CN114853685B - Broadband liquid crystal laser protection material prepared by multi-click chemistry and preparation method thereof - Google Patents
Broadband liquid crystal laser protection material prepared by multi-click chemistry and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001311 chemical methods and process Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 139
- 239000000047 product Substances 0.000 claims abstract description 67
- -1 azido alkyne Chemical class 0.000 claims abstract description 66
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 39
- APAJFZPFBHMFQR-UHFFFAOYSA-N anthraflavic acid Chemical compound OC1=CC=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1 APAJFZPFBHMFQR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000001681 protective effect Effects 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 402
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 126
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 108
- 238000010992 reflux Methods 0.000 claims description 98
- 239000007787 solid Substances 0.000 claims description 92
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 76
- 239000011259 mixed solution Substances 0.000 claims description 63
- 239000003208 petroleum Substances 0.000 claims description 63
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 54
- 229910052786 argon Inorganic materials 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 54
- 238000010898 silica gel chromatography Methods 0.000 claims description 49
- 239000003480 eluent Substances 0.000 claims description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- 238000005286 illumination Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 38
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 36
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 33
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 32
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 30
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 27
- 238000002390 rotary evaporation Methods 0.000 claims description 27
- 238000010025 steaming Methods 0.000 claims description 27
- 238000004440 column chromatography Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000002386 leaching Methods 0.000 claims description 24
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 16
- 150000008282 halocarbons Chemical class 0.000 claims description 16
- 239000013067 intermediate product Substances 0.000 claims description 16
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 14
- 229910002027 silica gel Inorganic materials 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- FTBCOQFMQSTCQQ-UHFFFAOYSA-N 4-bromobenzenethiol Chemical compound SC1=CC=C(Br)C=C1 FTBCOQFMQSTCQQ-UHFFFAOYSA-N 0.000 claims description 12
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 claims description 12
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 12
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 11
- SSVLWPBEYHGWJT-UHFFFAOYSA-N 4-ethynyl-n,n-dihexylaniline Chemical group CCCCCCN(CCCCCC)C1=CC=C(C#C)C=C1 SSVLWPBEYHGWJT-UHFFFAOYSA-N 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 11
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 10
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910001431 copper ion Inorganic materials 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 claims description 9
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 7
- 238000012650 click reaction Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- GYEJUFWGFHPFAR-UHFFFAOYSA-N n,n-dibutyl-4-ethynylaniline Chemical group CCCCN(CCCC)C1=CC=C(C#C)C=C1 GYEJUFWGFHPFAR-UHFFFAOYSA-N 0.000 claims description 7
- TZDXNFAAJNEYIO-UHFFFAOYSA-N 1-bromo-3-ethynylbenzene Chemical compound BrC1=CC=CC(C#C)=C1 TZDXNFAAJNEYIO-UHFFFAOYSA-N 0.000 claims description 6
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 6
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical compound INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 claims description 5
- LTLVZQZDXQWLHU-UHFFFAOYSA-N 1-bromo-4-ethynylbenzene Chemical compound BrC1=CC=C(C#C)C=C1 LTLVZQZDXQWLHU-UHFFFAOYSA-N 0.000 claims description 4
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 claims description 3
- ZWMAYLMVFSCMMS-UHFFFAOYSA-N 4-ethynyl-n,n-dimethylaniline Chemical group CN(C)C1=CC=C(C#C)C=C1 ZWMAYLMVFSCMMS-UHFFFAOYSA-N 0.000 claims description 3
- 238000007385 chemical modification Methods 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- 229940102396 methyl bromide Drugs 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 20
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 10
- 238000000746 purification Methods 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000013077 target material Substances 0.000 description 7
- IITRNNAMIWGXFZ-UHFFFAOYSA-N 6-bromopyridine-3-thiol Chemical compound SC1=CC=C(Br)N=C1 IITRNNAMIWGXFZ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- NTKWNZUTMJIAKN-UHFFFAOYSA-N n,n-dihexyl-4-(2-trimethylsilylethynyl)aniline Chemical compound CCCCCCN(CCCCCC)C1=CC=C(C#C[Si](C)(C)C)C=C1 NTKWNZUTMJIAKN-UHFFFAOYSA-N 0.000 description 4
- VGLAJERHBBEPQP-UHFFFAOYSA-N 5-bromo-2-ethynylpyridine Chemical compound BrC1=CC=C(C#C)N=C1 VGLAJERHBBEPQP-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 239000001000 anthraquinone dye Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- WMKJYNKENIUAFJ-UHFFFAOYSA-N n,n-dibutyl-4-(2-trimethylsilylethynyl)aniline Chemical compound CCCCN(CCCC)C1=CC=C(C#C[Si](C)(C)C)C=C1 WMKJYNKENIUAFJ-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003385 ring cleavage reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a multi-click chemistry preparation broadband liquid crystal laser protective material and a preparation method thereof, wherein the liquid crystal laser protective material capable of absorbing broadband spectrum is prepared by esterification reaction, sulfhydryl clicking reaction, [2+2] cycloaddition-cyclocleavage clicking reaction, azido alkyne 1,3 dipole cycloaddition clicking reaction and the like based on 2, 6-dihydroxyanthraquinone, and the preparation method is simple and convenient, high-efficiency, high in product yield and easy to purify, and has no byproducts, thus being an ideal preparation mode; the prepared anthraquinone derivative has excellent property, wide absorption wave band and strong absorption capacity, wherein the change of the group and the side group can change the maximum absorption wavelength, the absorption wavelength range is mutually enlarged, the anthraquinone derivative has liquid crystal property, the application aspect is more flexible, and the anthraquinone derivative has great application value.
Description
Technical Field
The invention relates to the field of laser protection, in particular to a broadband liquid crystal laser protection material prepared by multiple click chemistry and a preparation method thereof.
Background
With the progress of modern technology, laser technology is one of the fastest growing technical fields, and has very important development significance for both civil and military fields. The laser has the advantages of concentrated energy and good monochromaticity, but also has potential threats of causing harm to human bodies, damaging photoelectric elements and the like. In military terms, laser weapons are being the focus of military development in all countries. It is worth mentioning that the development of laser weapons in the united states is the most leading, and is a potential and serious challenge for the development in China. Aiming at the harm of the laser technology, the laser protection technology becomes a research hotspot of various countries, and the research of the efficient laser protection material has very important significance.
Click chemistry is the first proposed concept of Nobel chemistry in the United states, namely, the advanced and strong and effective synthesis method for realizing the connection of carbon-heteroatom through stable and high-efficiency chemical reaction rich in free selectivity, thereby realizing rapid synthesis and generating a large number of new compounds, and the click chemistry reaction has the advantages of rapidness, high efficiency, mild reaction conditions, good stereoselectivity, high product purity and easy separation, and has great application potential in the preparation of laser protection materials.
The existing inorganic laser protective material has weak broadband absorption capacity. The anthraquinone absorbing dye is an important laser protective material, and the excellent broadband absorbing capability is also not possessed by inorganic laser protective materials, so that the laser protective material prepared by modifying the anthraquinone material has excellent protective performance.
Disclosure of Invention
The invention aims to provide a broadband liquid crystal laser protection material prepared by multi-click chemistry and a preparation method thereof, wherein the prepared laser protection material can absorb broadband spectrum, and the preparation method is quick, efficient and convenient, has high product yield, is easy to separate and has no byproducts.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A broadband liquid crystal laser protective material has the following structural general formula:
Wherein:
A preparation method of a broadband liquid crystal laser protective material comprises the following steps:
step one, esterification of 2, 6-dihydroxyanthraquinone with 4-vinylbenzoic acid
Taking 0.1-20 parts of 2, 6-dihydroxyanthraquinone and 0.2-40 parts of 4-vinylbenzoic acid according to the mass ratio of 1 (2-4), dissolving in 50-300mL of anhydrous dichloromethane, putting into a flask, adding 0.2-40 parts of dicyclohexylcarbodiimide and 0.01-5 parts of 4-dimethylaminopyridine into the flask, stirring at room temperature for 23-26h, rotary evaporating for 10-60min, and performing silica gel column chromatography, wherein dichloromethane is used as eluent to obtain a sample 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4-vinyl benzoate);
Step two, 4-azidothioate is introduced into the product of the step one through a sulfhydryl double bond click reaction
Taking 0.1-20 parts of 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4-vinyl benzoate) and 0.2-40 parts of 4-azidothioate, putting the mixture into a reaction flask by taking 50-300mL of N, N-dimethylformamide as a solvent, and filling argon gas into the reaction flask to carry out ultrasonic deoxidization for 20-60min; placing the flask into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, maintaining the system temperature at 20-100 ℃ and irradiating for 0.5-12h, and simultaneously using ultraviolet irradiation and laser irradiation when starting microwave irradiation; spin-steaming to remove the solvent after the reaction is finished; further performing silica gel column chromatography by taking a mixed solution with the volume ratio of dichloromethane to petroleum ether being 1:6 as a leaching agent to obtain a target product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate);
Step three, introducing 1-bromo-4-ethynyl benzene into the second product through 1,3 dipolar addition click reaction
Dissolving 0.1-20 parts of 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2-40 parts of 1-bromo-3-ethynyl benzene into a 50-500mL round bottom flask under stirring, adding 0.1-10 parts GuBr, introducing argon to ultrasonically deoxidize for 20-60min, adding 0.01-1 parts of N, N-diisopropylethylamine under the dark condition, placing the flask into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and with normal pressure and reflux, starting a microwave irradiation and reflux condensing device, maintaining the system temperature at 80-110 ℃ through the microwave reactor, irradiating for 0.5-12h, adding 2-10mL of concentrated copper ions in the system after the reaction is finished, extracting with methylene dichloride, washing with water, drying, filtering and concentrating, and performing column chromatography to obtain the product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (4- (4-bromophenyl) -1-bromo-phenyl) 1, 3-thio) benzoate;
Step four, preparation of p- (di-X-amino) phenylacetylene
Dissolving 0.1-20 parts of para-iodoaniline and 0.2-40 parts of halogenated hydrocarbon in a 50-500mL flask filled with 50-300mL of N, N-dimethylformamide, adding 0.1-20 parts of potassium carbonate and 0.1-20 parts of potassium iodide, introducing argon and carrying out ultrasonic deoxidation for 10-60 minutes, putting the flask in a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, and ensuring the system temperature to be 20-100 ℃ and the irradiation time to be 0.5-12 hours; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.5-12h; centrifuging to remove solids after the reaction is finished; removing the solvent by rotary evaporation, and then further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as a leaching agent to obtain a p- (diX group) iodoaniline intermediate product;
Dissolving 0.1-20 parts of the prepared intermediate p- (di-X-group) iodoaniline in 50-300mL of a 50-500mL flask of a mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 0.1-20 parts of trimethylsilyl acetylene, 0.01-3 parts of bis (triphenylphosphine) palladium dichloride and 0.01-9 parts of cuprous iodide, introducing argon, and carrying out ultrasonic deoxidation for 10-60min; then transferring the flask into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, starting microwave irradiation for 0.5-12h, and keeping the system temperature at 10-100 ℃; ultraviolet irradiation and laser irradiation are used for 0.1-6h when microwave irradiation is started; centrifuging to remove solids, steaming to remove solvent, and further purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether with volume ratio of 1:6 as eluent to obtain yellow liquid N, N-di-X-4- ((trimethylsilyl) ethynyl) aniline;
Dissolving 0.1-20 parts of N, N-di-X-4- ((trimethylsilyl) ethynyl) aniline and 0.1-20 parts of potassium carbonate into a 50-500mL flask containing 50-300mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 10-60min; transferring the flask into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, starting microwave irradiation for 0.5-12h, and keeping the system temperature at 10-100 ℃; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used for 0.1-5 hours; centrifuging to remove solids after stopping the reaction; removing the solvent by rotary evaporation to obtain p- (di-X amino) phenylacetylene by dichloromethane column chromatography;
step five, introducing p- (di-X amino) phenylacetylene to anthraquinone derivative
The weight portion is 1:2, taking 0.1-20 parts of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4-bromophenyl) -1 hydrogen-1, 2, 3-triazole-1-yl) phenyl) thio) ethyl) benzoate) which is a product obtained in the step three, dissolving 0.2-40 parts of p- (diX amino) phenylacetylene which is obtained in the step four in a flask containing 50-300mL of a mixed solution with the volume ratio of triethylamine to tetrahydrofuran being 1:1, adding 0.01-5 parts of ditriphenylphosphine palladium dichloride and 0.01-5 parts of cuprous iodide, introducing argon and carrying out ultrasonic deoxidation for 10-60min; then transferring the flask into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, starting microwave irradiation for 0.5-12h, and keeping the system temperature at 10-100 ℃; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.5-6 hours; after the reaction is finished, centrifuging to remove solids, removing a solvent by rotary evaporation, and then further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as a leaching agent to obtain anthraquinone derivatives;
Step six, click chemical modification is carried out on the anthraquinone derivative
The weight portion is 1:2, 0.1 to 20 parts of anthraquinone derivative prepared in the step five and 0.2 to 40 parts of click reagent are taken and dissolved in a certain amount of dichloromethane, and stirred for 0.5 to 3 hours at room temperature; initiating chemical reaction by microwave irradiation, wherein the irradiation time is 0.5-6h, and the system temperature is kept at 20-100 ℃; and (3) irradiating with ultraviolet radiation and laser for 0.5-12h when microwave irradiation is started, performing rotary evaporation for 10-120min after the reaction is finished, preparing eluent with petroleum ether and dichloromethane in a volume ratio of 1:1, and purifying with a silica gel column to obtain the product.
Further, the click reagent is 7, 8-tetracyanoquinodimethane, tetracyanoethylene or 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinodimethane.
And in the second step, the reactant 4-azidophenylthiophenol is generated by reacting 4-bromothiophenol with NaN3, wherein the specific reaction process is that 0.2-40 parts of 4-bromothiophenol and 0.2-40 parts of NaN3 are added into a 50-500mL flask, then 50-300mL of dimethyl sulfoxide is added, and the mixture is heated and stirred to dissolve the mixture, the oil bath is heated for reaction at 50 ℃, the oil bath is removed after the reaction is finished, the mixture is washed with water for a plurality of times, dichloromethane (DCM) is used for extraction, the organic phase of the mixture is collected, dried by anhydrous sodium sulfate, silica gel column chromatography is carried out, and petroleum ether is used as an eluent to obtain the 4-azidophenylthiophenol.
Further, in the second step, the reaction temperature is kept through a microwave reactor, the microwave frequency is 2350-2500MHz, and the microwave power is 400-1500W; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of ultraviolet light is 190-380nm, and the illumination intensity is 5mW/cm 2-5W/cm2. .
In the third step, the reaction temperature is kept through a microwave reactor, the microwave frequency is 2350-2500MHz, the microwave power is 400-1500W, and petroleum ether is used in column chromatography: the volume ratio of the ethyl acetate is 6:1, and the eluent is chromatographed.
Further, in the fourth step, according to the difference of the number n of alkyl carbon atoms, the halogenated hydrocarbon is different, when n=1, the halogenated hydrocarbon is methyl iodide and methyl bromide, and the obtained product is p- (dimethylamino) phenylacetylene; when n=4, the halocarbon is bromobutane, and the obtained product is p- (dibutylamino) phenylacetylene; when n=6, the halogenated hydrocarbon is bromohexane, and the obtained product is p- (dihexylamino) phenylacetylene; at n=16, the halocarbon is 1-bromohexadecane and the resulting product is p- (hexacosamino) phenylacetylene.
The invention has the following beneficial effects:
(1) The liquid crystal laser protective material capable of absorbing broadband spectrum is prepared by esterification reaction, sulfhydryl clicking reaction, [2+2] cycloaddition-cyclocrack clicking reaction, azido alkyne 1,3 dipole cycloaddition clicking reaction and the like based on 2, 6-dihydroxyanthraquinone, and the broadband laser absorbing material is anthraquinone derivative, has excellent photoelectric property, shows nonlinear optical performance, and has fast response and wide absorption band. The material with the structure has the property of liquid crystal and stability, and the flexibility and the two-phase color property of the material are greatly improved compared with other anthraquinone materials. The triazole, benzene ring, ester group and other structures in the anthraquinone derivative expand the conjugation range, are favorable for improving the stability and the laser absorption capacity of the material, and the side groups are favorable for improving the solubility of the series of materials and are favorable for further improving the light absorption performance of the materials by doping with other materials. The anthraquinone derivative has different maximum absorption wavelengths of side groups according to the structure, and the wave band range and absorption capacity of the anthraquinone derivative are mutually enlarged.
(2) The invention adds thioether structure on anthraquinone derivative by using sulfhydryl alkene click chemistry mode, which increases flexibility of anthraquinone material. The microwave irradiation, ultraviolet and solid pulse laser technology are creatively and simultaneously used in the reaction process, the energy supply is flexibly adjusted, the thiophenol and the olefin can be rapidly reacted without a catalyst in the click reaction, the reaction speed is improved, the reaction time is shortened, and the conversion rate is higher.
(3) According to the invention, an azido alkyne 1,3 dipole cycloaddition click chemistry method is used, and a triazole structure is added on an anthraquinone material, so that the conjugation range is enlarged, and the light absorption capacity is better. The reaction between azide and alkyne is promoted by microwave and catalyst, so that the reaction progress is shortened and the yield is higher.
(4) According to the invention, the performance of the anthraquinone dye can be changed by the [2+2] cycloaddition-ring cleavage click chemistry method on the anthraquinone material with different click reagents, so that the performance of the anthraquinone dye is more diversified. Through microwave irradiation, ultraviolet and solid pulse technology, the microwave frequency, laser intensity and ultraviolet wavelength are flexibly adjusted, the click reaction conversion rate is greatly improved on the basis of original click chemistry, and the reaction is accelerated.
Drawings
FIG. 1 is a diagram showing the construction of a laser protection material prepared according to the present invention;
FIG. 2 is a synthetic reaction scheme of the laser shielding material prepared by the invention.
Detailed Description
The following examples illustrate the invention in further detail.
The broadband liquid crystal laser protective material has the following structural general formula:
Wherein:
a preparation method for preparing a broadband liquid crystal laser protective material by multi-click chemistry comprises the following steps:
step one, esterification of 2, 6-dihydroxyanthraquinone with 4-vinylbenzoic acid
Dissolving 0.1-20 parts of 2, 6-dihydroxyanthraquinone and 0.2-40 parts of 4-vinylbenzoic acid (the ratio is 1:2-1:4) in 50-300mL of anhydrous dichloromethane, putting into a 50-500mL flask, adding 0.2-40 parts of dicyclohexylcarbodiimide and 0.01-5 parts of 4-dimethylaminopyridine into the anhydrous dichloromethane, stirring at room temperature for 23-26h, rotationally evaporating for 10-60min, performing silica gel column chromatography, wherein dichloromethane is used as eluent to obtain a sample 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4-vinylbenzoate), wherein the chemical formula of the sample is shown as follows
Step two, taking 4-azidothioate as an example, introducing the 4-azidothioate into the product in the step one through a sulfhydryl double bond clicking reaction
Taking 0.1-20 parts of 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4-vinyl benzoate) and 0.2-40 parts of 4-azidothioate, putting the mixture into a 50-500mL reaction flask by taking 50-300mLN and N-dimethylformamide as solvents, and filling argon into the reaction flask to remove oxygen for 20-60min by ultrasonic. Placing the flask into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, starting a microwave irradiation and reflux condensing device, and keeping the reaction temperature through the microwave reactor, wherein the microwave frequency is 2350-2500MHz, the microwave power is 400-1500W, the irradiation time is 0.5-12h, and the system temperature is 20-100 ℃. Simultaneously using ultraviolet irradiation and laser irradiation when starting microwave irradiation, wherein the ultraviolet wavelength is 190-380nm, and the illumination intensity is 5mW/cm2-5W/cm2; and (5) removing the solvent by rotary steaming for 10-120min after the reaction is finished. Further performing silica gel column chromatography by taking a mixed solution with the volume ratio of dichloromethane to petroleum ether being 1:6 as a leaching agent to obtain a target product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate), wherein the prepared product is shown as follows:
Wherein the reactant 4-azidothioate is produced by reacting 4-bromothiophenol with NaN3 under certain conditions, the specific reaction process is that 0.2-40 parts of 4-bromothiophenol and 0.2-40 parts of NaN3 are added into a 50-500mL flask, then 50-300mL of dimethyl sulfoxide is added and heated and stirred to dissolve, the oil bath is heated for a certain time at about 50 ℃, the oil bath is removed after the reaction is finished, the water is washed for a plurality of times, dichloromethane (DCM) is used for extraction, the organic phase is collected, anhydrous sodium sulfate is used for drying, silica gel column chromatography is carried out, and petroleum ether is used as eluent. The 4-azidothioate is obtained, and the structure is shown as follows:
Step three, taking 1-bromo-4-ethynyl benzene as an example, introducing the 1-bromo-4-ethynyl benzene into the product through 1,3 dipole-addition click reaction
The prepared 0.1-20 parts of 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2-40 parts of 1-bromo-3-ethynylbenzene are stirred and dissolved in a 50-500mL round bottom flask by using 50-200mL tetrahydrofuran, 0.1-10 parts of GuBr are added, argon is introduced to carry out ultrasonic deoxygenation for 20-60min, 0.01-1 parts of N, N-diisopropylethylamine is added under the condition of avoiding light, the flask is placed into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and with normal pressure and reflux, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept by the microwave reactor, the microwave frequency is 2350-2500MHz, the microwave power is 400-1500W, the irradiation time is 0.5-12h, and the system temperature is 80-110 ℃ and the reaction is avoided. After the reaction is finished, adding 2-10mL of concentrated ammonia water to remove copper ions in the system, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, filtering, concentrating, performing column chromatography, and using petroleum ether: ethyl acetate=6:1 as eluent to give the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4-bromophenyl) -1-hydro-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate) having the structure:
Step four, preparation of p- (di-X-amino) phenylacetylene
Dissolving 0.1-20 parts of p-iodoaniline and 0.2-40 parts of halohydrocarbon in a 50-500mL flask filled with 50-300mLN and N-dimethylformamide, adding 0.1-20 parts of potassium carbonate and 0.1-20 parts of potassium iodide, introducing argon gas, carrying out ultrasonic deoxidation for 10-60 minutes, putting the flask into a normal-pressure microwave reactor with ultraviolet and Nd: YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2350-2500MHz, the microwave power is 300-1500W, the irradiation time is 0.5-12h, the system temperature is 20-100 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the temperature exceeds a preset temperature, and starting the microwave generator to heat when the temperature is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 340-380nm, the illumination intensity is 5mW/cm < 2 > -5W/cm < 2 >, the temperature is 10-100 ℃, and the irradiation time is 0.5-12h; centrifuging at a speed of 5000-10000r/min for 1-10min after the reaction is finished to remove solids; and (3) removing the solvent by rotary evaporation for 10-120min, and then further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as a leaching agent to obtain the p- (di-X-group) iodoaniline intermediate product.
Wherein the halogenated hydrocarbon may also be different depending on the number n of alkyl carbon atoms. If n=1, the halohydrocarbon can be methyl iodide or methyl bromide, and the obtained product is p- (dimethylamino) phenylacetylene; when n=4, the halogenated hydrocarbon may be bromobutane, and the resulting product is p- (dibutylamino) phenylacetylene; when n=6, the halogenated hydrocarbon may be bromohexane, and the resulting product is p- (dihexylamino) phenylacetylene; when n=16, the halogenated hydrocarbon may be 1-bromohexadecane, and the resulting product is p- (hexacosamino) phenylacetylene.
Dissolving 0.1-20 parts of the prepared intermediate product in a 50-500mL flask with 50-300mL of a mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 0.1-20 parts of trimethylsilyl acetylene, 0.01-3 parts of bis (triphenylphosphine) palladium dichloride and 0.01-9 parts of cuprous iodide, introducing argon, and carrying out ultrasonic deoxidation for 10-60min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2300-2500MHz, the microwave power is 300-1500W, the irradiation time is 0.5-12h min, the system temperature is 10-100 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, and starting the microwave generator to heat when the temperature is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 350-370nm, the illumination intensity is 5mW/cm < 2 > -5W/cm < 2 >, the temperature is 10-100 ℃, and the irradiation time is 0.1-6h; centrifuging at a speed of 5000-10000r/min for 1-10min to remove solids, steaming for 10-120min to remove solvent, and purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:6 as eluent to obtain yellow liquid N, N-di-X-4- ((trimethylsilyl) ethynyl) aniline.
The following is a synthetic scheme for the target product p- (di-X-ylamino) phenylacetylene:
Dissolving 0.1-20 parts of the prepared product and 0.1-20 parts of potassium carbonate in a 50-500mL flask containing 50-300mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 10-60min; transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2300-2500MHz, the microwave power is 300-1500W, the irradiation time is 0.5-12h, the system temperature is 10-100 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 360-380nm, the illumination intensity is 5mW/cm 2-5W/cm2, the temperature is 10-100 ℃, and the irradiation time is 0.1-5 hours; centrifuging at a speed of 5000-10000r/min for 1-10min to remove solids after stopping the reaction; spin-evaporating for 10-120min to remove solvent, and performing dichloromethane column chromatography to obtain p- (di X amino) phenylacetylene.
Step five, introducing p- (di-X amino) phenylacetylene to anthraquinone derivative
Taking 0.1-20 parts of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4-bromophenyl) -1 hydrogen-1, 2, 3-triazole-1-yl) phenyl) thio) ethyl) benzoate) which is a product obtained in the step three and 0.2-40 parts of p- (diX amino) phenylacetylene (the ratio of the two is about 1:2) which is obtained in the step four, dissolving the product into a flask which contains 50-300mL of a mixed solution with the volume ratio of triethylamine to tetrahydrofuran being 1:1, adding 0.01-5 parts of ditriphenylphosphine palladium dichloride and 0.01-5 parts of cuprous iodide, introducing argon and carrying out ultrasonic deoxidation for 10-60min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2300-2500MHz, the microwave power is 300-1500W, the irradiation time is 0.5-12h, the system temperature is 10-100 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and starting the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of ultraviolet light is 350-380nm, the illumination intensity is 5mW/cm 2-5W/cm2, the temperature is 10-100 ℃, and the irradiation time is 0.5-6h; after the reaction is finished, centrifuging at a speed of 5000-10000r/min for 1-10min to remove solids, steaming for 10-120min to remove solvent, and further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:6 as a leaching agent to obtain anthraquinone derivatives, wherein the structural general formula is as follows:
Step six, click chemical modification is carried out on the anthraquinone derivative
Dissolving 0.1-20 parts of anthraquinone derivative prepared in the step five and 0.2-40 parts of click reagent (the ratio is about 1:2) in a certain amount of dichloromethane, and stirring for 0.5-3 hours at room temperature; the chemical reaction is initiated by microwave irradiation, the microwave frequency is 2350-2500MHz, the microwave power is 400-1500W, the temperature is 20-100 ℃, and the irradiation is carried out for 0.5-6h. The temperature of the system is 20-100 ℃. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of ultraviolet light is 350-370nm, the illumination intensity is 5mW/cm 2-5W/cm2, the temperature is 20-100 ℃, and the irradiation time is 0.5-12h. After the reaction is finished, rotary steaming is carried out for 10-120min, then, the eluent is prepared by using petroleum ether and dichloromethane with the volume ratio of 1:1, and the silica gel column is used for purification. The obtained product is a target material, and the structural general formula is as follows:
Wherein,
The click reagent is specifically 7, 8-tetracyanoquinodimethane (7, 8-Tetracyanoquinodimethane) abbreviated as TCNQ, tetracyanoethylene (Tetracyanoethylene) abbreviated as TCNE, 2,3,5,6-tetrafluoro-7,7 'abbreviated as F4-TCNQ, 8,8' -tetracyanoquino-dimethane (2, 3,5,6-Tetrafluoro-7, 8-tetracyanodiquinomethane) has a molecular formula as follows:
Tetracyanoethylene of abbreviation TCNE; /(I) 7, 8-Tetracyanoquinodimethane abbreviated as TCNQ
2,3,5, 6-Tetrafluoro-7, 7', 8' -tetracyanoquino-dimethane abbreviated as F4-TCNQ.
Example 1: r1 and R2 take benzene rings as examples, bromobutane is used as halogenated alkane, TCNE is used as a click reagent in [2+2] click chemistry to manufacture the broadband laser protection material.
Step one, 0.1 part of 2, 6-dihydroxyanthraquinone and 0.2 part of 4-vinylbenzoic acid (ratio 1:2-1:4) are dissolved in 50mL of anhydrous dichloromethane and put into a 100mL flask, 0.2 part of Dicyclohexylcarbodiimide (DCC) and 0.01 part of 4-Dimethylaminopyridine (DMAP) are added into the mixture, the mixture is stirred for 24 hours at room temperature, the mixture is subjected to rotary evaporation for 30 minutes, and silica gel column chromatography is carried out, wherein dichloromethane is used as eluent, so that a sample 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4-vinyl benzoate) is obtained, and the yield is 92%.
Step two, 0.1 part of 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4-vinyl benzoate) and 0.2 part of 4-azidophenylthiophenol are taken and put into a 100mL reaction flask by taking 50mLN and N-Dimethylformamide (DMF) as solvents, and argon is filled for ultrasonic deoxidation for 30min. The flask is placed into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept through the microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, and the system temperature is 40 ℃. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2; and (5) removing the solvent by rotary steaming for 50min after the reaction is finished. And (3) further performing silica gel column chromatography by taking a mixed solution with the volume ratio of Dichloromethane (DCM) to Petroleum Ether (PE) being 1:6 as a leaching agent to obtain a target product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) with the yield of 93%.
The reactant 4-azidothioate is produced by reacting 4-bromothiophenol with NaN3, wherein the specific reaction process is that 0.2 part of 4-bromothiophenol and 0.2 part of NaN3 are added into a 100mL flask, then 100mL of dimethyl sulfoxide is added and heated and stirred to dissolve the mixture, the oil bath is heated for reaction at 50 ℃, the oil bath is removed after the reaction is finished, the mixture is washed for a plurality of times, dichloromethane (DCM) is used for extraction, the organic phase is collected, anhydrous sodium sulfate is used for drying, silica gel column chromatography is carried out, and petroleum ether is used as eluent to obtain the 4-azidothioate.
Step three, using 50mL Tetrahydrofuran (THF), stirring and dissolving 0.1 part of 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2 part of 1-bromo-3-ethynyl benzene in a 100mL round bottom flask, adding 0.1 part GuBr part, introducing argon to ultrasonically deoxidize for 30min, adding 0.01 part of N, N-Diisopropylethylamine (DIPEA) under the dark condition, placing the flask into a microwave reactor with normal pressure belt reflux of ultraviolet and Nd: YAG solid pulse laser, starting a microwave irradiation and reflux condensing device, maintaining the reaction temperature through the microwave reactor, keeping the microwave frequency at 2450MHz, keeping the microwave power at 900W, keeping the irradiation time at 6h, keeping the system temperature at 80 ℃ and keeping the dark during the reaction. After the reaction is finished, adding 2ml of concentrated ammonia water to remove copper ions in the system, extracting with Dichloromethane (DCM), washing with water, drying with anhydrous sodium sulfate, filtering, concentrating, performing column chromatography, and adding Petroleum Ether (PE): ethyl Acetate (EA) =6:1 as eluent chromatography afforded the product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4- (4-bromophenyl) -1-hydro-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate) in 90% yield.
Dissolving 0.1 part of p-iodoaniline and 0.2 part of bromobutane in a 100mL flask filled with 50mLN, N-Dimethylformamide (DMF), adding 0.1 part of potassium carbonate and 0.1 part of potassium iodide, introducing argon gas, ultrasonically deoxidizing for 30 minutes, putting the flask into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and normal pressure belt reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm < 2 >, and the irradiation is carried out for 3 hours at the temperature of 80 ℃; then centrifuging at 8000r/min for 10min to remove solids; the solvent is removed by rotary evaporation for 30min, and then the mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 is used as a leaching agent for further silica gel column chromatography purification, so as to obtain the p- (dibutyl) iodoaniline intermediate product with the yield of 89%.
Dissolving 0.1 part of the prepared intermediate product into a 100mL flask with 50mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 0.1 part of trimethylsilyl acetylene, 0.01 part of bis (triphenylphosphine) palladium dichloride and 0.01 part of cuprous iodide, introducing argon, and carrying out ultrasonic deoxygenation for 30min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm 2, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; the solid was then removed by centrifugation at 8000r/min for 10min, the solvent was removed by spin evaporation for 50min, and then further purified by column chromatography on silica gel using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) in a volume ratio of 1:6 as eluent to give the yellow liquid N, N-dibutyl-4- ((trimethylsilyl) ethynyl) aniline in 91% yield.
Dissolving 0.1 part of the prepared product and 0.1 part of potassium carbonate in a 100mL flask containing 50mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon, and carrying out ultrasonic deoxygenation for 30min; transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the temperature is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 3650nm, the illumination intensity is 10mW/cm 2, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; centrifuging at 8000r/min for 10min to remove solids after stopping the reaction; the solvent was removed by rotary evaporation for 30min, and column chromatography with methylene chloride gave p- (dibutylamino) phenylacetylene in 92% yield.
Step five, 0.1 part of the 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4-bromophenyl) -1 hydrogen-1, 2, 3-triazole-1-yl) phenyl) thio) ethyl) benzoate) obtained in the step three and 0.2 part of the p- (dibutylamino) phenylacetylene obtained in the step four are taken and dissolved in a 100mL flask containing a mixed solution of 50mL of triethylamine and tetrahydrofuran in a volume ratio of 1:1, and then 0.01 part of bis triphenylphosphine palladium dichloride and 0.01 part of cuprous iodide are added, argon is introduced and the mixture is subjected to ultrasonic deoxidation for 30min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 60 ℃, a reflux condensing device is started in the microwave irradiation process, when the temperature in the microwave reactor exceeds the preset temperature, the microwave generator is closed for cooling, and when the temperature is lower than the preset temperature, the microwave generator is opened for heating; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm <2 >, the temperature is 60 ℃, and the irradiation is carried out for 3 hours; after the reaction is finished, centrifuging at a rate of 8000r/min for 10min to remove solids, steaming for 30min to remove solvent, and further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:6 as a leaching agent to obtain the anthraquinone derivative with a yield of 90%.
Step six, 0.1 part of the anthraquinone derivative prepared in the step five and 0.1 part TCNE part of the anthraquinone derivative are dissolved in 50mL of dichloromethane, and stirred for 0.5h at room temperature; the chemical reaction is initiated by microwave irradiation, the microwave frequency is 2450MHz, the microwave power is 1200W, the system temperature is 50 ℃, and the irradiation is carried out for 3 hours. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 1W/cm 2. After the reaction is finished, steaming for 30min, preparing eluent with the volume ratio of petroleum ether to dichloromethane being 1:1, and purifying by a silica gel column. The product obtained is the final target material in 92% yield.
Example 2: r1, R2 take benzene ring as an example, halogenated alkane uses bromobutane, and [2+2] click chemistry adopts TCNQ as click reagent to prepare broadband laser protection material
Step one, 20 parts of 2, 6-dihydroxyanthraquinone and 40 parts of 4-vinylbenzoic acid (the ratio is 1:2-1:4) are dissolved in 300mL of anhydrous dichloromethane and put into a 500mL flask, 0.2 part of Dicyclohexylcarbodiimide (DCC) and 0.01-part of 4-Dimethylaminopyridine (DMAP) are added into the anhydrous dichloromethane, stirring is carried out at room temperature for 24 hours, rotary evaporation is carried out for 30 minutes, silica gel column chromatography is carried out, dichloromethane is taken as eluent, and sample 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4-vinyl benzoate) is obtained, and the yield is 91%.
Step two, 20 parts of 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4-vinyl benzoate) and 40 parts of 4-azidophenylthiophenol are placed into a 500mL reaction flask with 300mLN and N-Dimethylformamide (DMF) as solvents, and argon is filled for ultrasonic deoxygenation for 50min. The flask is placed into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept through the microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, and the system temperature is 40 ℃. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2; and (5) removing the solvent by rotary steaming for 50min after the reaction is finished. And (3) further performing silica gel column chromatography by taking a mixed solution with the volume ratio of Dichloromethane (DCM) to Petroleum Ether (PE) being 1:6 as a leaching agent to obtain a target product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) with the yield of 90%.
The reactant 4-azidophenylthiophenol is generated by reacting 4-bromothiophenol with NaN3, wherein the specific reaction process is that 30 parts of 4-bromothiophenol and 40 parts of NaN3 are added into a 50mL flask, then 50mL dimethyl sulfoxide is added, the mixture is heated and stirred to be dissolved, the heating reaction is carried out at the temperature of 50 ℃ in an oil bath, the oil bath is removed after the reaction is finished, the mixture is washed by water for multiple times, dichloromethane (DCM) is used for extraction, an organic phase of the mixture is collected, anhydrous sodium sulfate is used for drying, silica gel column chromatography is carried out, and petroleum ether is used as an eluent to obtain the 4-azidophenylthiophenol.
Step three, using 300mL Tetrahydrofuran (THF), stirring and dissolving 20 parts of 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 40 parts of 1-bromo-3-ethynyl benzene into a 500mL round bottom flask, adding 10 parts GuBr, introducing argon to ultrasonically deoxidize for 30min, adding 1 part of N, N-Diisopropylethylamine (DIPEA) under a dark condition, placing the flask into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and normal pressure belt reflux, starting a microwave irradiation and reflux condensing device, and keeping the reaction temperature through the microwave reactor, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, and the system temperature is 80 ℃ and the reaction is dark. After the reaction is finished, adding 10ml of concentrated ammonia water to remove copper ions in the system, extracting with Dichloromethane (DCM), washing with water, drying with anhydrous sodium sulfate, filtering, concentrating, performing column chromatography, and adding Petroleum Ether (PE): ethyl Acetate (EA) =6:1 was chromatographed as an eluent to give the product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4- (4-bromophenyl) -1-hydro-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate) in 92% yield.
Step four, dissolving 20 parts of para-iodoaniline and 40 parts of bromobutane in a 500mL flask filled with 300mLN and N-Dimethylformamide (DMF), adding 20 parts of potassium carbonate and 20 parts of potassium iodide, introducing argon and carrying out ultrasonic deoxygenation for 40 minutes, putting the flask into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and normal pressure and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, the system temperature is 80 ℃, a reflux condensing device is started in the microwave irradiation process, when the microwave reactor exceeds the preset temperature, the microwave generator is closed for cooling, and when the microwave reactor is lower than the preset temperature, the microwave generator is opened for heating; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm 2, and the irradiation is carried out for 6 hours at the temperature of 80 ℃; then centrifuging at 8000r/min for 10min to remove solids; the solvent is removed by rotary evaporation for 60min, and then the mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 is used as a leaching agent for further silica gel column chromatography purification, so as to obtain the p- (dibutyl) iodoaniline intermediate product with the yield of 90 percent.
Dissolving 20 parts of the prepared intermediate product in a 500mL flask with 300mL of a mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 20 parts of trimethylsilyl acetylene, 3 parts of bis (triphenylphosphine) palladium dichloride and 9 parts of cuprous iodide, introducing argon, and carrying out ultrasonic deoxygenation for 30min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm 2, the temperature is 80 ℃, and the irradiation is carried out for 6 hours; then centrifuging at 8000r/min for 10min to remove solids, steaming for 60min to remove solvent, and further purifying by silica gel column chromatography with a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with a volume ratio of 1:6 as a leaching agent to obtain yellow liquid N, N-dibutyl-4- ((trimethylsilyl) ethynyl) aniline with a yield of 90%.
Dissolving 20 parts of the prepared product and 20 parts of potassium carbonate in a 500mL flask containing 300mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and carrying out ultrasonic deoxygenation for 30min; transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the temperature is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 3650nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 80 ℃, and the irradiation is carried out for 6 hours; centrifuging at 8000r/min for 10min to remove solids after stopping the reaction; the solvent was removed by rotary evaporation for 60min, and column chromatography with methylene chloride gave p- (dibutylamino) phenylacetylene in 93% yield.
Step five, taking 20 parts of the 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4-bromophenyl) -1 hydrogen-1, 2, 3-triazole-1-yl) phenyl) thio) ethyl) benzoate) obtained in the step three and 40 parts of the p- (dibutylamino) phenylacetylene obtained in the step four, dissolving in a 500mL flask containing 300mL of a mixed solution with the volume ratio of triethylamine to tetrahydrofuran being 1:1, adding 5 parts of bis (triphenylphosphine) palladium dichloride and 5 parts of cuprous iodide, introducing argon and carrying out ultrasonic deoxidization for 30min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, the system temperature is 60 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm 2, the temperature is 60 ℃, and the irradiation is carried out for 6 hours; after the reaction is finished, centrifuging at a rate of 8000r/min for 10min to remove solids, steaming for 60min to remove solvent, and further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:6 as a leaching agent to obtain the anthraquinone derivative with a yield of 92%.
Step six, 20 parts of the anthraquinone derivative prepared in the step five and 20 parts of TCNQ are dissolved in 50mL of dichloromethane, and stirred for 1h at room temperature; the chemical reaction is initiated by microwave irradiation, the microwave frequency is 2450MHz, the microwave power is 1200W, the system temperature is 50 ℃, and the irradiation is carried out for 3 hours. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 1W/cm < 2 >. After the reaction is finished, steaming for 60min, preparing eluent with the volume ratio of petroleum ether to dichloromethane being 1:1, and purifying by a silica gel column. The product obtained is the final target material in 93% yield.
Example 3: r1, R2 take benzene ring as an example, halogenated alkane uses bromohexane, and [2+2] click chemistry adopts F4-TCNQ as click reagent to prepare the broadband laser protection material
Step one, 0.1 part of 2, 6-dihydroxyanthraquinone and 0.2 part of 4-vinylbenzoic acid (ratio 1:2-1:4) are dissolved in 50mL of anhydrous dichloromethane and put into a 100mL flask, 0.2 part of Dicyclohexylcarbodiimide (DCC) and 0.01 part of 4-Dimethylaminopyridine (DMAP) are added into the mixture, the mixture is stirred for 24 hours at room temperature, the mixture is subjected to rotary evaporation for 30 minutes, and silica gel column chromatography is carried out, wherein dichloromethane is used as eluent, so that a sample 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4-vinyl benzoate) is obtained, and the yield is 92%.
Step two, 0.1 part of 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4-vinyl benzoate) and 0.2 part of 4-azidophenylthiophenol are taken and put into a 100mL reaction flask by taking 50mLN and N-Dimethylformamide (DMF) as solvents, and argon is filled for ultrasonic deoxidation for 30min. The flask is placed into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept through the microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, and the system temperature is 40 ℃. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2; and (5) removing the solvent by rotary steaming for 50min after the reaction is finished. And (3) further performing silica gel column chromatography by taking a mixed solution with the volume ratio of Dichloromethane (DCM) to Petroleum Ether (PE) being 1:6 as a leaching agent to obtain a target product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) with the yield of 92%.
The reactant 4-azidothioate is produced by reacting 4-bromothiophenol with NaN3, wherein the specific reaction process is that 40 parts of 4-bromothiophenol and 40 parts of NaN3 are added into a 500mL flask, 300mL of dimethyl sulfoxide is added and heated and stirred to dissolve the mixture, the oil bath is heated for reaction at 50 ℃, the oil bath is removed after the reaction is finished, the mixture is washed with water for multiple times, dichloromethane (DCM) is used for extraction, an organic phase of the mixture is collected, anhydrous sodium sulfate is used for drying, silica gel column chromatography is carried out, and petroleum ether is used as an eluent to obtain the 4-azidothioate.
Step three, using 50mL Tetrahydrofuran (THF), stirring and dissolving 0.1 part of 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2 part of 1-bromo-3-ethynyl benzene in a 100mL round bottom flask, adding 0.1 part GuBr part, introducing argon to ultrasonically deoxidize for 30min, adding 0.01 part of N, N-Diisopropylethylamine (DIPEA) under the dark condition, placing the flask into a microwave reactor with normal pressure belt reflux of ultraviolet and Nd: YAG solid pulse laser, starting a microwave irradiation and reflux condensing device, maintaining the reaction temperature through the microwave reactor, keeping the microwave frequency at 2450MHz, keeping the microwave power at 900W, keeping the irradiation time at 6h, keeping the system temperature at 80 ℃ and keeping the dark during the reaction. After the reaction is finished, adding 2ml of concentrated ammonia water to remove copper ions in the system, extracting with Dichloromethane (DCM), washing with water, drying with anhydrous sodium sulfate, filtering, concentrating, performing column chromatography, and adding Petroleum Ether (PE): ethyl Acetate (EA) =6:1 as eluent chromatography afforded the product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4- (4-bromophenyl) -1-hydro-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate) in 90% yield.
Dissolving 0.1 part of p-iodoaniline and 0.2 part of bromohexane in a 100mL flask filled with 50mLN, N-Dimethylformamide (DMF), adding 0.1 part of potassium carbonate and 0.1 part of potassium iodide, introducing argon gas, ultrasonically deoxidizing for 30 minutes, putting the flask into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and normal pressure belt reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm 2, and the irradiation is carried out for 3 hours at the temperature of 80 ℃; then centrifuging at 8000r/min for 10min to remove solids; the solvent was removed by rotary evaporation for 30min, and then the mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 was used as a eluent for further purification by silica gel column chromatography to obtain the p- (dihexyl) iodoaniline intermediate product with the yield of 91%.
Dissolving 0.1 part of the prepared intermediate product into a 100mL flask with 50mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 0.1 part of trimethylsilyl acetylene, 0.01 part of bis (triphenylphosphine) palladium dichloride and 0.01 part of cuprous iodide, introducing argon, and carrying out ultrasonic deoxygenation for 30min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm 2, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; the solid was then removed by centrifugation at 8000r/min for 10min, the solvent was removed by spin evaporation for 50min, and then further purified by column chromatography on silica gel using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) in a volume ratio of 1:6 as eluent to give the yellow liquid N, N-dihexyl-4- ((trimethylsilyl) ethynyl) aniline in 92% yield.
Dissolving 0.1 part of the prepared product and 0.1 part of potassium carbonate in a 100mL flask containing 50mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon, and carrying out ultrasonic deoxygenation for 30min; transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the temperature is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 3650nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; centrifuging at 8000r/min for 10min to remove solids after stopping the reaction; the solvent was removed by rotary evaporation for 30min, and column chromatography with methylene chloride gave p- (dihexylamino) phenylacetylene in 92% yield.
Step five, 0.1 part of the 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4-bromophenyl) -1 hydrogen-1, 2, 3-triazole-1-yl) phenyl) thio) ethyl) benzoate) obtained in the step three and 0.2 part of the p- (dihexylamino) phenylacetylene obtained in the step three are taken and dissolved in a 100mL flask containing a mixed solution with the volume ratio of triethylamine to tetrahydrofuran of 50mL being 1:1, and then 0.01 part of bis triphenylphosphine palladium dichloride and 0.01 part of cuprous iodide are added, argon is introduced and the mixture is subjected to ultrasonic deoxidation for 30min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 60 ℃, a reflux condensing device is started in the microwave irradiation process, when the temperature in the microwave reactor exceeds the preset temperature, the microwave generator is closed for cooling, and when the temperature is lower than the preset temperature, the microwave generator is opened for heating; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm <2 >, the temperature is 60 ℃, and the irradiation is carried out for 3 hours; after the reaction is finished, centrifuging at a rate of 8000r/min for 10min to remove solids, steaming for 30min to remove solvent, and further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:6 as a leaching agent to obtain the anthraquinone derivative with a yield of 91%.
Step six, 0.1 part of the anthraquinone derivative prepared in the step five and 0.1 part of F4-TCNQ are dissolved in 50mL of dichloromethane, and stirred for 0.5h at room temperature; the chemical reaction is initiated by microwave irradiation, the microwave frequency is 2450MHz, the microwave power is 1200W, the system temperature is 50 ℃, and the irradiation is carried out for 3 hours. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 1W/cm < 2 >. After the reaction is finished, steaming for 30min, preparing eluent with the volume ratio of petroleum ether to dichloromethane being 1:1, and purifying by a silica gel column. The product obtained is the final target material in 92% yield.
Example 4: r1, R2 are pyridine for example, halogenated alkane uses bromohexane, and [2+2] click chemistry adopts F4-TCNQ as click reagent to prepare the broadband laser protection material
Step one, 0.1 part of 2, 6-dihydroxyanthraquinone and 0.2 part of 4-vinylbenzoic acid (ratio 1:2-1:4) are dissolved in 50mL of anhydrous dichloromethane and put into a 100mL flask, 0.2 part of Dicyclohexylcarbodiimide (DCC) and 0.01 part of 4-Dimethylaminopyridine (DMAP) are added into the mixture, the mixture is stirred for 24 hours at room temperature, the mixture is subjected to rotary evaporation for 30 minutes, and silica gel column chromatography is carried out, wherein dichloromethane is used as eluent, so that a sample 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4-vinyl benzoate) is obtained, and the yield is 92%.
Step two, 0.1 part of 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4-vinyl benzoate) and 0.2 part of 6-azidopyridine-3-thiol are taken and put into a 100mL reaction flask by taking 50mLN and N-Dimethylformamide (DMF) as solvents, and argon is filled for ultrasonic deoxygenation for 30min. The flask is placed into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept through the microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, and the system temperature is 40 ℃. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 10mW/cm < 2 >; and (5) removing the solvent by rotary steaming for 50min after the reaction is finished. Further performing silica gel column chromatography by taking a mixed solution with the volume ratio of Dichloromethane (DCM) to Petroleum Ether (PE) being 1:6 as a leaching agent to obtain a target product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((6-azidopyridine-3-yl) thio) ethyl) benzoate) with the yield of 91%.
The reactant 6-azidopyridine-3-thiol is produced by the reaction of 6-bromopyridine-3-thiol and NaN3, the specific reaction process is that 20 parts of 6-bromopyridine-3-thiol and 30 parts of NaN3 are added into a 250mL flask, then 250mL of dimethyl sulfoxide is added and heated and stirred to dissolve, the oil bath is heated for reaction at 50 ℃, the oil bath is removed after the reaction is finished, the water is washed for a plurality of times, dichloromethane (DCM) is used for extraction, the organic phase is collected, anhydrous sodium sulfate is used for drying, silica gel column chromatography is carried out, and petroleum ether is used as eluent to obtain the 6-azidopyridine-3-thiol.
Step three, using 50mL Tetrahydrofuran (THF), stirring and dissolving 0.1 part of 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4- (2- ((6-azidopyridine-3-yl) thio) ethyl) benzoate) and 0.2 part of 5-bromo-2-ethynylpyridine into a 100mL round bottom flask, adding 0.1 part GuBr part, introducing argon to ultrasonically deoxidize for 30min, adding 0.01 part of N, N-Diisopropylethylamine (DIPEA) under the dark condition, placing the flask into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and reflux under normal pressure, starting a microwave irradiation and reflux condensing device, maintaining the reaction temperature through the microwave reactor, keeping the microwave frequency at 2450MHz, keeping the microwave power at 900W, keeping the irradiation time at 6h, keeping the system temperature at 80 ℃ and keeping the reaction dark. After the reaction is finished, adding 2ml of concentrated ammonia water to remove copper ions in the system, extracting with Dichloromethane (DCM), washing with water, drying with anhydrous sodium sulfate, filtering, concentrating, performing column chromatography, and adding Petroleum Ether (PE): ethyl Acetate (EA) =6:1 was chromatographed as an eluent to give the product 6- ((4- (2- ((6- (4- (4-bromophenyl) -1H-1,2, 3-triazol-1-yl) pyridin-3-yl) thio) ethyl) benzoyl) oxy) -9, 10-dioxo-9, 10-dihydro-anthracene-2-yl 4- (2- ((6- (4- (6-bromopyridin-3-yl) -1H-1,2, 3-triazol-1-yl) pyridin-3-yl) thio) ethyl) benzoate) in 90% yield.
Dissolving 0.1 part of p-iodoaniline and 0.2 part of bromohexane in a 100mL flask filled with 50mLN, N-Dimethylformamide (DMF), adding 0.1 part of potassium carbonate and 0.1 part of potassium iodide, introducing argon gas, ultrasonically deoxidizing for 30 minutes, putting the flask into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and normal pressure belt reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm < 2 >, and the irradiation is carried out for 3 hours at the temperature of 80 ℃; then centrifuging at 8000r/min for 10min to remove solids; the solvent was removed by rotary evaporation for 30min, and then the mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 was used as a eluent for further purification by silica gel column chromatography to obtain the p- (dihexyl) iodoaniline intermediate product with the yield of 91%.
Dissolving 0.1 part of the prepared intermediate product into a 100mL flask with 50mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 0.1 part of trimethylsilyl acetylene, 0.01 part of bis (triphenylphosphine) palladium dichloride and 0.01 part of cuprous iodide, introducing argon, and carrying out ultrasonic deoxygenation for 30min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; the solid was then removed by centrifugation at 8000r/min for 10min, the solvent was removed by spin evaporation for 50min, and then further purified by column chromatography on silica gel using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) in a volume ratio of 1:6 as eluent to give the yellow liquid N, N-dihexyl-4- ((trimethylsilyl) ethynyl) aniline in 92% yield.
Dissolving 0.1 part of the prepared product and 0.1 part of potassium carbonate in a 100mL flask containing 50mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon, and carrying out ultrasonic deoxygenation for 30min; transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the temperature is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 3650nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; centrifuging at 8000r/min for 10min to remove solids after stopping the reaction; the solvent was removed by rotary evaporation for 30min, and column chromatography with methylene chloride gave p- (dihexylamino) phenylacetylene in 92% yield.
Step five, taking 0.1 part of the product 6- ((4- (2- ((6- (4-bromophenyl) -1H-1,2, 3-triazol-1-yl) pyridine-3-yl) sulfur) ethyl) benzoyl) oxy) -9, 10-dioxo-9, 10-dihydro-anthracene-2-yl 4- (2- ((6-bromopyridin-3-yl) -1H-1,2, 3-triazol-3-yl) pyridine-3-yl) sulfur) ethyl) benzoate) prepared in the step three and 0.2 part of the product p- (dihexylamino) phenylacetylene obtained in the step four, dissolving in 100mL of a mixed solution containing 50mL of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 0.01 part of bis triphenylphosphine palladium dichloride and 0.01 part of cuprous iodide, introducing argon gas, and ultrasonically deoxidizing for 30min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 60 ℃, a reflux condensing device is started in the microwave irradiation process, when the temperature in the microwave reactor exceeds the preset temperature, the microwave generator is closed for cooling, and when the temperature is lower than the preset temperature, the microwave generator is opened for heating; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 60 ℃, and the irradiation is carried out for 3 hours; after the reaction is finished, centrifuging at a rate of 8000r/min for 10min to remove solids, steaming for 30min to remove solvent, and further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:6 as a leaching agent to obtain the anthraquinone derivative with a yield of 91%.
Step six, 0.1 part of the anthraquinone derivative prepared in the step five and 0.1 part of F4-TCNQ are dissolved in 50mL of dichloromethane, and stirred for 0.5h at room temperature; the chemical reaction is initiated by microwave irradiation, the microwave frequency is 2450MHz, the microwave power is 1200W, the system temperature is 50 ℃, and the irradiation is carried out for 3 hours. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 1W/cm < 2 >. After the reaction is finished, rotary steaming is carried out for 30min, then the eluent is prepared by using petroleum ether and dichloromethane with the volume ratio of 1:1, and the silica gel column is used for purification. The product obtained is the final target material in 92% yield.
TABLE 1 laser light transmittance for each band when the product was injected into a 50 μm liquid crystal cell by injection
TABLE 2 thermal decomposition temperatures of the products of the examples
Example 5: r1, R2 are pyridine for example, halogenated alkane uses bromohexane, and [2+2] click chemistry adopts F4-TCNQ as click reagent to prepare the broadband laser protection material
Step one, 0.1 part of 2, 6-dihydroxyanthraquinone and 0.4 part of 4-vinylbenzoic acid (ratio 1:2-1:4) are dissolved in 100mL of anhydrous dichloromethane and put into a 100mL flask, 0.6 part of Dicyclohexylcarbodiimide (DCC) and 0.5 part of 4-Dimethylaminopyridine (DMAP) are added into the mixture, the mixture is stirred for 23h at room temperature, the mixture is subjected to rotary evaporation for 10min, and silica gel column chromatography is carried out, wherein dichloromethane is used as eluent, so that a sample 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4-vinyl benzoate) is obtained, and the yield is 92%.
Step two, 0.5 part of 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4-vinyl benzoate) and 0.5 part of 6-azidopyridine-3-thiol are taken and put into a 100mL reaction flask by taking 100mLN, N-Dimethylformamide (DMF) as a solvent, and argon is filled for ultrasound deoxidization for 20min. The flask is placed into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept through the microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 0.5h, and the system temperature is 100 ℃. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2; and (5) removing the solvent by rotary steaming for 50min after the reaction is finished. Further performing silica gel column chromatography by taking a mixed solution with the volume ratio of Dichloromethane (DCM) to Petroleum Ether (PE) being 1:6 as a leaching agent to obtain a target product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((6-azidopyridine-3-yl) thio) ethyl) benzoate) with the yield of 91%.
The reactant 6-azidopyridine-3-thiol is produced by the reaction of 6-bromopyridine-3-thiol and NaN3, the specific reaction process is that 20 parts of 6-bromopyridine-3-thiol and 30 parts of NaN3 are added into a 250mL flask, then 250mL of dimethyl sulfoxide is added and heated and stirred to dissolve, the oil bath is heated for reaction at 50 ℃, the oil bath is removed after the reaction is finished, the water is washed for a plurality of times, dichloromethane (DCM) is used for extraction, the organic phase is collected, anhydrous sodium sulfate is used for drying, silica gel column chromatography is carried out, and petroleum ether is used as eluent to obtain the 6-azidopyridine-3-thiol.
Step three, using 50mL Tetrahydrofuran (THF), stirring and dissolving 10 parts of 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4- (2- ((6-azidopyridine-3-yl) thio) ethyl) benzoate) and 20 parts of 5-bromo-2-ethynylpyridine into a 50mL round bottom flask, adding 5 parts GuBr, introducing argon to ultrasonically deoxidize for 20min, adding 0.05 part of N, N-Diisopropylethylamine (DIPEA) under the dark condition, placing the flask into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and reflux, starting a microwave irradiation and reflux condensing device, maintaining the reaction temperature through the microwave reactor, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 0.5h, and the system temperature is 110 ℃ and the dark condition is generated during the reaction. After the reaction is finished, 5ml of concentrated ammonia water is added to remove copper ions in the system, dichloromethane (DCM) extraction, water washing, anhydrous sodium sulfate drying, filtration concentration, column chromatography and Petroleum Ether (PE): ethyl Acetate (EA) =6:1 was chromatographed as an eluent to give the product 6- ((4- (2- ((6- (4- (4-bromophenyl) -1H-1,2, 3-triazol-1-yl) pyridin-3-yl) thio) ethyl) benzoyl) oxy) -9, 10-dioxo-9, 10-dihydro-anthracene-2-yl 4- (2- ((6- (4- (6-bromopyridin-3-yl) -1H-1,2, 3-triazol-1-yl) pyridin-3-yl) thio) ethyl) benzoate) in 90% yield.
Step four, dissolving 10 parts of p-iodoaniline and 20 parts of bromohexane in a 200mL flask filled with 150mLN and N-Dimethylformamide (DMF), adding 10 parts of potassium carbonate and 10 parts of potassium iodide, introducing argon and carrying out ultrasonic deoxygenation for 60 minutes, putting the flask into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and normal pressure belt reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 0.5h, the system temperature is 100 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm < 2 >, and the irradiation is carried out for 12 hours at the temperature of 80 ℃; then centrifuging at 8000r/min for 10min to remove solids; the solvent was removed by rotary evaporation for 30min, and then the mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 was used as a eluent for further purification by silica gel column chromatography to obtain the p- (dihexyl) iodoaniline intermediate product with the yield of 91%.
10 Parts of the prepared intermediate product is dissolved in a 200mL flask with 150mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, and then 10 parts of trimethylsilyl acetylene, 0.5-part of bis (triphenylphosphine) palladium dichloride and 5 parts of cuprous iodide are added, argon is introduced, and ultrasonic deoxygenation is carried out for 60min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 0.5h, the system temperature is 100 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; the solid was then removed by centrifugation at 8000r/min for 10min, the solvent was removed by spin evaporation for 50min, and then further purified by column chromatography on silica gel using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) in a volume ratio of 1:6 as eluent to give the yellow liquid N, N-dihexyl-4- ((trimethylsilyl) ethynyl) aniline in 92% yield.
Dissolving 10 parts of the prepared product and 10 parts of potassium carbonate in a 200mL flask containing 100mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and carrying out ultrasonic deoxygenation for 60min; transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 0.5h, the system temperature is 100 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 3650nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 80 ℃, and the irradiation is carried out for 5 hours; centrifuging at 8000r/min for 10min to remove solids after stopping the reaction; the solvent was removed by rotary evaporation for 30min, and column chromatography with methylene chloride gave p- (dihexylamino) phenylacetylene in 92% yield.
Step five, 10 parts of the product 6- ((4- (2- ((6- (4-bromophenyl) -1H-1,2, 3-triazol-1-yl) pyridine-3-yl) sulfur) ethyl) benzoyl) oxy) -9, 10-dioxo-9, 10-dihydro-anthracene-2-yl 4- (2- ((6-bromopyridin-3-yl) -1H-1,2, 3-triazol-1-yl) pyridine-3-yl) sulfur) ethyl) benzoate) obtained in the step three and 20 parts of the p- (dihexylamino) phenylacetylene obtained in the step four are dissolved in a 100mL flask containing a mixed solution of 150mL of triethylamine and 1:1 in volume ratio, 0.5 part of bis triphenylphosphine palladium dichloride and 0.5 part of cuprous iodide are added, argon is introduced and the mixture is subjected to ultrasonic deoxygenation for 60min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 0.5h, the system temperature is 100 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 60 ℃, and the irradiation is carried out for 3 hours; after the reaction is finished, centrifuging at a rate of 8000r/min for 10min to remove solids, steaming for 30min to remove solvent, and further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:6 as a leaching agent to obtain the anthraquinone derivative with a yield of 91%.
Step six, 10 parts of the anthraquinone derivative prepared in the step five and 20 parts of F4-TCNQ are dissolved in 50mL of dichloromethane, and stirred for 3 hours at room temperature; the chemical reaction is initiated by microwave irradiation, the microwave frequency is 2450MHz, the microwave power is 1200W, the system temperature is 100 ℃, and the irradiation time is 0.5h. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 1W/cm 2. After the reaction is finished, -steaming for 120min, preparing eluent with petroleum ether and dichloromethane in a volume ratio of 1:1, and purifying by a silica gel column. The product obtained is the final target material in 92% yield.
Example 6: r1, R2 are pyridine for example, halogenated alkane uses bromohexane, and [2+2] click chemistry adopts F4-TCNQ as click reagent to prepare the broadband laser protection material
Step one, 10 parts of 2, 6-dihydroxyanthraquinone and 20 parts of 4-vinylbenzoic acid (the ratio is 1:2-1:4) are dissolved in 100mL of anhydrous dichloromethane and put into a 100mL flask, 40 parts of Dicyclohexylcarbodiimide (DCC) and 5 parts of 4-Dimethylaminopyridine (DMAP) are added into the anhydrous dichloromethane, the mixture is stirred for 26 hours at room temperature, the mixture is subjected to rotary evaporation for 60 minutes, silica gel column chromatography, dichloromethane is used as eluent, and a sample 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4-vinyl benzoate) is obtained, and the yield is 92%.
Step two, 0.5 part of 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4-vinyl benzoate) and 0.5 part of 6-azidopyridine-3-thiol are taken and put into a100 mL reaction flask by taking 100mLN, N-Dimethylformamide (DMF) as a solvent, and argon is filled for ultrasonic deoxygenation for 60min. The flask is placed into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept through the microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, and the system temperature is 20 ℃. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2; and (5) removing the solvent by rotary steaming for 50min after the reaction is finished. Further performing silica gel column chromatography by taking a mixed solution with the volume ratio of Dichloromethane (DCM) to Petroleum Ether (PE) being 1:6 as a leaching agent to obtain a target product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((6-azidopyridine-3-yl) thio) ethyl) benzoate) with the yield of 91%.
The reactant 6-azidopyridine-3-thiol is produced by the reaction of 6-bromopyridine-3-thiol and NaN3, the specific reaction process is that 20 parts of 6-bromopyridine-3-thiol and 30 parts of NaN3 are added into a 250mL flask, then 250mL of dimethyl sulfoxide is added and heated and stirred to dissolve, the oil bath is heated for reaction at 50 ℃, the oil bath is removed after the reaction is finished, the water is washed for a plurality of times, dichloromethane (DCM) is used for extraction, the organic phase is collected, anhydrous sodium sulfate is used for drying, silica gel column chromatography is carried out, and petroleum ether is used as eluent to obtain the 6-azidopyridine-3-thiol.
Step three, using 50mL Tetrahydrofuran (THF), stirring and dissolving 10 parts of 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4- (2- ((6-azidopyridine-3-yl) thio) ethyl) benzoate) and 20 parts of 5-bromo-2-ethynylpyridine into a 50mL round bottom flask, adding 5 parts GuBr, introducing argon to ultrasonically deoxidize for 60min, adding 0.05 parts of N, N-Diisopropylethylamine (DIPEA) under the dark condition, placing the flask into a microwave reactor with ultraviolet and Nd: YAG with a normal pressure belt reflux of solid pulse laser, starting a microwave irradiation and reflux condensing device, maintaining the reaction temperature through the microwave reactor, keeping the microwave frequency at 2450MHz, keeping the microwave power at 900W for 8h, keeping the system temperature at 90 ℃ and avoiding light during the reaction. After the reaction is finished, 5ml of concentrated ammonia water is added to remove copper ions in the system, dichloromethane (DCM) extraction, water washing, anhydrous sodium sulfate drying, filtration concentration, column chromatography and Petroleum Ether (PE): ethyl Acetate (EA) =6:1 was chromatographed as an eluent to give the product 6- ((4- (2- ((6- (4- (4-bromophenyl) -1H-1,2, 3-triazol-1-yl) pyridin-3-yl) thio) ethyl) benzoyl) oxy) -9, 10-dioxo-9, 10-dihydro-anthracene-2-yl 4- (2- ((6- (4- (6-bromopyridin-3-yl) -1H-1,2, 3-triazol-1-yl) pyridin-3-yl) thio) ethyl) benzoate) in 90% yield.
Step four, 10 parts of para-iodoaniline and 10 parts of bromohexane are dissolved in a 300mL flask filled with 100mLN, N-Dimethylformamide (DMF), 10 parts of potassium carbonate and 10 parts of potassium iodide are added, argon is introduced and ultrasound deoxidization is carried out for 10 minutes, the flask is put into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and normal pressure belt reflux, microwave irradiation is started, microwave frequency 2450MHz, microwave power 900W, irradiation time is 12h, system temperature is 00 ℃, a reflux condensing device is started in the microwave irradiation process, when the microwave reactor exceeds the preset temperature, the microwave generator is closed for cooling, and when the microwave reactor is lower than the preset temperature, the microwave generator is opened for heating; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm < 2 >, and the irradiation is carried out for 12 hours at the temperature of 80 ℃; then centrifuging at 8000r/min for 10min to remove solids; the solvent was removed by rotary evaporation for 30min, and then the mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 was used as a eluent for further purification by silica gel column chromatography to obtain the p- (dihexyl) iodoaniline intermediate product with the yield of 91%.
10 Parts of the prepared intermediate product is dissolved in a 100mL flask with 50mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, and then 10 parts of trimethylsilyl acetylene, 0.5-part of bis (triphenylphosphine) palladium dichloride and 5 parts of cuprous iodide are added, argon is introduced, and ultrasonic deoxygenation is carried out for 10min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, the system temperature is 10 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; the solid was then removed by centrifugation at 8000r/min for 10min, the solvent was removed by spin evaporation for 50min, and then further purified by column chromatography on silica gel using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) in a volume ratio of 1:6 as eluent to give the yellow liquid N, N-dihexyl-4- ((trimethylsilyl) ethynyl) aniline in 92% yield.
Dissolving 10 parts of the prepared product and 10 parts of potassium carbonate in a 200mL flask containing 100mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and carrying out ultrasonic deoxygenation for 10min; transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, the system temperature is 10 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the temperature is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of ultraviolet light is 3650nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 80 ℃, and the irradiation time is 0.1h; centrifuging at 8000r/min for 10min to remove solids after stopping the reaction; the solvent was removed by rotary evaporation for 30min, and column chromatography with methylene chloride gave p- (dihexylamino) phenylacetylene in 92% yield.
Step five, 10 parts of the product 6- ((4- (2- ((6- (4-bromophenyl) -1H-1,2, 3-triazol-1-yl) pyridine-3-yl) sulfur) ethyl) benzoyl) oxy) -9, 10-dioxo-9, 10-dihydro-anthracene-2-yl 4- (2- ((6-bromopyridin-3-yl) -1H-1,2, 3-triazol-1-yl) pyridine-3-yl) sulfur) ethyl) benzoate) obtained in the step three and 20 parts of the p- (dihexylamino) phenylacetylene obtained in the step four are dissolved in a 100mL flask containing a mixed solution of 150mL of triethylamine and 1:1 in volume ratio, 0.5 part of bis triphenylphosphine palladium dichloride and 0.5 part of cuprous iodide are added, argon is introduced and the mixture is subjected to ultrasonic deoxygenation for 10min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet and Nd-YAG solid pulse laser and reflux, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, the system temperature is 10 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to cool when the microwave reactor exceeds a preset temperature, and opening the microwave generator to heat when the microwave reactor is lower than the preset temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm < 2 >, the temperature is 60 ℃, and the irradiation time is 0.5h; after the reaction is finished, centrifuging at a rate of 8000r/min for 10min to remove solids, steaming for 30min to remove solvent, and further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:6 as a leaching agent to obtain the anthraquinone derivative with a yield of 91%.
Step six, 0.1 part of the anthraquinone derivative prepared in the step five and 0.2 part of F4-TCNQ are dissolved in 50mL of dichloromethane, and stirred for 3 hours at room temperature; the chemical reaction is initiated by microwave irradiation, the microwave frequency is 2450MHz, the microwave power is 1200W, the system temperature is 120 ℃, and the irradiation is performed for 6 hours. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 365nm, and the illumination intensity is 1W/cm 2. After the reaction is finished, steaming for 120min, preparing eluent with the volume ratio of petroleum ether to dichloromethane being 1:1, and purifying by a silica gel column. The product obtained is the final target material in 92% yield.
Claims (7)
1. A broadband liquid crystal laser protective material is characterized by having the following structural general formula:
Wherein:
2. the method for preparing the broadband liquid crystal laser protection material according to claim 1, which is characterized by comprising the following steps:
step one, esterification of 2, 6-dihydroxyanthraquinone with 4-vinylbenzoic acid
Taking 0.1-20 parts of 2, 6-dihydroxyanthraquinone and 0.2-40 parts of 4-vinylbenzoic acid according to the mass ratio of 1 (2-4), dissolving in 50-300mL of anhydrous dichloromethane, putting into a flask, adding 0.2-40 parts of dicyclohexylcarbodiimide and 0.01-5 parts of 4-dimethylaminopyridine into the flask, stirring at room temperature for 23-26h, rotary evaporating for 10-60min, and performing silica gel column chromatography, wherein dichloromethane is used as eluent to obtain 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4-vinylbenzoate);
Step two, 4-azidothioate is introduced into the product of the step one through a sulfhydryl double bond click reaction
Taking 0.1-20 parts of 9, 10-dioxo-9, 10-dihydro anthracene-2, 6-diylbis (4-vinyl benzoate) and 0.2-40 parts of 4-azidothioate, putting the mixture into a reaction flask by taking 50-300mL of N, N-dimethylformamide as a solvent, and filling argon gas into the reaction flask to carry out ultrasonic deoxidization for 20-60min; placing the flask into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, maintaining the system temperature at 20-100 ℃ and irradiating for 0.5-12h, and simultaneously using ultraviolet irradiation and laser irradiation when starting microwave irradiation; spin-steaming to remove the solvent after the reaction is finished; further performing silica gel column chromatography by taking a mixed solution with the volume ratio of dichloromethane to petroleum ether being 1:6 as a leaching agent to obtain a target product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate);
Step three, introducing 1-bromo-4-ethynyl benzene into the second product through 1,3 dipolar addition click reaction
Dissolving 0.1-20 parts of 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2-40 parts of 1-bromo-3-ethynyl benzene into a 50-500mL round bottom flask under stirring, adding 0.1-10 parts GuBr, introducing argon to ultrasonically deoxidize for 20-60min, adding 0.01-1 parts of N, N-diisopropylethylamine under the dark condition, placing the flask into a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and with normal pressure and reflux, starting a microwave irradiation and reflux condensing device, maintaining the system temperature at 80-110 ℃ through the microwave reactor, irradiating for 0.5-12h, adding 2-10mL of concentrated copper ions in the system after the reaction is finished, extracting with methylene dichloride, washing with water, drying, filtering and concentrating, and performing column chromatography to obtain the product 9, 10-dioxo-9, 10-dihydro-anthracene-2, 6-diylbis (4- (4- (4-bromophenyl) -1-bromo-phenyl) 1, 3-thio) benzoate;
Step four, preparation of p- (di-X-amino) phenylacetylene
Dissolving 0.1-20 parts of para-iodoaniline and 0.2-40 parts of halogenated hydrocarbon in a 50-500mL flask filled with 50-300mL of N, N-dimethylformamide, adding 0.1-20 parts of potassium carbonate and 0.1-20 parts of potassium iodide, introducing argon and carrying out ultrasonic deoxidation for 10-60 minutes, putting the flask in a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, and ensuring the system temperature to be 20-100 ℃ and the irradiation time to be 0.5-12 hours; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.5-12h; centrifuging to remove solids after the reaction is finished; removing the solvent by rotary evaporation, and then further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as a leaching agent to obtain a p- (diX group) iodoaniline intermediate product;
Dissolving 0.1-20 parts of the prepared intermediate p- (di-X-group) iodoaniline in 50-300mL of a 50-500mL flask of a mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 0.1-20 parts of trimethylsilyl acetylene, 0.01-3 parts of bis (triphenylphosphine) palladium dichloride and 0.01-9 parts of cuprous iodide, introducing argon, and carrying out ultrasonic deoxidation for 10-60min; then transferring the flask into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, starting microwave irradiation for 0.5-12h, and keeping the system temperature at 10-100 ℃; ultraviolet irradiation and laser irradiation are used for 0.1-6h when microwave irradiation is started; centrifuging to remove solids, steaming to remove solvent, and further purifying by silica gel column chromatography with mixed solution of dichloromethane and petroleum ether with volume ratio of 1:6 as eluent to obtain yellow liquid N, N-di-X-4- ((trimethylsilyl) ethynyl) aniline;
Dissolving 0.1-20 parts of N, N-di-X-4- ((trimethylsilyl) ethynyl) aniline and 0.1-20 parts of potassium carbonate into a 50-500mL flask containing 50-300mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 10-60min; transferring the flask into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, starting microwave irradiation for 0.5-12h, and keeping the system temperature at 10-100 ℃; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used for 0.1-5 hours; centrifuging to remove solids after stopping the reaction; removing the solvent by rotary evaporation, and performing column chromatography on methylene dichloride to obtain p- (di-X-amino) phenylacetylene;
step five, introducing p- (di-X amino) phenylacetylene to anthraquinone derivative
The weight portion is 1:2, taking 0.1-20 parts of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4-bromophenyl) -1 hydrogen-1, 2, 3-triazole-1-yl) phenyl) thio) ethyl) benzoate) which is a product obtained in the step three, dissolving 0.2-40 parts of p- (diX amino) phenylacetylene which is obtained in the step four in a flask containing 50-300mL of a mixed solution with the volume ratio of triethylamine to tetrahydrofuran being 1:1, adding 0.01-5 parts of ditriphenylphosphine palladium dichloride and 0.01-5 parts of cuprous iodide, introducing argon and carrying out ultrasonic deoxidation for 10-60min; then transferring the flask into a microwave reactor with ultraviolet and Nd-YAG solid pulse laser and normal pressure and reflux, starting microwave irradiation for 0.5-12h, and keeping the system temperature at 10-100 ℃; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.5-6 hours; after the reaction is finished, centrifuging to remove solids, removing a solvent by rotary evaporation, and then further purifying by silica gel column chromatography by taking a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as a leaching agent to obtain anthraquinone derivatives;
Step six, click chemical modification is carried out on the anthraquinone derivative
The weight portion is 1:2, 0.1 to 20 parts of anthraquinone derivative prepared in the step five and 0.2 to 40 parts of click reagent are taken and dissolved in a certain amount of dichloromethane, and stirred for 0.5 to 3 hours at room temperature; initiating chemical reaction by microwave irradiation, wherein the irradiation time is 0.5-6h, and the system temperature is kept at 20-100 ℃; and (3) irradiating with ultraviolet radiation and laser for 0.5-12h when microwave irradiation is started, performing rotary evaporation for 10-120min after the reaction is finished, preparing eluent with petroleum ether and dichloromethane in a volume ratio of 1:1, and purifying with a silica gel column to obtain the product.
3. The method for preparing the broadband liquid crystal laser protection material according to claim 2, wherein the method comprises the following steps: the click reagent is 7, 8-tetracyanoquinodimethane, tetracyanoethylene or 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinodimethane.
4. The method for preparing the broadband liquid crystal laser protection material according to claim 2, wherein the method comprises the following steps: in the second step, the reactant 4-azidophenylthiophenol is generated by reacting 4-bromothiophenol with NaN3, wherein the specific reaction process is that 0.2-40 parts of 4-bromothiophenol and 0.2-40 parts of NaN3 are added into a 50-500mL flask, then 50-300mL of dimethyl sulfoxide is added and heated and stirred to dissolve, the oil bath is heated for reaction at 50 ℃, the oil bath is removed after the reaction is finished, the water is washed for multiple times, dichloromethane (DCM) is used for extraction, the organic phase is collected, dried by anhydrous sodium sulfate, silica gel column chromatography is carried out, and petroleum ether is used as eluent to obtain the 4-azidophenylthiophenol.
5. The method for preparing the broadband liquid crystal laser protection material according to claim 2, wherein the method comprises the following steps: in the second step, the reaction temperature is kept through a microwave reactor, the microwave frequency is 2350-2500MHz, and the microwave power is 400-1500W; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of ultraviolet light is 190-380nm, and the illumination intensity is 5mW/cm 2-5 W/cm2.
6. The method for preparing the broadband liquid crystal laser protection material according to claim 2, wherein the method comprises the following steps: in the third step, the reaction temperature is kept through a microwave reactor, the microwave frequency is 2350-2500MHz, the microwave power is 400-1500W, and petroleum ether is used in column chromatography: the volume ratio of the ethyl acetate is 6:1, and the eluent is chromatographed.
7. The method for preparing the broadband liquid crystal laser protection material according to claim 2, wherein the method comprises the following steps: in the fourth step, according to the difference of the number n of alkyl carbon atoms, the halogenated hydrocarbon is different, when n=1, the halogenated hydrocarbon is methyl iodide and methyl bromide, and the obtained product is p- (dimethylamino) phenylacetylene; when n=4, the halocarbon is bromobutane, and the obtained product is p- (dibutylamino) phenylacetylene; when n=6, the halogenated hydrocarbon is bromohexane, and the obtained product is p- (dihexylamino) phenylacetylene; at n=16, the halocarbon is 1-bromohexadecane and the resulting product is p- (hexacosamino) phenylacetylene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN108863961A (en) * | 2018-08-01 | 2018-11-23 | 河南师范大学 | A kind of triazole anthraquinone derivative silver ion fluorescence probe and its preparation method and application |
| CN110437166A (en) * | 2018-05-03 | 2019-11-12 | 优缔新材料科技(苏州)有限公司 | A kind of anti-blue light compound, preparation method and applications |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013185098A (en) * | 2012-03-08 | 2013-09-19 | Nippon Shokubai Co Ltd | Phthalocyanine compound and heat-ray absorbing material including the same |
| CN110437166A (en) * | 2018-05-03 | 2019-11-12 | 优缔新材料科技(苏州)有限公司 | A kind of anti-blue light compound, preparation method and applications |
| CN108863961A (en) * | 2018-08-01 | 2018-11-23 | 河南师范大学 | A kind of triazole anthraquinone derivative silver ion fluorescence probe and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Dong Wang等.The application of double click to synthesize a third-order nonlinear polymer containing donor–acceptor chromophores.《Polym. Chem.,》.2016,第7卷第3714–3721页. * |
| 激光防护材料的研究进展;孟献丰等;《激光与红外》;第35卷(第2期);第71-73页 * |
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