 4, 9.70g of N-Boc-bromoethylamine (3.5 equiv), 17.13g K 2 CO 3 (10 equiv) and 50ml of DMF were sequentially added to a 100ml round bottom flask, reacted at 80℃for 12 hours, and then the reaction solution was poured into 200ml of saturated saline solution to precipitate a product, and the product was filtered, washed with water and dried in vacuo to give 5.41 g of the product.
Synthesis of 3,3' -bis (β -amino-ethoxy) azobenzene compound 6: 2.41g of Compound 5, 30ml of dichloromethane and 15ml of trifluoroacetic acid are sequentially added into a 100ml round-bottomed flask, after reaction for 2 hours at room temperature, dichloromethane and trifluoroacetic acid are removed by distillation under reduced pressure, 50ml of 1mol/l NaOH solution is added into the round-bottomed flask, ethyl acetate is added for extraction, and the product 6.03 g is obtained by drying over anhydrous sodium sulfate, distillation under reduced pressure and recrystallization of acetonitrile.
Synthesis of branched polymeric azobenzene: 0.3g of compound 6 and 0.48g of 1,3, 5-tris (bromomethyl) benzene are taken and dissolved in ethanol, stirred for 2 hours at room temperature, distilled water is added to separate out the target compound, the product is filtered, and the yellow solid material of 0.65g is obtained by vacuum drying.
Claims (8)
1. A method for synthesizing 3,3' -dihydroxyazobenzene is characterized in that the synthetic route is shown in a formula I:
the synthesis method comprises the following steps: 3-aminophenol is used as a starting material, dimethyl tertiary butyl silicon base is firstly used for protecting hydroxyl groups to obtain 3- (tertiary butyl dimethyl silicon base) aniline, then under the catalysis of cuprous bromide, air is used as an oxidant to synthesize 3,3' -di (tertiary butyl dimethyl silicon base) azobenzene, and finally the 3,3' -di (tertiary butyl dimethyl silicon base) azobenzene is subjected to silicon base protection removal, and the target product 3,3' -dihydroxyazobenzene with high purity is obtained through recrystallization and purification.
2. The method for synthesizing 3,3' -dihydroxyazobenzene according to claim 1, wherein: the synthesis of the compound 2 in the formula I comprises the following steps: reacting 3-aminophenol, namely a compound 1, 4-dimethylaminopyridine, dimethyl tertiary butyl chlorosilane and triethylamine at room temperature, detecting the reaction by TLC until the reaction is complete, and distilling under reduced pressure to obtain 3- (tertiary butyl dimethyl siloxy) aniline, namely a compound 2; the mass ratio of the 3-aminophenol to the 4-dimethylaminopyridine to the dimethyl tertiary butyl chlorosilane to the triethylamine is 10:1:30:30.
3. The method for synthesizing 3,3' -dihydroxyazobenzene according to claim 1, wherein the step of synthesizing the compound 3 is as follows: exposing the compound 2, pyridine and CuBr in toluene to air for reaction at 60 ℃, and distilling under reduced pressure to obtain a compound 3, namely 3,3' -di (tert-butyldimethylsilyloxy) azobenzene; the mass ratio of the compound 2 to the pyridine to the CuBr is 100:3:9.
4. The method for synthesizing 3,3' -dihydroxyazobenzene according to claim 1, wherein: the synthesis of the compound 4 in the formula I comprises the following steps: adding the compound 3, tetrabutylammonium fluoride and tetrahydrofuran into a flask to react at room temperature, adding hydrochloric acid to make a reaction system acidic, distilling under reduced pressure to remove tetrahydrofuran and water, adding DMF to fully dissolve solids in the flask, adding 100ml of saturated saline solution to separate out solid substances, filtering, and drying in vacuum to obtain the compound 4, namely 3,3' -dihydroxyazobenzene; the mass ratio of the compound 3 to the tetrabutylammonium fluoride is 2:3.
5. A process for the preparation of hyperbranched azobenzene polymers derived from 3,3' -dihydroxyazobenzene according to any one of claims 1 to 4, characterized in that the synthetic route is:
the synthesis method comprises the following steps: 3,3' -dihydroxyazobenzene, N-Boc-bromoethylamine, K 2 CO 3 Sequentially adding DMF (dimethyl formamide) into a round bottom flask, reacting for 12 hours at 80 ℃, pouring the reaction solution into saturated saline solution to separate out a product, filtering, washing with water, and drying in vacuum to obtain a product 3,3' -di (N-Boc-ethoxy) azobenzene, namely a compound 5; sequentially adding 3,3 '-di (N-Boc-ethoxy) azobenzene, methylene dichloride and trifluoroacetic acid into a round bottom flask, reacting for 2 hours at room temperature, removing methylene dichloride and trifluoroacetic acid by reduced pressure distillation, adding a NaOH solution to adjust Ph to alkalinity, adding ethyl acetate for extraction, drying by anhydrous sodium sulfate, distilling under reduced pressure, and recrystallizing acetonitrile to obtain a product 3,3' -di (beta-amino-ethoxy) azobenzene, namely a compound 6; dissolving the compound 6 and polybrominated methylbenzene in ethanol, stirring for 2 hours at room temperature, adding distilled water, and separating out a target compound, namely branched polymeric azobenzene.
6. The method of preparing the hyperbranched azobenzene polymer of claim 5, wherein: the mass ratio of the 3,3' -dihydroxyazobenzene to the N-Boc-bromoethylamine to the potassium carbonate is 2:7:20.
7. The method of preparing the hyperbranched azobenzene polymer of claim 5, wherein: the polybasic bromomethylbenzene is one of 1, 4-dibromomethylbenzene, 1, 35-tribromomethylbenzene and 1,3,4, 6-tetrabromomethylbenzene.
8. The method for producing hyperbranched azobenzene polymer according to claim 5, wherein the hyperbranched azobenzene polymer is used as a light responsive functional compound or as a reaction intermediate for introducing functional azobenzene groups and amino groups.
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