CN114853685A - 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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- CN114853685A CN114853685A CN202210680576.1A CN202210680576A CN114853685A CN 114853685 A CN114853685 A CN 114853685A CN 202210680576 A CN202210680576 A CN 202210680576A CN 114853685 A CN114853685 A CN 114853685A
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000001311 chemical methods and process Methods 0.000 title description 3
- 239000000047 product Substances 0.000 claims abstract description 76
- -1 azide alkyne Chemical class 0.000 claims abstract description 59
- 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 34
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 34
- 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 15
- 238000012650 click reaction Methods 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 393
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 122
- 238000006243 chemical reaction Methods 0.000 claims description 122
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 108
- 238000010992 reflux Methods 0.000 claims description 93
- 239000007787 solid Substances 0.000 claims description 92
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 74
- 239000003480 eluent Substances 0.000 claims description 65
- 239000003208 petroleum Substances 0.000 claims description 61
- 239000002904 solvent Substances 0.000 claims description 61
- 238000002390 rotary evaporation Methods 0.000 claims description 60
- 239000011259 mixed solution Substances 0.000 claims description 57
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 claims description 56
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims description 56
- 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
- 238000010898 silica gel chromatography Methods 0.000 claims description 54
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- 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 37
- 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
- 238000003756 stirring Methods 0.000 claims description 35
- OLADDCIYVOEUDD-UHFFFAOYSA-N 4-azidobenzenethiol Chemical compound SC1=CC=C(N=[N+]=[N-])C=C1 OLADDCIYVOEUDD-UHFFFAOYSA-N 0.000 claims description 32
- 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 238000005286 illumination Methods 0.000 claims description 22
- FTBCOQFMQSTCQQ-UHFFFAOYSA-N 4-bromobenzenethiol Chemical compound SC1=CC=C(Br)C=C1 FTBCOQFMQSTCQQ-UHFFFAOYSA-N 0.000 claims description 19
- 238000004440 column chromatography Methods 0.000 claims description 19
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 18
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 150000008282 halocarbons Chemical class 0.000 claims description 18
- 239000013067 intermediate product Substances 0.000 claims description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 18
- 238000005406 washing Methods 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
- 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 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 15
- 230000001678 irradiating effect Effects 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 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
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 229910001431 copper ion Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical compound INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 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
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000011049 filling Methods 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
- 239000000376 reactant Substances 0.000 claims description 7
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-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
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 6
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-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
- SVLFYCVERCZSRS-UHFFFAOYSA-N 4-ethynyl-N-hexacosylaniline Chemical group C(CCCCCCCCCCCCCCCCCCCCCCCCC)NC1=CC=C(C=C1)C#C SVLFYCVERCZSRS-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
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- 229940102396 methyl bromide Drugs 0.000 claims description 3
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 27
- 238000000746 purification Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 7
- 239000013077 target material Substances 0.000 description 7
- 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
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000126 substance Substances 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
- 230000031700 light absorption Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 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 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000001000 anthraquinone dye Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- ISSUNVDQFLJNRZ-UHFFFAOYSA-N CCCCCC.[Br] Chemical compound CCCCCC.[Br] ISSUNVDQFLJNRZ-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 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
- 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 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QJPQVXSHYBGQGM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003385 ring cleavage reaction Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000001308 synthesis method 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
- 238000002604 ultrasonography Methods 0.000 description 1
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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 broadband liquid crystal laser protective material prepared by multiple click chemistry and a preparation method thereof, wherein the liquid crystal laser protective material capable of absorbing broadband spectrum is prepared by esterification reaction, sulfydryl click reaction, [2+2] cycloaddition-cyclocleavage click reaction, azide alkyne 1,3 dipolar cycloaddition click reaction and the like on the basis of 2, 6-dihydroxy anthraquinone, and the preparation method is simple, convenient and efficient, has high product yield, is easy to purify, has no by-product, and is an ideal preparation method; the prepared anthraquinone derivative has excellent property, wide absorption waveband and strong absorption capacity, wherein the maximum absorption wavelength can be changed by changing the groups and the side groups, the absorption wavelength range is mutually expanded, and the anthraquinone derivative has liquid crystal property, is more flexible in application and 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 multi-click chemistry and a preparation method thereof.
Background
With the progress of modern science and technology, the laser technology is one of the fastest-developing technical fields, and the laser technology has very important development significance for both civil use and military field. The laser has the advantages of concentrated energy and good monochromaticity, but has potential threats of harming human bodies, damaging photoelectric elements and the like. In military terms, laser weapons are the key point for military development in all countries. It is worth mentioning that the laser weapon in the united states is the most advanced development, and is a potential and serious challenge for the development of China. Aiming at the harm of the laser technology, the laser protection technology becomes a research hotspot of all countries, and the development of high-efficiency laser protection materials has very important significance.
Click chemistry is the first concept proposed by sharp of the nobel chemical prize in usa, and refers to an advanced, strong and effective synthesis method for realizing the connection of carbon-heteroatom through stable and efficient chemical reaction rich in free selectivity, thereby realizing the rapid synthesis and generating a large amount of new compounds.
The existing inorganic laser protective material has weak broadband absorption capacity. Anthraquinone absorbing dye is a very important laser protection material, excellent broadband absorption capacity is not possessed by inorganic laser protection materials, and the laser protection material prepared by modifying the anthraquinone material has excellent protection 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.
In order to achieve the purpose, the invention adopts the following technical scheme:
a broadband liquid crystal laser protective material prepared by multi-click chemistry has the following structural general formula:
wherein:
a preparation method for preparing a broadband liquid crystal laser protection material by multi-click chemistry comprises the following steps:
step one, esterification reaction of 2, 6-dihydroxy anthraquinone and 4-vinyl benzoic acid
Dissolving 0.1-20 parts of 2, 6-dihydroxyanthraquinone and 0.2-40 parts of 4-vinylbenzoic acid in 50-300mL of anhydrous dichloromethane according to the mass part ratio 1 (2-4), putting the mixture into a flask, adding 0.2-40 parts of dicyclohexylcarbodiimide and 0.01-5 parts of 4-dimethylaminopyridine into the flask, stirring the mixture at room temperature for 23-26h, performing rotary evaporation for 10-60min, and performing silica gel column chromatography, wherein dichloromethane is used as eluent to obtain a sample 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4-vinylbenzoate);
step two, introducing 4-azido thiophenol into the product in the step one through a sulfydryl double bond click reaction
Taking 0.1-20 parts of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4-vinyl benzoate) and 0.2-40 parts of 4-azido thiophenol, putting the mixture into a reaction flask by taking 50-300mL of N, N-dimethylformamide as a solvent, and filling argon for ultrasonic deoxidization for 20-60 min; placing the flask into a normal-pressure reflux microwave reactor with ultraviolet, Nd and YAG solid pulse laser, maintaining the system temperature at 20-100 ℃ and irradiating for 0.5-12h, and simultaneously using ultraviolet irradiation and laser irradiation when starting the microwave irradiation; removing the solvent by rotary evaporation after the reaction is finished; taking a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent, and further performing silica gel column chromatography to obtain a target product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate);
step three, introducing 1-bromo-4-ethynylbenzene into a product in step two through 1,3 dipolar addition click reaction
Stirring and dissolving 0.1-20 parts of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2-40 parts of 1-bromo-3-ethynylbenzene in a 50-500mL round-bottom flask, adding 0.1-10 parts of GuBr, introducing argon, ultrasonically deoxidizing for 20-60min, adding 0.01-1 part of N, N-diisopropylethylamine under the dark condition, putting the flask into a microwave reactor with ultraviolet and Nd, YAG solid pulse laser and normal pressure backflow, starting a microwave irradiation and backflow condensing device, keeping the temperature of the system by the microwave reactor at 80-110 ℃ for 0.5-12h, after the reaction is finished, adding 2-10mL of strong ammonia water to remove copper ions in the system, extracting with dichloromethane, washing with water, drying, filtering, concentrating, and performing column chromatography to obtain 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate);
step four, preparation of p- (diXylamino) phenylacetylene
Dissolving 0.1-20 parts of p-iodoaniline and 0.2-40 parts of halogenated hydrocarbon into 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, ultrasonically deoxidizing for 10-60 minutes, putting the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, YAG (yttrium aluminum garnet) solid pulse laser to ensure that the system temperature is 20-100 ℃, and irradiating for 0.5-12 hours; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.5-12 h; centrifuging to remove solids after the reaction is finished; removing the solvent by rotary evaporation, and then further purifying the mixture by silica gel column chromatography by using a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as an eluent to obtain a p- (diX group) iodoaniline intermediate product;
dissolving 0.1-20 parts of the prepared intermediate product p- (diX group) iodoaniline in 50-300mL of 50-500mL flask containing a mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, then 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 ultrasonically deoxidizing for 10-60 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, starting microwave irradiation for 0.5-12h, and keeping the temperature of the system at 10-100 ℃; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.1-6 h; then centrifuging to remove solids, removing the solvent by rotary evaporation, and then further purifying by silica gel column chromatography by using a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent to obtain yellow liquid N, N-diX-4- ((trimethylsilyl) ethynyl) aniline;
dissolving 0.1-20 parts of prepared N, N-diX-based-4- ((trimethylsilyl) ethynyl) aniline and 0.1-20 parts of potassium carbonate into a 50-500mL flask containing a mixed solution of 50-300mL of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 10-60 min; transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, starting microwave irradiation for 0.5-12h, and keeping the system temperature at 10-100 ℃; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used for 0.1-5 h; after the reaction is stopped, centrifuging to remove solids; removing the solvent by rotary evaporation to obtain dichloromethane, and performing column chromatography to obtain p- (diX-based amino) phenylacetylene;
step five, introducing p- (diXylamino) phenylacetylene into anthraquinone derivative
According to the mass part of 1:2, taking 0.1-20 parts of the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate) prepared in the third step and 0.2-40 parts of the product p- (diX-ylamino) phenylacetylene obtained in the fourth step, dissolving the product p- (diX-ylamino) phenylacetylene in a flask containing 50-300mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 0.01-5 parts of bis (triphenylphosphine) palladium dichloride and 0.01-5 parts of cuprous iodide, introducing argon and ultrasonically deoxidizing for 10-60 min; then transferring the flask into a normal-pressure microwave reactor with reflux and ultraviolet, Nd and YAG solid pulse laser, starting microwave irradiation for 0.5-12h, and keeping the temperature of the system at 10-100 ℃; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.5-6 h; after the reaction is finished, removing solids by centrifugation, 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 an eluent to obtain an anthraquinone derivative;
step six, carrying out click chemical modification on anthraquinone derivative R1
According to the mass part of 1:2, dissolving 0.1-20 parts of anthraquinone derivative prepared in the step five and 0.2-40 parts of click reagent in a certain amount of dichloromethane, and stirring for 0.5-3h at room temperature; microwave irradiation is utilized to initiate chemical reaction, the irradiation time is 0.5-6h, and the system temperature is kept at 20-100 ℃; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.5-12h, after the reaction is finished, rotary evaporation is carried out for 10-120min, then eluent is prepared by using petroleum ether and dichloromethane in a volume ratio of 1:1, and a silica gel column is purified to obtain a product.
Further, the click reagent is 7,7,8, 8-tetracyanoterephthalquinodimethane, tetracyanoethylene or 2,3,5,6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane.
Further, in the second step, the reactant 4-azidothiophenol is generated by reacting 4-bromophenylthiol with NaN3, specifically, 0.2-40 parts of 4-bromophenylthiol 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 be dissolved, the oil bath is heated at 50 ℃ for reaction, the oil bath is removed after the reaction is finished, the mixture is washed for multiple times by water, 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 used, and petroleum ether is used as an eluent to obtain the 4-azidothiophenol.
Further, in the second step, the reaction temperature is maintained by a microwave reactor, the microwave frequency is 2350-; when the microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of the ultraviolet light is 190-380nm, and the illumination intensity is 5mW/cm 2 -5W/cm 2 。.
Further, in the third step, the reaction temperature is kept by a microwave reactor, the microwave frequency is 2350-: eluting with ethyl acetate at a volume ratio of 6: 1.
Further, in the fourth step, according to the difference of the number n of alkyl carbon atoms, halogenated hydrocarbon is different, when n is 1, the halogenated hydrocarbon is methyl iodide and methyl bromide, and the obtained product is p- (dimethylamino) phenylacetylene; when n is 4, the halogenated hydrocarbon is bromobutane, and the obtained product is p- (dibutylamino) phenylacetylene; when n is 6, the halogenated hydrocarbon is bromohexane, and the obtained product is p- (dihexylamino) phenylacetylene; when n is 16, the halogenated hydrocarbon is 1-bromohexadecane, and the obtained product is p- (hexacosanylamino) phenylacetylene.
The invention has the following beneficial effects:
(1) the liquid crystal laser protective material capable of absorbing the broadband spectrum is prepared by esterification reaction, sulfydryl click reaction, [2+2] cycloaddition-cyclocleavage click reaction, azide alkyne 1,3 dipolar cycloaddition click reaction and the like on the basis of 2, 6-dihydroxy anthraquinone, and the mentioned broadband laser absorbing material is anthraquinone derivatives, has excellent photoelectric properties, shows nonlinear optical performance, is fast in response and is wide in absorbing waveband. The material with the structure has liquid crystal property, stability, flexibility and diphase property which are greatly improved compared with other anthraquinone materials. The structures of triazole, benzene ring, ester group and the like in the anthraquinone derivative provided by the invention expand the conjugation range, are beneficial to improving the stability of the material and the capability of absorbing laser, and the existing side group is beneficial to improving the solubility of the series of materials and is beneficial to doping with other materials to further improve the light absorption performance of the series of materials. The anthraquinone derivative has different maximum absorption wavelengths of the side groups according to the structure, and the wave band range and the absorption capacity of light absorption are mutually expanded.
(2) According to the invention, a thioether structure is added to the anthraquinone derivative in a mercapto olefin click chemistry manner, so that the flexibility of the anthraquinone material is increased. Microwave irradiation, ultraviolet and solid pulse laser technologies are used in the reaction process, energy supply is flexibly adjusted, the click reaction can be carried out quickly with thiophenol and olefin without a catalyst, the reaction speed is improved, the reaction time is shortened, and the conversion rate is higher.
(3) The invention uses azide alkyne 1,3 dipolar cycloaddition click chemistry method, adds triazole structure on anthraquinone material, enlarges conjugation range, and has better light absorption capacity. The microwave irradiation technology is innovatively used in the reaction process, the reaction of azide and alkyne is promoted under the action of microwaves and a catalyst, the reaction process is shortened, and the yield is higher.
(4) The invention can change the performance of the anthraquinone dye by the difference of the click reagent on the anthraquinone material through the [2+2] cycloaddition-ring cleavage click chemical method, so that the performance of the anthraquinone dye is more diversified. By microwave irradiation, ultraviolet and solid pulse technology, the microwave frequency, the laser intensity and the ultraviolet wavelength are flexibly adjusted, the click reaction conversion rate is greatly improved on the basis of the original click chemistry, and the reaction is accelerated.
Drawings
FIG. 1 is a structural diagram of a laser protective material prepared by the present invention;
FIG. 2 is a schematic diagram of a synthesis reaction route of the laser protective material prepared by the present invention.
Detailed Description
The present invention will be explained in further detail with reference to examples.
The invention relates to a broadband liquid crystal laser protective material prepared by multiple click chemistry, which has the following structural general formula:
wherein:
a preparation method for preparing a broadband liquid crystal laser protection material by multi-click chemistry comprises the following steps:
step one, esterification reaction of 2, 6-dihydroxy anthraquinone and 4-vinyl benzoic acid
Dissolving 0.1-20 parts of 2, 6-dihydroxyanthraquinone and 0.2-40 parts of 4-vinylbenzoic acid (the proportion is 1: 2-1: 4) in 50-300mL of anhydrous dichloromethane, putting the obtained solution into a 50-500mL flask, adding 0.2-40 parts of dicyclohexylcarbodiimide and 0.01-5 parts of 4-dimethylaminopyridine into the flask, stirring the obtained solution at room temperature for 23-26h, performing rotary evaporation for 10-60min, performing silica gel column chromatography, wherein dichloromethane is used as eluent to obtain a sample 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4-vinylbenzoate), and the chemical formula of the sample is shown in the specification
Step two, taking 4-azido thiophenol as an example, introducing the 4-azido thiophenol into the product in the step one through a sulfydryl double bond click reaction
0.1-20 parts of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4-vinyl benzoate) and 0.2-40 parts of 4-azido thiophenol are put into a 50-500mL reaction flask by taking 50-300mLN and N-dimethylformamide as a solvent, and argon is filled for ultrasonic deoxygenation for 20-60 min. Putting the flask into a normal-pressure reflux microwave reactor with ultraviolet, Nd and YAG solid pulse laser, starting a microwave irradiation and reflux condensing device, and keeping the reaction temperature through the microwave reactor, wherein the microwave frequency is 2350-. Simultaneously using ultraviolet irradiation and laser irradiation when starting microwave irradiation, wherein the wavelength of the ultraviolet light is 190-380nm, and the irradiation intensity is 5mW/cm2-5W/cm 2; and (5) after the reaction is finished, carrying out rotary evaporation for 10-120min to remove the solvent. Taking a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent, and further performing silica gel column chromatography to obtain a target product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate), wherein the obtained product is as follows:
the reaction product 4-azidothiophenol is generated by reacting 4-bromophenylthiol with NaN3 under certain conditions, wherein the specific reaction process comprises the steps of adding 0.2-40 parts of 4-bromophenylthiol and 0.2-40 parts of NaN3 into a 50-500mL flask, then adding 50-300mL of dimethyl sulfoxide, heating and stirring to dissolve the dimethyl sulfoxide, heating the mixture at about 50 ℃ for a certain time, removing the oil bath after the reaction is finished, washing the mixture with water for multiple times, extracting the mixture with Dichloromethane (DCM), collecting an organic phase of the mixture, drying the mixture with anhydrous sodium sulfate, performing silica gel column chromatography, and using petroleum ether as an eluent. To obtain 4-azidothiophenol, the structure of which is shown as follows:
step three, taking 1-bromo-4-ethynylbenzene as an example, introducing the 1-bromo-4-ethynylbenzene into the product through 1,3 dipolar addition click reaction
Dissolving 0.1-20 parts of prepared 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2-40 parts of 1-bromo-3-ethynylbenzene into a 50-500mL round-bottom flask by using 50-200mL tetrahydrofuran through stirring, adding 0.1-10 parts of GuBr, introducing argon, ultrasonically deoxidizing for 20-60min, adding 0.01-1 part of N, N-diisopropylethylamine under the condition of keeping out of the sun, putting the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd: YAG solid pulse laser, starting a microwave irradiation and reflux condensing device, keeping the reaction temperature through the microwave reactor, keeping the microwave frequency at 2350 ℃ and 2500MHz, and the microwave power at 400 ℃ and 1500W, the irradiation time is 0.5-12h, the system temperature is 80-110 ℃, and the reaction is protected from light. And 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 performing column chromatography with petroleum ether: ethyl acetate ═ 6:1 as eluent chromatography gave the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4- (4-bromophenyl) -1h-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate) having the following structure:
step four, preparation of p- (diXylamino) phenylacetylene
Dissolving 0.1-20 parts of iodoaniline and 0.2-40 parts of halogenated hydrocarbon 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 and ultrasonically deoxidizing for 10-60 minutes, putting the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, YAG solid pulse laser, starting microwave irradiation, wherein the microwave frequency is 2350-; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of the ultraviolet light is 340-380nm, the irradiation intensity is 5mW/cm2-5W/cm2, the temperature is 10-100 ℃, and the irradiation time is 0.5-12 h; after the reaction is finished, centrifuging at the speed of 5000-10000r/min for 1-10min to remove solids; and (3) performing rotary evaporation for 10-120min to remove the solvent, and then performing silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as an eluent to obtain a p- (diX-based) iodoaniline intermediate product.
Wherein the halogenated hydrocarbon may be different depending on the number n of alkyl carbon atoms. The halogenated hydrocarbon can be methyl iodide and methyl bromide when n is 1, and the obtained product is p- (dimethylamino) phenyl acetylene; when n is 4, the halogenated hydrocarbon can be bromobutane, and the obtained product is p- (dibutylamino) phenylacetylene; when n is 6, the halogenated hydrocarbon can be bromohexane, and the obtained product is p- (dihexylamino) phenylacetylene; when n is 16, the halogenated hydrocarbon may be 1-bromohexadecane, and the resulting product is p- (hexacosanylamino) phenylacetylene.
Dissolving 0.1-20 parts of the prepared intermediate product in 50-300mL of a 50-500mL flask containing a mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, then 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 ultrasonically deoxidizing for 10-60 min; then transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, YAG solid pulse laser, 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 ℃, a reflux condensing device is started in the microwave irradiation process, the microwave generator is closed to cool when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to heat when the temperature is lower than the set temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 350-370nm, the irradiation intensity is 5mW/cm2-5W/cm2, the temperature is 10-100 ℃, and the irradiation time is 0.1-6 h; then centrifuging at the speed of 5000-10000r/min for 1-10min to remove solids, carrying out rotary evaporation for 10-120min to remove the solvent, and then further purifying by silica gel column chromatography by using a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as an eluent to obtain yellow liquid N, N-diX-base-4- ((trimethylsilyl) ethynyl) aniline.
The following is a synthetic route of a target product p- (diXylamino) phenylacetylene:
dissolving 0.1-20 parts of the prepared product and 0.1-20 parts of potassium carbonate into a 50-500mL flask containing a mixed solution of 50-300mL of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 10-60 min; transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet, Nd and YAG solid pulse laser, 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 ℃, a reflux condensing device is started in the microwave irradiation process, the microwave generator is closed to cool when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to heat when the temperature is lower than the set temperature; when the microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of the ultraviolet light is 360-380nm, and the illumination intensity is 5mW/cm 2 -5W/cm 2 Irradiating at 10-100 deg.C for 0.1-5 hr; after the reaction is stopped, centrifuging at the speed of 5000-10000r/min for 1-10min to remove solids; and (4) performing rotary evaporation for 10-120min to remove the solvent, and performing dichloromethane column chromatography to obtain the p- (diXylamino) phenylacetylene.
Step five, introducing p- (diXylamino) phenylacetylene into anthraquinone derivative
Taking 0.1-20 parts of the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate prepared in the third step and 0.2-40 parts of the product p- (diXylamino) phenylacetylene (the ratio of the two is about 1:2) obtained in the fourth step, dissolving the product p- (diXylamino) phenylacetylene in a flask containing 50-300mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, and then adding 0.01-5 parts of bis (triphenylphosphine) palladium dichlorideAnd 0.01-5 parts of cuprous iodide, introducing argon and ultrasonically deoxidizing for 10-60 min; then transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, YAG solid pulse laser, 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 ℃, a reflux condensing device is started in the microwave irradiation process, when the temperature in the microwave reactor exceeds a set temperature, a microwave generator is closed to reduce the temperature, and when the temperature is lower than the set temperature, the microwave generator is opened to increase the temperature; when the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of the ultraviolet light is 350-380nm, and the illumination intensity is 5mW/cm 2 -5W/cm 2 Irradiating at 10-100 deg.C for 0.5-6 hr; after the reaction is finished, centrifuging at the speed of 5000-10000r/min for 1-10min to remove solids, performing rotary evaporation for 10-120min to remove solvents, and then performing further silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as an eluent to obtain the anthraquinone derivative, wherein the structural general formula is as follows:
step six, carrying out click chemical modification on anthraquinone derivative R1
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 at room temperature for 0.5-3 h; 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 time is 0.5-6 h. The system temperature is 20-100 ℃. When the microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of the ultraviolet light is 350-370nm, and the illumination intensity is 5mW/cm 2 -5W/cm 2 Irradiating for 0.5-12h at the temperature of 20-100 ℃. After the reaction is finished, rotary steaming is carried out for 10-120min, then eluting liquid is prepared by using petroleum ether and dichloromethane with the volume ratio of 1:1, and silica gel column purification is carried out. The obtained product is a target material, and the structural general formula of the product is as follows:
wherein the content of the first and second substances,
the click reagent is specifically any one of 7,7,8,8-Tetracyanoquinodimethane (7,7,8,8-Tetracyanoquinodimethane) abbreviated as TCNQ, Tetracyanoethylene (Tetracyanoethylene) abbreviated as TCNE, and 2,3,5,6-Tetrafluoro-7, 7',8,8' -Tetracyanoquinodimethane (2,3,5, 6-Tetracyanoquinodimethane) abbreviated as F4-TCNQ, and has a molecular formula as follows:
Example 1: r1 and R2 take benzene ring as an example, bromobutane is used as halogenated alkane, and TNCE is used as a click reagent in [2+2] click chemistry to prepare the broadband laser protective material.
Step one, dissolving 0.1 part of 2, 6-dihydroxyanthraquinone and 0.2 part of 4-vinylbenzoic acid (ratio is 1: 2-1: 4) in 50mL of anhydrous dichloromethane, putting the obtained solution into a 100mL flask, adding 0.2 part of Dicyclohexylcarbodiimide (DCC) and 0.01-part of 4-Dimethylaminopyridine (DMAP), stirring the obtained solution at room temperature for 24 hours, performing rotary evaporation for 30 minutes, performing silica gel column chromatography, wherein dichloromethane is used as eluent, and obtaining a sample of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4-vinylbenzoate) with the yield of 92%.
Step two, 0.1 part of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4-vinyl benzoic acid)Ester) and 0.2 part of 4-azidothiophenol were put in a 100mL reaction flask with 50mL of N-Dimethylformamide (DMF) as a solvent, and argon was introduced to remove oxygen by ultrasound for 30 min. Putting the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and 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 6h, and the system temperature is 40 ℃. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 (ii) a And (5) after the reaction is finished, carrying out rotary evaporation for 50min to remove the solvent. And (3) performing silica gel column chromatography by using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) in a volume ratio of 1:6 as an eluent to obtain a target product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) with the yield of 93%.
The reaction product 4-azidothiophenol is generated by reacting 4-bromophenylthiol with NaN3, wherein the specific reaction process comprises the steps of adding 0.2 part of 4-bromophenylthiol and 0.2 part of NaN3 into a 100mL flask, then adding 100mL of dimethyl sulfoxide, heating and stirring to dissolve the dimethyl sulfoxide, heating and reacting at 50 ℃ in an oil bath, removing the oil bath after the reaction is finished, washing for multiple times, extracting with Dichloromethane (DCM), collecting an organic phase, drying with anhydrous sodium sulfate, performing silica gel column chromatography, and using petroleum ether as an eluent to obtain the 4-azidothiophenol.
Step three, 0.1 part of the thus-obtained 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2 part of 1-bromo-3-ethynylbenzene were dissolved in a 100mL round-bottomed flask with stirring with 50mL of Tetrahydrofuran (THF), adding 0.1 part of GuBr, introducing argon, ultrasonically deoxidizing for 30min, adding 0.01 part of N, N-Diisopropylethylamine (DIPEA) under the condition of keeping out of the light, putting the flask into a reaction kettle with ultraviolet rays and Nd: in a normal-pressure reflux microwave reactor of YAG solid pulse laser, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept by a microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, and the reaction is protected from light. 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, and carrying out column chromatography with Petroleum Ether (PE): ethyl Acetate (EA) ═ 6:1 chromatography with eluent gave the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4- (4-bromophenyl) -1h-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate) in 90% yield.
Dissolving 0.1 part of 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 and 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 6 hours, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing the microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the preset temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 365nm, the irradiation intensity is 10mW/cm2, and the irradiation is carried out for 3 hours at the temperature of 80 ℃; then centrifuging at 8000r/min for 10min to remove solid; removing the solvent by rotary evaporation for 30min, and then further purifying the solvent by silica gel column chromatography by using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 as an eluent to obtain the p- (dibutyl) iodoaniline intermediate product with the yield of 89%.
Dissolving 0.1 part of the prepared intermediate product in 50mL of a 100mL flask containing a 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 ultrasonically deoxidizing for 30 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 Irradiating for 3h at the temperature of 80 ℃; then, the solid was removed by centrifugation at 8000r/min for 10min, the solvent was removed by rotary evaporation for 50min, and then the mixture of Dichloromethane (DCM) and Petroleum Ether (PE) at a volume ratio of 1:6 was used as eluent for further purification by silica gel column chromatography to obtain N, N-dibutyl-4- ((trimethylsilyl) ethynyl) aniline as a yellow liquid in 91% yield.
Dissolving 0.1 part of the prepared product and 0.1 part of potassium carbonate into a 100mL flask containing 50mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 30 min; transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet, Nd and YAG solid pulse laser, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to cool when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to heat when the temperature is lower than the set temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of the ultraviolet light is 3650nm, and the illumination intensity is 10mW/cm 2 Irradiating for 3h at the temperature of 80 ℃; after the reaction is stopped, centrifuging at the speed of 8000r/min for 10min to remove solids; and (3) removing the solvent by rotary evaporation for 30min, and carrying out column chromatography by using dichloromethane to obtain the p- (dibutylamino) phenylacetylene with the yield of 92%.
Step five, taking 0.1 part of the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate prepared in the step three and 0.2 part of the product p- (dibutylamino) phenylacetylene obtained in the step four to dissolve in a 100mL flask containing a mixed solution of 50mL of triethylamine and 1:1 in volume ratio, then adding 0.01 part of bis (triphenylphosphine) palladium dichloride and 0.01 part of cuprous iodide, introducing argon and ultrasonically deoxidizing for 30 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 365nm, the irradiation intensity is 10mW/cm2, the temperature is 60 ℃, and the irradiation is carried out for 3 hours; after the reaction is finished, centrifuging at 8000r/min for 10min to remove solid, performing rotary evaporation for 30min to remove solvent, and performing silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether at a volume ratio of 1:6 as eluent to obtain the anthraquinone derivative with a yield of 90%.
Sixthly, dissolving 0.1 part of the anthraquinone derivative prepared in the step five and 0.1 part of TNCE in 50mL of dichloromethane, and stirring at room temperature for 0.5 h; 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 h. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 1W/cm 2 . After the reaction is finished, rotary evaporation is carried out for 30min, then eluting liquid is prepared by using petroleum ether and dichloromethane in the volume ratio of 1:1, and silica gel column purification is carried out. The product was obtained as the final target material in 92% yield.
Example 2: r1 and R2 take benzene ring as an example, bromobutane is used as halogenated alkane, TNCQ is used as a click reagent in [2+2] click chemistry to manufacture a broadband laser protective material
Step one, dissolving 20 parts of 2, 6-dihydroxyanthraquinone and 40 parts of 4-vinylbenzoic acid (proportion is 1: 2-1: 4) in 300mL of anhydrous dichloromethane, putting the obtained solution into a 500mL flask, adding 0.2 part of Dicyclohexylcarbodiimide (DCC) and 0.01-part of 4-Dimethylaminopyridine (DMAP), stirring the obtained solution at room temperature for 24 hours, performing rotary evaporation for 30 minutes, performing silica gel column chromatography, wherein dichloromethane is used as eluent to obtain a sample 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4-vinylbenzoate), and the yield is 91%.
And step two, taking 20 parts of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4-vinyl benzoate) and 40 parts of 4-azido thiophenol, and putting the mixture into a 500mL reaction flask by taking 300mL of N-Dimethylformamide (DMF) as a solvent, and filling argon to perform ultrasonic deoxygenation for 50 min. Putting the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, starting a microwave irradiation and reflux condensing device, and passing through a microwave irradiation and reflux condensing deviceThe reactor keeps the reaction temperature, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, and the system temperature is 40 ℃. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 (ii) a And (5) after the reaction is finished, carrying out rotary evaporation for 50min to remove the solvent. And (3) performing silica gel column chromatography by using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) in a volume ratio of 1:6 as an eluent to obtain a target product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) with a yield of 90%.
The reactant 4-azidothiophenol is generated by reacting 4-bromophenylthiol with NaN3, wherein the specific reaction process comprises the steps of adding 30 parts of 4-bromophenylthiol and 40 parts of NaN3 into a 50mL flask, then adding 50mL of dimethyl sulfoxide, heating and stirring to dissolve the 4-azidothiophenol, heating and reacting at 50 ℃ in an oil bath, removing the oil bath after the reaction is finished, washing for multiple times, extracting with Dichloromethane (DCM), collecting an organic phase, drying with anhydrous sodium sulfate, performing silica gel column chromatography, and obtaining the 4-azidothiophenol by using petroleum ether as an eluent.
Step three, 20 parts of the prepared 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 40 parts of 1-bromo-3-ethynylbenzene were dissolved in a 500mL round-bottom flask with stirring using 300mL Tetrahydrofuran (THF), adding 10 parts of GuBr, introducing argon, ultrasonically deoxidizing for 30min, adding 1 part of N, N-Diisopropylethylamine (DIPEA) under the condition of keeping out of the light, and putting the flask into a reaction kettle with ultraviolet rays and Nd: in a normal-pressure reflux microwave reactor of YAG solid pulse laser, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept by a microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, the system temperature is 80 ℃, and the reaction is protected from light. 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, and carrying out column chromatography with Petroleum Ether (PE): ethyl Acetate (EA) ═ 6:1 chromatography with eluent gave the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4- (4-bromophenyl) -1h-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate) in 92% yield.
Dissolving 20 parts of p-iodoaniline and 40 parts of bromobutane in a 500mL flask filled with 300mLN, N-Dimethylformamide (DMF), adding 20 parts of potassium carbonate and 20 parts of potassium iodide, introducing argon and ultrasonically deoxidizing for 40 minutes, putting the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, namely YAG solid pulse laser, 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 reduce the temperature when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to increase the temperature when the temperature in the microwave reactor is lower than the preset temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 Irradiating for 6h at 80 ℃; then centrifuging at 8000r/min for 10min to remove solid; removing the solvent by rotary evaporation for 60min, and then further purifying the solvent by silica gel column chromatography by using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 as an eluent to obtain the p- (dibutyl) iodoaniline intermediate product with the yield of 90%.
Dissolving 20 parts of the prepared intermediate product in a 500mL flask containing a mixed solution of 300mL 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 ultrasonically deoxidizing for 30 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 Irradiating for 6h at 80 ℃; centrifuging at 8000r/min for 10min to remove solid, rotary evaporating for 60min to remove solvent, and purifying by silica gel column chromatography with mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) at volume ratio of 1:6 as eluent to obtain yellow liquid N, N-dibutyl-4- ((trimethyl-trimethyl)Silyl) ethynyl) aniline, yield 90%.
Dissolving 20 parts of the prepared product and 20 parts of potassium carbonate into a 500mL flask containing a mixed solution of 300mL of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 30 min; transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet, Nd and YAG solid pulse laser, 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, a microwave generator is closed to cool when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to heat when the temperature is lower than the set temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 3650nm, the irradiation intensity is 10mW/cm2, the temperature is 80 ℃, and the irradiation is carried out for 6 hours; after the reaction is stopped, centrifuging at the speed of 8000r/min for 10min to remove solids; the solvent was removed by rotary evaporation for 60min, and column chromatography was performed with dichloromethane to give p- (dibutylamino) phenylacetylene in 93% yield.
Step five, taking 20 parts of the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate prepared in the step three and 40 parts of the product p- (dibutylamino) phenylacetylene obtained in the step four to dissolve in a 500mL flask containing a mixed solution of 300mL of triethylamine and 1:1 in volume ratio, then adding 5 parts of bis-triphenylphosphine palladium dichloride and 5 parts of cuprous iodide, introducing argon and ultrasonically deoxidizing for 30 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 Irradiating for 6h at the temperature of 60 ℃; after the reaction is finished, centrifuging at 8000r/min for 10min to remove solid, rotary evaporating for 60min to remove solvent, and then removing solvent by twoThe mixed solution of chloromethane and petroleum ether with the volume ratio of 1:6 is used as eluent to be further purified by silica gel column chromatography to obtain anthraquinone derivatives with the yield of 92 percent.
Step six, dissolving 20 parts of the anthraquinone derivative prepared in the step five and 20 parts of TNCQ in 50mL of dichloromethane, and stirring at room temperature for 1 h; 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 h. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of the ultraviolet light is 365nm, and the irradiation intensity is 1W/cm 2. After the reaction is finished, rotary evaporation is carried out for 60min, then eluting liquid is prepared by using petroleum ether and dichloromethane in the volume ratio of 1:1, and silica gel column purification is carried out. The product was obtained as the final target material in 93% yield.
Example 3: r1 and R2 take benzene ring as an example, bromine hexane is used as halogenated alkane, F4-TNCQ is used as a click reagent in [2+2] click chemistry to prepare a broadband laser protective material
Step one, dissolving 0.1 part of 2, 6-dihydroxyanthraquinone and 0.2 part of 4-vinylbenzoic acid (ratio is 1: 2-1: 4) in 50mL of anhydrous dichloromethane, putting the anhydrous dichloromethane into a 100mL flask, adding 0.2 part of Dicyclohexylcarbodiimide (DCC) and 0.01-part of 4-Dimethylaminopyridine (DMAP), stirring at room temperature for 24h, performing rotary evaporation for 30min, performing silica gel column chromatography, wherein dichloromethane is used as eluent, and obtaining a sample 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4-vinylbenzoate) with a yield of 92%.
And step two, taking 0.1 part of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4-vinyl benzoate) and 0.2 part of 4-azido thiophenol, putting the mixture into a 100mL reaction flask by taking 50mLN, N-Dimethylformamide (DMF) as a solvent, and filling argon to perform ultrasonic deoxygenation for 30 min. Putting the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and 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 6h, and the system temperature is 40 ℃. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 (ii) a And (4) after the reaction is finished, carrying out rotary evaporation for 50min to remove the solvent. With Dichloromethane (DC)M) and Petroleum Ether (PE) in a volume ratio of 1:6 are used as eluent to be further subjected to silica gel column chromatography to obtain a target product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) with a yield of 92%.
The reactant 4-azidothiophenol is generated by reacting 4-bromophenylthiol with NaN3, the specific reaction process comprises the steps of adding 40 parts of 4-bromophenylthiol and 40 parts of NaN3 into a 500mL flask, then adding 300mL of dimethyl sulfoxide, heating and stirring to dissolve the 4-azidothiophenol, heating and reacting at 50 ℃ in an oil bath, removing the oil bath after the reaction is finished, washing for multiple times, extracting with Dichloromethane (DCM), collecting an organic phase, drying with anhydrous sodium sulfate, performing silica gel column chromatography, and using petroleum ether as an eluent to obtain the 4-azidothiophenol.
Step three, 0.1 part of the thus-obtained 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2 part of 1-bromo-3-ethynylbenzene were dissolved in a 100mL round-bottomed flask with stirring with 50mL of Tetrahydrofuran (THF), adding 0.1 part of GuBr, introducing argon, ultrasonically deoxidizing for 30min, adding 0.01 part of N, N-Diisopropylethylamine (DIPEA) under the condition of keeping out of the light, putting the flask into a reaction kettle with ultraviolet rays and Nd: in a normal-pressure reflux microwave reactor of YAG solid pulse laser, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept by a microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, and the reaction is protected from light. 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, and carrying out column chromatography with Petroleum Ether (PE): ethyl Acetate (EA) ═ 6:1 chromatography with eluent gave the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4- (4-bromophenyl) -1h-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate) in 90% yield.
Step four, dissolving 0.1 part of 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 and ultrasonically deoxidizing for 30 minutes, placing the flask in a microwave reactor with ultraviolet and Nd: YAG solid pulse laser and normal pressure and backflow, starting microwavesIrradiating, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in a microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 Irradiating for 3h at 80 ℃; then centrifuging at 8000r/min for 10min to remove solid; removing the solvent by rotary evaporation for 30min, and then further purifying the solvent by silica gel column chromatography by using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 as an eluent to obtain a p- (dihexyl) iodoaniline intermediate product with the yield of 91%.
Dissolving 0.1 part of the prepared intermediate product in 50mL of a 100mL flask containing a 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 ultrasonically deoxidizing for 30 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 Irradiating for 3h at the temperature of 80 ℃; then, the solid was removed by centrifugation at 8000r/min for 10min, the solvent was removed by rotary evaporation for 50min, and then the mixture of Dichloromethane (DCM) and Petroleum Ether (PE) at a volume ratio of 1:6 was used as eluent for further purification by silica gel column chromatography to obtain N, N-dihexyl-4- ((trimethylsilyl) ethynyl) aniline as a yellow liquid in 92% yield.
Dissolving 0.1 part of the prepared product and 0.1 part of potassium carbonate into a 100mL flask containing a mixed solution of 50mL of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 30 min; transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet, Nd and YAG solid pulse laser, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to cool when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to heat when the temperature is lower than the set temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 3650nm, the irradiation intensity is 10mW/cm2, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; after the reaction is stopped, centrifuging at the speed of 8000r/min for 10min to remove solids; the solvent is removed by rotary evaporation for 30min, and the column chromatography is carried out by dichloromethane to obtain the p- (dihexylamino) phenylacetylene with the yield of 92 percent.
Step five, taking 0.1 part of the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate prepared in the step three and 0.2 part of the product p- (dihexylamino) phenylacetylene obtained in the step three to be dissolved in a 100mL flask containing a mixed solution of 50mL of triethylamine and 1:1 in volume ratio, then adding 0.01 part of bis (triphenylphosphine) palladium dichloride and 0.01 part of cuprous iodide, introducing argon and ultrasonically deoxidizing for 30 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm2, the temperature is 60 ℃, and the irradiation is performed for 3 hours; after the reaction is finished, centrifuging at 8000r/min for 10min to remove solid, performing rotary evaporation for 30min to remove solvent, and performing silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether at a volume ratio of 1:6 as eluent to obtain the anthraquinone derivative with a yield of 91%.
Step six, dissolving 0.1 part of the anthraquinone derivative prepared in the step five and 0.1 part of F4-TNCQ in 50mL of dichloromethane, and stirring at room temperature for 0.5 h; 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 h. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of the ultraviolet light is 365nm, and the irradiation intensity is 1W/cm 2. After the reaction is finished, rotary evaporation is carried out for 30min, then eluting liquid is prepared by using petroleum ether and dichloromethane in the volume ratio of 1:1, and silica gel column purification is carried out. The product was obtained as the final target material in 92% yield.
Example 4: r1 and R2 take pyridine as an example, bromohexane is used as halogenated alkane, TNCE is used as a click reagent in [2+2] click chemistry to prepare a broadband laser protective material
Step one, dissolving 0.1 part of 2, 6-dihydroxyanthraquinone and 0.2 part of 4-vinylbenzoic acid (ratio is 1: 2-1: 4) in 50mL of anhydrous dichloromethane, putting the obtained solution into a 100mL flask, adding 0.2 part of Dicyclohexylcarbodiimide (DCC) and 0.01-part of 4-Dimethylaminopyridine (DMAP), stirring the obtained solution at room temperature for 24 hours, performing rotary evaporation for 30 minutes, performing silica gel column chromatography, wherein dichloromethane is used as eluent, and obtaining a sample of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4-vinylbenzoate) with the yield of 92%.
And step two, taking 0.1 part of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4-vinyl benzoate) and 0.2 part of 6-azidopyridine-3-thiol, putting the mixture into a 100mL reaction flask by taking 50mLN, N-Dimethylformamide (DMF) as a solvent, and filling argon to carry out ultrasonic deoxygenation for 30 min. Putting the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and 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 6h, and the system temperature is 40 ℃. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, wherein the wavelength of the ultraviolet light is 365nm, and the irradiation intensity is 10mW/cm 2; and (5) after the reaction is finished, carrying out rotary evaporation for 50min to remove the solvent. And (3) performing silica gel column chromatography by using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) in a volume ratio of 1:6 as an eluent to obtain the target product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((6-azidopyridin-3-yl) thio) ethyl) benzoate) with a yield of 91%.
The reactant 4-azidothiophenol is generated by reacting 4-bromophenylthiol with NaN3, wherein the specific reaction process comprises the steps of adding 20 parts of 4-bromophenylthiol and 30 parts of NaN3 into a 250mL flask, then adding 250mL of dimethyl sulfoxide, heating and stirring to dissolve the 4-azidothiophenol, heating and reacting at 50 ℃ in an oil bath, removing the oil bath after the reaction is finished, washing for multiple times, extracting with Dichloromethane (DCM), collecting an organic phase, drying with anhydrous sodium sulfate, performing silica gel column chromatography, and obtaining the 4-azidothiophenol by using petroleum ether as an eluent.
Step three, 0.1 part of the thus-obtained 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2 part of 5-bromo-2-ethynylpyridine are dissolved in a 100mL round-bottomed flask with stirring with 50mL Tetrahydrofuran (THF), adding 0.1 part of GuBr, introducing argon, ultrasonically deoxidizing for 30min, adding 0.01 part of N, N-Diisopropylethylamine (DIPEA) under the condition of keeping out of the light, putting the flask into a reaction kettle with ultraviolet rays and Nd: in a normal-pressure reflux microwave reactor of YAG solid pulse laser, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept by a microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6h, the system temperature is 80 ℃, and the reaction is protected from light. 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, and carrying out column chromatography with Petroleum Ether (PE): ethyl Acetate (EA) ═ 6:1 chromatography with eluent gave 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-dihydroanthracen-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 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 and ultrasonically deoxidizing for 30 minutes, putting the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, YAG solid pulse laser, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 6 hours, the system temperature is 80 ℃, starting a reflux condensing device in the microwave irradiation process, closing the microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to increase the temperature when the temperature is lower than the preset temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 365nm, the illumination intensity is 10mW/cm2, and the irradiation is carried out for 3 hours at the temperature of 80 ℃; then centrifuging at 8000r/min for 10min to remove solid; removing the solvent by rotary evaporation for 30min, and then further purifying the solvent by silica gel column chromatography by using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 as an eluent to obtain a p- (dihexyl) iodoaniline intermediate product with the yield of 91%.
Dissolving 0.1 part of the prepared intermediate product in 50mL of a 100mL flask containing a 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 ultrasonically deoxidizing for 30 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 365nm, the irradiation intensity is 10mW/cm2, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; then, the solid was removed by centrifugation at 8000r/min for 10min, the solvent was removed by rotary evaporation for 50min, and then the mixture of Dichloromethane (DCM) and Petroleum Ether (PE) at a volume ratio of 1:6 was used as eluent for further purification by silica gel column chromatography to obtain N, N-dihexyl-4- ((trimethylsilyl) ethynyl) aniline as a yellow liquid in 92% yield.
Dissolving 0.1 part of the prepared product and 0.1 part of potassium carbonate into a 100mL flask containing a mixed solution of 50mL of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 30 min; transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 3650nm, the irradiation intensity is 10mW/cm2, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; after the reaction is stopped, centrifuging at the speed of 8000r/min for 10min to remove solids; the solvent is removed by rotary evaporation for 30min, and the column chromatography is carried out by dichloromethane to obtain the p- (dihexylamino) phenylacetylene with the yield of 92 percent.
Step five, taking 0.1 part of the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate prepared in the step three and 0.2 part of the product p- (dihexylamino) phenylacetylene obtained in the step four to dissolve in a 100mL flask containing a mixed solution of 50mL of triethylamine and tetrahydrofuran in a volume ratio of 1:1, then adding 0.01 part of bis (triphenylphosphine) palladium dichloride and 0.01 part of cuprous iodide, introducing argon and ultrasonically deoxidizing for 30 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 365nm, the irradiation intensity is 10mW/cm2, the temperature is 60 ℃, and the irradiation is carried out for 3 hours; after the reaction is finished, centrifuging at 8000r/min for 10min to remove solid, performing rotary evaporation for 30min to remove solvent, and performing silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether at a volume ratio of 1:6 as eluent to obtain the anthraquinone derivative with a yield of 91%.
Step six, dissolving 0.1 part of the anthraquinone derivative prepared in the step five and 0.1 part of F4-TNCQ in 50mL of dichloromethane, and stirring at room temperature for 0.5 h; 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 h. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of the ultraviolet light is 365nm, and the irradiation intensity is 1W/cm 2. After the reaction is finished, carrying out rotary evaporation for 30min, preparing eluent by using petroleum ether and dichloromethane in a volume ratio of 1:1, and purifying by using a silica gel column. The product was obtained as the final target material in 92% yield.
TABLE 1 laser transmittance for each band when the product was injected into a 50 μm cell by injection
TABLE 2 thermal decomposition temperatures of the products of the examples
Example 5: r1 and R2 take pyridine as an example, bromohexane is used as halogenated alkane, TNCE is used as a click reagent in [2+2] click chemistry to prepare a broadband laser protective material
Step one, dissolving 0.1 part of 2, 6-dihydroxyanthraquinone and 0.4 part of 4-vinylbenzoic acid (ratio is 1: 2-1: 4) in 100mL of anhydrous dichloromethane, putting the obtained solution into a 100mL flask, adding 0.6 part of Dicyclohexylcarbodiimide (DCC) and 0.5-part of 4-Dimethylaminopyridine (DMAP), stirring at room temperature for 23h, performing rotary evaporation for 10min, and performing silica gel column chromatography, wherein dichloromethane is used as eluent, so as to obtain a sample 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4-vinylbenzoate) with the yield of 92%.
And step two, taking 0.5 part of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4-vinyl benzoate) and 0.5 part of 6-azidopyridine-3-thiol, putting the mixture into a 100mL reaction flask by taking 100mLN, N-Dimethylformamide (DMF) as a solvent, and filling argon to carry out ultrasonic deoxygenation for 20 min. Putting the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and 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 0.5h, and the system temperature is 100 ℃. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 (ii) a And (5) after the reaction is finished, carrying out rotary evaporation for 50min to remove the solvent. And (3) performing silica gel column chromatography by using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) in a volume ratio of 1:6 as an eluent to obtain a target product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((6-azidopyridin-3-yl) thio) ethyl) benzoate) with a yield of 91%.
The reactant 4-azidothiophenol is generated by reacting 4-bromophenylthiol with NaN3, the specific reaction process comprises the steps of adding 20 parts of 4-bromophenylthiol and 30 parts of NaN3 into a 250mL flask, then adding 250mL of dimethyl sulfoxide, heating and stirring to dissolve the 4-bromophenylthiol, heating and reacting at 50 ℃ in an oil bath, removing the oil bath after the reaction is finished, washing for multiple times, extracting with Dichloromethane (DCM), collecting an organic phase, drying with anhydrous sodium sulfate, performing silica gel column chromatography, and using petroleum ether as an eluent to obtain the 4-azidothiophenol.
Step three, dissolving 10 parts of the prepared 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 20 parts of 5-bromo-2-ethynylpyridine in a 50mL round-bottom flask with stirring using 50mL Tetrahydrofuran (THF), adding 5 parts of GuBr, introducing argon, ultrasonically deoxidizing for 20min, adding 0.05 part of N, N-Diisopropylethylamine (DIPEA) under the condition of keeping out of the light, putting the flask into a reaction kettle with ultraviolet rays and Nd: in a normal-pressure reflux microwave reactor of YAG solid pulse laser, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept by a microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 0.5h, the system temperature is 110 ℃, and the reaction is protected from light. After the reaction is finished, adding 5ml 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, and carrying out column chromatography with Petroleum Ether (PE): ethyl Acetate (EA) ═ 6:1 chromatography with eluent gave 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-dihydroanthracen-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 10 parts of p-iodoaniline and 20 parts of bromohexane in a 200mL flask filled with 150mLN, N-Dimethylformamide (DMF), adding 10 parts of potassium carbonate and 10 parts of potassium iodide, introducing argon and ultrasonically deoxidizing for 60 minutes, putting the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, namely YAG solid pulse laser, 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 reduce the temperature when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to increase the temperature when the temperature in the microwave reactor is lower than the preset temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 365nm, the irradiation intensity is 10mW/cm2, and the irradiation is carried out for 12 hours at the temperature of 80 ℃; then centrifuging at 8000r/min for 10min to remove solid; removing the solvent by rotary evaporation for 30min, and then further purifying the solvent by silica gel column chromatography by using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 as an eluent to obtain a p- (dihexyl) iodoaniline intermediate product with the yield of 91%.
Dissolving 10 parts of the prepared intermediate product in a 200mL flask containing 150mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 10 parts of trimethylsilyl acetylene, 0.5-part of bis (triphenylphosphine) palladium dichloride and 5 parts of cuprous iodide, introducing argon and ultrasonically deoxidizing for 60 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 365nm, the irradiation intensity is 10mW/cm2, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; then, the solid was removed by centrifugation at 8000r/min for 10min, the solvent was removed by rotary evaporation for 50min, and then the mixture of Dichloromethane (DCM) and Petroleum Ether (PE) at a volume ratio of 1:6 was used as eluent for further purification by silica gel column chromatography to obtain N, N-dihexyl-4- ((trimethylsilyl) ethynyl) aniline as a yellow liquid in 92% yield.
Dissolving 10 parts of the prepared product and 10 parts of potassium carbonate into a 200mL flask containing 100mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 60 min; transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet, Nd and YAG solid pulse laser, 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 3650nm, the irradiation intensity is 10mW/cm2, the temperature is 80 ℃, and the irradiation is carried out for 5 hours; after the reaction is stopped, centrifuging at the speed of 8000r/min for 10min to remove solids; the solvent is removed by rotary evaporation for 30min, and the column chromatography is carried out by dichloromethane to obtain the p- (dihexylamino) phenylacetylene with the yield of 92 percent.
Step five, taking 10 parts of the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate prepared in the step three and 20 parts of the product p- (dihexylamino) phenylacetylene obtained in the step four to dissolve in a 100mL flask containing a mixed solution of 150mL of triethylamine and tetrahydrofuran in a volume ratio of 1:1, then adding 0.5 part of bis (triphenylphosphine) palladium dichloride and 0.5 part of cuprous iodide, introducing argon and ultrasonically deoxidizing for 60 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature is lower than the set temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 365nm, the irradiation intensity is 10mW/cm2, the temperature is 60 ℃, and the irradiation is carried out for 3 hours; after the reaction is finished, centrifuging at 8000r/min for 10min to remove solid, performing rotary evaporation for 30min to remove solvent, and performing silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether at a volume ratio of 1:6 as eluent to obtain the anthraquinone derivative with a yield of 91%.
Step six, dissolving 10 parts of the anthraquinone derivative prepared in the step five and 20 parts of F4-TNCQ in 50mL of dichloromethane, and stirring at room temperature for 3 hours; 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 is carried out for 0.5 h. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 1W/cm 2 . After the reaction is finished, performing rotary evaporation for 120min, preparing eluent by using petroleum ether and dichloromethane in a volume ratio of 1:1, and purifying by using a silica gel column. The product was obtained as the final target material in 92% yield.
Example 6: r1 and R2 take pyridine as an example, bromohexane is used as halogenated alkane, TNCE is used as a click reagent in [2+2] click chemistry to prepare a broadband laser protective material
Step one, dissolving 10 parts of 2, 6-dihydroxyanthraquinone and 20 parts of 4-vinylbenzoic acid (proportion is 1: 2-1: 4) in 100mL of anhydrous dichloromethane, putting the obtained solution into a 100mL flask, adding 40 parts of Dicyclohexylcarbodiimide (DCC) and 5 parts of 4-Dimethylaminopyridine (DMAP), stirring the obtained solution at room temperature for 26 hours, performing rotary evaporation for 60 minutes, performing silica gel column chromatography, wherein dichloromethane is used as eluent, and obtaining a sample of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4-vinyl benzoate) with the yield of 92%.
And step two, putting 0.5 part of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4-vinyl benzoate) and 0.5 part of 6-azidopyridine-3-thiol into a 100mL reaction flask by taking 100mLN, N-Dimethylformamide (DMF) as a solvent, and filling argon for ultrasonic deoxygenation for 60 min. Putting the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and 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 20 ℃. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 10mW/cm 2 (ii) a And (5) after the reaction is finished, carrying out rotary evaporation for 50min to remove the solvent. Taking a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 as an eluent, and further performing silica gel column chromatography to obtain a target product9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((6-azidopyridin-3-yl) thio) ethyl) benzoate) yield 91%.
The reactant 4-azidothiophenol is generated by reacting 4-bromophenylthiol with NaN3, wherein the specific reaction process comprises the steps of adding 20 parts of 4-bromophenylthiol and 30 parts of NaN3 into a 250mL flask, then adding 250mL of dimethyl sulfoxide, heating and stirring to dissolve the 4-azidothiophenol, heating and reacting at 50 ℃ in an oil bath, removing the oil bath after the reaction is finished, washing for multiple times, extracting with Dichloromethane (DCM), collecting an organic phase, drying with anhydrous sodium sulfate, performing silica gel column chromatography, and obtaining the 4-azidothiophenol by using petroleum ether as an eluent.
Step three, dissolving 10 parts of the prepared 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 20 parts of 5-bromo-2-ethynylpyridine in a 50mL round-bottom flask with stirring using 50mL Tetrahydrofuran (THF), adding 5 parts of GuBr, introducing argon, ultrasonically deoxidizing for 60min, adding 0.05 part of N, N-Diisopropylethylamine (DIPEA) under the condition of keeping out of the light, putting the flask into a reaction kettle with ultraviolet rays and Nd: in a normal-pressure reflux microwave reactor of YAG solid pulse laser, a microwave irradiation and reflux condensing device is started, the reaction temperature is kept by a microwave reactor, the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 8h, the system temperature is 90 ℃, and the reaction is protected from light. After the reaction is finished, adding 5ml 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, and carrying out column chromatography with Petroleum Ether (PE): ethyl Acetate (EA) ═ 6:1 chromatography with eluent gave 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-dihydroanthracen-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 10 parts of p-iodoaniline and 10 parts of bromohexane in a 300mL flask filled with 100mLN, N-Dimethylformamide (DMF), adding 10 parts of potassium carbonate and 10 parts of potassium iodide, introducing argon and ultrasonically deoxidizing for 10 minutes, putting the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, namely YAG solid pulse laser, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, the system temperature is 00 ℃, starting a reflux condensing device in the microwave irradiation process, closing a microwave generator to reduce the temperature when the temperature in the microwave reactor exceeds a preset temperature, and opening the microwave generator to increase the temperature when the temperature in the microwave reactor is lower than the preset temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 365nm, the irradiation intensity is 10mW/cm2, and the irradiation is carried out for 12 hours at the temperature of 80 ℃; then centrifuging at 8000r/min for 10min to remove solid; removing the solvent by rotary evaporation for 30min, and then further purifying the solvent by silica gel column chromatography by using a mixed solution of Dichloromethane (DCM) and Petroleum Ether (PE) with the volume ratio of 1:6 as an eluent to obtain a p- (dihexyl) iodoaniline intermediate product with the yield of 91%.
Dissolving 10 parts of the prepared intermediate product in 50mL of a 100mL flask containing a mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 10 parts of trimethylsilyl acetylene, 0.5-part of bis (triphenylphosphine) palladium dichloride and 5 parts of cuprous iodide, introducing argon and ultrasonically deoxidizing for 10 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, wherein the wavelength of ultraviolet light is 365nm, the irradiation intensity is 10mW/cm2, the temperature is 80 ℃, and the irradiation is carried out for 3 hours; then, the solid was removed by centrifugation at 8000r/min for 10min, the solvent was removed by rotary evaporation for 50min, and then the mixture of Dichloromethane (DCM) and Petroleum Ether (PE) at a volume ratio of 1:6 was used as eluent for further purification by silica gel column chromatography to obtain N, N-dihexyl-4- ((trimethylsilyl) ethynyl) aniline as a yellow liquid in 92% yield.
Dissolving 10 parts of the prepared product and 10 parts of potassium carbonate into a 200mL flask containing 100mL of mixed solution of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 10 min; transferring the flask into a normal-pressure reflux microwave reactor with ultraviolet, Nd and YAG solid pulse laser, starting microwave irradiation, wherein the microwave frequency is 2450MHz, the microwave power is 900W, the irradiation time is 12h, the system temperature is 10 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to cool when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to heat when the temperature is lower than the set temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 3650nm, the irradiation intensity is 10mW/cm2, the temperature is 80 ℃, and the irradiation is carried out for 0.1 h; after the reaction is stopped, centrifuging at the speed of 8000r/min for 10min to remove solids; the solvent is removed by rotary evaporation for 30min, and the column chromatography is carried out by dichloromethane to obtain the p- (dihexylamino) phenylacetylene with the yield of 92 percent.
Step five, taking 10 parts of the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate prepared in the step three and 20 parts of the product p- (dihexylamino) phenylacetylene obtained in the step four to dissolve in a 100mL flask containing a mixed solution of 150mL of triethylamine and tetrahydrofuran in a volume ratio of 1:1, then adding 0.5 part of bis (triphenylphosphine) palladium dichloride and 0.5 part of cuprous iodide, introducing argon and ultrasonically deoxidizing for 10 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and 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 ℃, a reflux condensing device is started in the microwave irradiation process, a microwave generator is closed to reduce the temperature when the temperature in the microwave reactor exceeds a set temperature, and the microwave generator is opened to increase the temperature when the temperature in the microwave reactor is lower than the set temperature; when microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of ultraviolet light is 365nm, the irradiation intensity is 10mW/cm2, the temperature is 60 ℃, and the irradiation is carried out for 0.5 h; after the reaction is finished, centrifuging at 8000r/min for 10min to remove solid, performing rotary evaporation for 30min to remove solvent, and performing silica gel column chromatography purification by using a mixed solution of dichloromethane and petroleum ether at a volume ratio of 1:6 as eluent to obtain the anthraquinone derivative with a yield of 91%.
Step six, dissolving 0.1 part of the anthraquinone derivative prepared in the step five and 0.2 part of F4-TNCQ in 50mL of dichloromethane, and stirring at room temperature for 3 hours; by means of microwave radiationCarrying out chemical reaction, wherein the microwave frequency is 2450MHz, the microwave power is 1200W, the system temperature is 120 ℃, and the irradiation is carried out for 6 h. When microwave irradiation is started, ultraviolet irradiation and laser irradiation are used, the wavelength of the ultraviolet light is 365nm, and the illumination intensity is 1W/cm 2 . After the reaction is finished, rotary evaporation is carried out for 120min, then eluting liquid is prepared by using petroleum ether and dichloromethane in the volume ratio of 1:1, and silica gel column purification is carried out. The product was obtained as the final target material in 92% yield.
Claims (7)
1. A broadband liquid crystal laser protective material prepared by multi-click chemistry 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 comprises the following steps:
step one, esterification reaction of 2, 6-dihydroxy anthraquinone and 4-vinyl benzoic acid
Dissolving 0.1-20 parts of 2, 6-dihydroxyanthraquinone and 0.2-40 parts of 4-vinylbenzoic acid in 50-300mL of anhydrous dichloromethane according to the mass part ratio 1 (2-4), putting the mixture into a flask, adding 0.2-40 parts of dicyclohexylcarbodiimide and 0.01-5 parts of 4-dimethylaminopyridine into the flask, stirring the mixture at room temperature for 23-26h, performing rotary evaporation for 10-60min, and performing silica gel column chromatography, wherein dichloromethane is used as eluent to obtain a sample 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4-vinylbenzoate);
step two, introducing 4-azido thiophenol into the product in the step one through a sulfydryl double bond click reaction
Taking 0.1-20 parts of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4-vinyl benzoate) and 0.2-40 parts of 4-azido thiophenol, putting the mixture into a reaction flask by taking 50-300mL of N, N-dimethylformamide as a solvent, and filling argon for ultrasonic deoxidization for 20-60 min; placing the flask into a normal-pressure reflux microwave reactor with ultraviolet, Nd and YAG solid pulse laser, maintaining the system temperature at 20-100 ℃ and irradiating for 0.5-12h, and simultaneously using ultraviolet irradiation and laser irradiation when starting the microwave irradiation; removing the solvent by rotary evaporation after the reaction is finished; taking a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent, and further performing silica gel column chromatography to obtain a target product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate);
step three, introducing 1-bromo-4-ethynylbenzene into a product in step two through 1,3 dipolar addition click reaction
Stirring and dissolving 0.1-20 parts of 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4-azidophenyl) thio) ethyl) benzoate) and 0.2-40 parts of 1-bromo-3-ethynylbenzene in a 50-500mL round-bottom flask, adding 0.1-10 parts of GuBr, introducing argon, ultrasonically deoxidizing for 20-60min, adding 0.01-1 part of N, N-diisopropylethylamine under the dark condition, putting the flask into a microwave reactor with ultraviolet and Nd, YAG solid pulse laser and normal pressure backflow, starting a microwave irradiation and backflow condensing device, keeping the temperature of the system by the microwave reactor at 80-110 ℃ for 0.5-12h, after the reaction is finished, adding 2-10mL of strong ammonia water to remove copper ions in the system, extracting with dichloromethane, washing with water, drying, filtering, concentrating, and performing column chromatography to obtain 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diylbis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate);
step four, preparation of p- (diXylamino) phenylacetylene
Dissolving 0.1-20 parts of p-iodoaniline and 0.2-40 parts of halogenated hydrocarbon into 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, ultrasonically deoxidizing for 10-60 minutes, putting the flask into a normal-pressure reflux microwave reactor with ultraviolet and Nd, YAG (yttrium aluminum garnet) solid pulse laser to ensure that the system temperature is 20-100 ℃, and irradiating for 0.5-12 hours; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.5-12 h; centrifuging to remove solids after the reaction is finished; removing the solvent by rotary evaporation, and then further purifying the mixture by silica gel column chromatography by using a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:6 as an eluent to obtain a p- (diX group) iodoaniline intermediate product;
dissolving 0.1-20 parts of the prepared intermediate product p- (diX group) iodoaniline in 50-300mL of a 50-500mL flask containing a mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, then 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 ultrasonically deoxidizing for 10-60 min; then transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, starting microwave irradiation for 0.5-12h, and keeping the temperature of the system at 10-100 ℃; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.1-6 h; then centrifuging to remove solids, removing the solvent by rotary evaporation, and then further purifying by silica gel column chromatography by using a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:6 as an eluent to obtain yellow liquid N, N-diX-4- ((trimethylsilyl) ethynyl) aniline;
dissolving 0.1-20 parts of prepared N, N-diX-based-4- ((trimethylsilyl) ethynyl) aniline and 0.1-20 parts of potassium carbonate into a 50-500mL flask containing a mixed solution of 50-300mL of tetrahydrofuran and absolute ethyl alcohol in a volume ratio of 7:3, introducing argon and ultrasonically deoxidizing for 10-60 min; transferring the flask into a normal-pressure microwave reactor with ultraviolet, Nd and YAG solid pulse laser and reflux, starting microwave irradiation for 0.5-12h, and keeping the system temperature at 10-100 ℃; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are simultaneously used for 0.1-5 h; after the reaction is stopped, centrifuging to remove solids; removing the solvent by rotary evaporation to obtain dichloromethane, and performing column chromatography to obtain p- (diX-based amino) phenylacetylene;
step five, introducing p- (diXylamino) phenylacetylene into anthraquinone derivative
According to the mass part of 1:2, taking 0.1-20 parts of the product 9, 10-dioxo-9, 10-dihydroanthracene-2, 6-diyl bis (4- (2- ((4- (4- (4-bromophenyl) -1H-1, 2, 3-triazol-1-yl) phenyl) thio) ethyl) benzoate) prepared in the third step and 0.2-40 parts of the product p- (diX-ylamino) phenylacetylene obtained in the fourth step, dissolving the product p- (diX-ylamino) phenylacetylene in a flask containing 50-300mL of mixed solution of triethylamine and tetrahydrofuran in a volume ratio of 1:1, adding 0.01-5 parts of bis (triphenylphosphine) palladium dichloride and 0.01-5 parts of cuprous iodide, introducing argon and ultrasonically deoxidizing for 10-60 min; then transferring the flask into a normal-pressure microwave reactor with reflux and ultraviolet, Nd and YAG solid pulse laser, starting microwave irradiation for 0.5-12h, and keeping the temperature of the system at 10-100 ℃; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.5-6 h; after the reaction is finished, removing solids by centrifugation, 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 an eluent to obtain an anthraquinone derivative;
step six, carrying out click chemical modification on anthraquinone derivative R1
According to the mass part of 1:2, dissolving 0.1-20 parts of anthraquinone derivative prepared in the step five and 0.2-40 parts of click reagent in a certain amount of dichloromethane, and stirring for 0.5-3h at room temperature; microwave irradiation is utilized to initiate chemical reaction, the irradiation time is 0.5-6h, and the system temperature is kept at 20-100 ℃; when microwave irradiation is started, ultraviolet irradiation and laser irradiation are used for 0.5-12h, after the reaction is finished, rotary evaporation is carried out for 10-120min, then eluent is prepared by using petroleum ether and dichloromethane in a volume ratio of 1:1, and a silica gel column is purified to obtain a 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 7,7,8, 8-tetracyano-p-benzoquinodimethane, tetracyanoethylene or 2,3,5,6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane.
4. The method for preparing the broadband liquid crystal laser protection material according to claim 2, wherein the method comprises the following steps: and in the second step, the reactant 4-azidothiophenol is generated by reacting 4-bromophenylthiol with NaN3, wherein the specific reaction process comprises the steps of adding 0.2-40 parts of 4-bromophenylthiol and 0.2-40 parts of NaN3 into a 50-500mL flask, then adding 50-300mL of dimethyl sulfoxide, heating and stirring to dissolve the dimethyl sulfoxide, heating and reacting at 50 ℃ in an oil bath, removing the oil bath after the reaction is finished, washing with water for multiple times, extracting with Dichloromethane (DCM), collecting an organic phase, drying with anhydrous sodium sulfate, carrying out silica gel column chromatography, and obtaining the 4-azidothiophenol by using petroleum ether as an eluent.
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 by a microwave reactor, the microwave frequency is 2350-2500MHz, and the microwave power is 400-1500W; when the microwave irradiation is started, simultaneously using ultraviolet irradiation and laser irradiation, wherein the wavelength of the ultraviolet light is 190-380nm, and the illumination intensity is 5mW/cm 2 -5W/cm 2 。.
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 by a microwave reactor, the microwave frequency is 2350-: eluting with ethyl acetate at a volume ratio of 6: 1.
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, halogenated hydrocarbons are different according to the number n of alkyl carbon atoms, when n is 1, the halogenated hydrocarbons are methyl iodide and methyl bromide, and the obtained product is p- (dimethylamino) phenylacetylene; when n is 4, the halogenated hydrocarbon is bromobutane, and the obtained product is p- (dibutylamino) phenylacetylene; when n is 6, the halogenated hydrocarbon is bromohexane, and the obtained product is p- (dihexylamino) phenylacetylene; when n is 16, the halogenated hydrocarbon is 1-bromohexadecane, and the obtained product is p- (hexacosanylamino) phenylacetylene.
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