CN109400543A - 三嗪系前驱物、制备三嗪系前驱物的方法及三嗪系前驱物的应用 - Google Patents
三嗪系前驱物、制备三嗪系前驱物的方法及三嗪系前驱物的应用 Download PDFInfo
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- CN109400543A CN109400543A CN201810914631.2A CN201810914631A CN109400543A CN 109400543 A CN109400543 A CN 109400543A CN 201810914631 A CN201810914631 A CN 201810914631A CN 109400543 A CN109400543 A CN 109400543A
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- China
- Prior art keywords
- amido
- triazine
- chloro
- compound
- unsubstituted
- Prior art date
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- Granted
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002243 precursor Substances 0.000 title abstract 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 61
- 239000002245 particle Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 13
- 230000000269 nucleophilic effect Effects 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical class ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000012643 polycondensation polymerization Methods 0.000 claims description 4
- 241001502050 Acis Species 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011246 composite particle Substances 0.000 abstract 4
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 230000007794 irritation Effects 0.000 abstract 1
- 229940127554 medical product Drugs 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 125000003368 amide group Chemical group 0.000 description 50
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 30
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 28
- 238000012360 testing method Methods 0.000 description 24
- -1 triazine radical Chemical class 0.000 description 20
- 239000012044 organic layer Substances 0.000 description 19
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000010183 spectrum analysis Methods 0.000 description 11
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 231100000263 cytotoxicity test Toxicity 0.000 description 6
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 239000007758 minimum essential medium Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001343 alkyl silanes Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 210000002615 epidermis Anatomy 0.000 description 4
- 210000002950 fibroblast Anatomy 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 210000002966 serum Anatomy 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 210000003491 skin Anatomy 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000004083 survival effect Effects 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 231100000433 cytotoxic Toxicity 0.000 description 3
- 230000001472 cytotoxic effect Effects 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
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- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- XJQMSHDKNMKUKH-UHFFFAOYSA-N 2,4-bis(octylsulfanyl)-1,3,5-triazine Chemical class CCCCCCCCSC1=NC=NC(SCCCCCCCC)=N1 XJQMSHDKNMKUKH-UHFFFAOYSA-N 0.000 description 1
- STWTVTCBSVFAMN-UHFFFAOYSA-N 2-octylsulfanyl-1,3,5-triazine Chemical compound CCCCCCCCSC1=NC=NC=N1 STWTVTCBSVFAMN-UHFFFAOYSA-N 0.000 description 1
- OHVVTDKYLMOKDH-UHFFFAOYSA-N 2-propoxy-1,3,5-triazine Chemical class CCCOC1=NC=NC=N1 OHVVTDKYLMOKDH-UHFFFAOYSA-N 0.000 description 1
- KVYRCBOUKXJXDK-UHFFFAOYSA-N 3,4-dimethylphenazine-1,2-diamine hydrochloride Chemical compound Cl.C1=CC=CC2=NC3=C(C)C(C)=C(N)C(N)=C3N=C21 KVYRCBOUKXJXDK-UHFFFAOYSA-N 0.000 description 1
- AURDEEIHMPRBLI-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1.CC1=CC=CN=C1 AURDEEIHMPRBLI-UHFFFAOYSA-N 0.000 description 1
- COAXWQGZPUFCJR-UHFFFAOYSA-N CCCCCCCC[O] Chemical compound CCCCCCCC[O] COAXWQGZPUFCJR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000002768 Kirby-Bauer method Methods 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HTRXGEPDTFSKLI-UHFFFAOYSA-N butanoic acid;ethyl acetate Chemical compound CCCC(O)=O.CCOC(C)=O HTRXGEPDTFSKLI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 239000013553 cell monolayer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000012817 gel-diffusion technique Methods 0.000 description 1
- JQOAQUXIUNVRQW-UHFFFAOYSA-N hexane Chemical compound CCCCCC.CCCCCC JQOAQUXIUNVRQW-UHFFFAOYSA-N 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- SYJRVVFAAIUVDH-UHFFFAOYSA-N ipa isopropanol Chemical compound CC(C)O.CC(C)O SYJRVVFAAIUVDH-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
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- 239000002609 medium Substances 0.000 description 1
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- 230000004899 motility Effects 0.000 description 1
- PEECTLLHENGOKU-UHFFFAOYSA-N n,n-dimethylpyridin-4-amine Chemical compound CN(C)C1=CC=NC=C1.CN(C)C1=CC=NC=C1 PEECTLLHENGOKU-UHFFFAOYSA-N 0.000 description 1
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 1
- 238000011587 new zealand white rabbit Methods 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N5/00—Radiation therapy
- A61N5/06—Radiation therapy using light
- A61N5/0613—Apparatus adapted for a specific treatment
- A61N5/0625—Warming the body, e.g. hyperthermia treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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Abstract
一种三嗪系前驱物、制备三嗪系前驱物的方法及三嗪系前驱物的应用,该三嗪系前驱物由式(I)所示:X及Y各自选自于‑NR1R2、‑OR3或‑SR4;R1选自于氢、未经取代的C1至C22的直链烷基,或未经取代的C1至C22的支链烷基;R2、R3及R4各自选自于未经取代的C1至C22的直链烷基、未经取代的C1至C22的支链烷基;且Z表示‑NH‑R5‑Si(OR6)3,R5表示C2至C4的亚烷基,且每一个R6各自表示C1至C2的烷基。本发明也提供一种制备二氧化硅微米复合粒子的方法,及一种二氧化硅微米复合粒子。因二氧化硅微米复合粒子具有对细胞无毒害且对皮肤无刺激的效果而可应用于医疗用品、保健用品或生活用品中。
Description
技术领域
本发明涉及一种三嗪系前驱物、制备三嗪系前驱物的方法及三嗪系前驱物的应用,特别是涉及一种含有硅氧烷基团的三嗪系前驱物、一种制备该三嗪系前驱物的方法,及一种该三嗪系前驱物的应用。
背景技术
中国大陆专利公开第104349848号揭示一种表面处理剂,且该表面处理剂包含式(1)所示的三嗪基硅氧烷化合物及式(2)所示的三嗪基硅氧烷化合物。
虽该表面处理剂具有较佳的密着性且因可应用至许多且不同的材料的表面上而具有多样性。然而,当该表面处理剂用来与四乙氧基硅烷反应而形成二氧化硅粒子时,由于该表面处理剂含有式(2)所示的三嗪基硅氧烷化合物,使得所获得的二氧化硅粒子的粒径分布广而不集中,甚至可能存在有呈结构的串联状型态的二氧化硅材与网状型态的二氧化硅材,使得应用至一些产品(例如化妆品或医疗用品等)中时不利于分散在所述产品中。在该串联状型态的二氧化硅材中,该X为由该四乙氧基硅烷所形成的二氧化硅,而Y为由式(2)所示的三嗪基硅氧烷化合物所形成并通过B及C与X连接。
Adv.Mater.2012,24,2409–2412揭示一种用于使织物的表面具有疏水性的表面处理剂,包含聚二甲基硅氧烷(polydimethylsiloxane,简称PDMS)、具有氟烷基硅烷基团[(fluorinated alkyl)silanyl group]的二氧化硅纳米粒子,及(氟烷基)硅烷(fluorinated alkyl silane)。该具有氟烷基硅烷基团的二氧化硅纳米粒子是由四乙氧基硅烷(tetraethyl orthosilicate)与氟烷基硅烷在碱性条件下进行共水解(co-hydrolysis)及共缩聚合(co-condensation)反应所形成。该氟烷基硅烷为CF3-(CF2)5-(CH2)2-Si(OC2H5)3。然而,该氟烷基硅烷易产生自聚现象,而存在有储存安定性不佳的问题,且使得该具有氟烷基硅烷基团的二氧化硅纳米粒子的产率不佳。再者,由于该具有氟烷基硅烷基团的二氧化硅纳米粒子含有氟,对人体具有伤害性,而不利于应用至医疗用品、化妆品或保养品中。
发明内容
本发明的第一目的在于提供一种具有储存安定性的三嗪系前驱物。
本发明三嗪系前驱物,由式(I)所示:
X及Y各自选自于-NR1R2、-OR3或-SR4;
R1选自于氢、未经取代的C1至C22的直链烷基,或未经取代的C1至C22的支链烷基;
R2、R3及R4各自选自于未经取代的C1至C22的直链烷基,或未经取代的C1至C22的支链烷基;且
Z表示-NH-R5-Si(OR6)3,R5表示C2至C4的亚烷基,且每一个R6各自表示C1至C2的烷基。
本发明的第二目的,即在提供一种制备上述三嗪系前驱物的方法。
本发明制备上述三嗪系前驱物的方法,包含以下步骤:步骤(a),使2,4,6-三氯-1,3,5-三嗪与表示为H-X的第一亲核化合物在第一溶剂的存在下且在第一温度范围为0℃至25℃下进行第一置换反应,形成式(i)所示的第一中间物,步骤(b),使该式(i)所示的第一中间物与表示为H-Y的第二亲核化合物在第二溶剂的存在下且在第二温度范围为15℃至40℃下进行第二置换反应,形成式(ii)所示的第二中间物,步骤(c),使该式(ii)所示的第二中间物与表示为H-Z的第三亲核化合物在第三溶剂的存在下且在第三温度范围为35℃至75℃下进行第三置换反应,形成该三嗪系前驱物。
本发明的第三目的,即在提供一种制备二氧化硅微米复合粒子的方法。
本发明制备二氧化硅微米复合粒子的方法,包含:使上述的三嗪系前驱物与四烷基硅酸酯进行水解及缩聚合反应。
本发明的第四目的,即在提供一种具有放射红外线、对细胞无毒害且对皮肤无刺激的效果的二氧化硅微米复合粒子。
本发明二氧化硅微米复合粒子,由上述制备二氧化硅微米复合粒子的方法所形成。
本发明的有益效果在于:通过的设计,使得该三嗪系前驱物不易产生自聚现象,而具有安定性,且通过使用三嗪系前驱物,使得该二氧化硅微米复合粒子具有对细胞无毒害且对皮肤无刺激的效果。
以下将就本发明内容进行详细说明。
<三嗪系前驱物>
在本发明三嗪系前驱物中,通过产生的立体障碍的设计,增加该三嗪系前驱物中Z的稳定性,而使该三嗪系前驱物不易产生自聚现象,因而具有安定性,且通过R1、R2、R3及R4的设计,使得该三嗪系前驱物用来成为二氧化硅微米复合粒子中的一部分时,可使得该二氧化硅微米复合粒子不具有细胞毒性及皮肤刺激性。
为使该三嗪系前驱物更不易自聚而具有更佳的储存安定性,较佳地,R1选自于氢、未经取代的C2至C16的直链烷基,或未经取代的C2至C16的支链烷基;R2、R3及R4各自选自于未经取代的C2至C16的直链烷基,或未经取代的C2至C16的支链烷基。
<制备三嗪系前驱物的方法>
该第一亲核化合物选自于HNR1R2、HOR3,或HSR4。R1选自于氢、未经取代的C1至C22的直链烷基,或未经取代的C1至C22的支链烷基;R2、R3及R4各自选自于未经取代的C1至C22的直链烷基,或未经取代的C1至C22的支链烷基。
该第一溶剂可单独一种使用或混合多种使用,且该第一溶剂例如但不限于己烷(n-hexane)、环己烷(cyclohexane)、二氯甲烷(dichloromethane)、1,2-二氯乙烷(1,2-dichloroethane)、氯仿(chloroform)、丙酮(acetone)、乙酸乙酯(ethyl acetate)、四氢呋喃(tetrahydrofuran)、乙醚(ether)、甲醇(methanol)、乙醇(ethanol),或异丙醇(isopropanol)等。
在该第一置换反应中,是在第一碱性试剂的存在下进行。该第一碱性试剂可单独一种使用或混合多种使用,且该第一碱性试剂例如但不限于氢化钠(sodium hydride)、碳酸氢钠(sodium bicarbonate)、碳酸钠(sodium carbonate)、氢氧化钠(sodiumhydroxide)、碳酸钾(potassium carbonate)、氢氧化钾(potassium hydroxide)、三乙基胺(triethylamine)、吡啶(pyridine)、N,N-二异丙基乙基胺(N,N-diisopropylethylamine)、4-二甲胺基吡啶(4-dimethylaminopyridine)、3-甲基吡啶(3-picoline),或2,4,6-三甲基吡啶(2,4,6-collidine)等。
该第二亲核化合物与该第一亲核化合物可为相同或不同。该第二溶剂与该第一溶剂可为相同或不同。在该第二置换反应中,是在第二碱性试剂的存在下进行。该第二碱性试剂与该第一碱性试剂可为相同或不同。
该第三亲核化合物选自于H2N-R5-Si(OR6)3。R5表示C2至C4的亚烷基,且每一个R6各自表示C1至C2的烷基。该第三溶剂与该第一溶剂可为相同或不同。在该第三置换反应,是在第三碱性试剂的存在下进行。该第三碱性试剂与该第一碱性试剂可为相同或不同。
<制备二氧化硅微米复合粒子的方法及二氧化硅微米复合粒子>
该四烷基硅酸酯例如但不限于四乙氧基硅烷。该水解及缩聚合反应的操作温度范围为25℃至60℃。该水解及缩聚合反应的操作时间范围为24小时至72小时。在该水解及缩聚合反应的过程中,该四烷基硅酸酯会形成二氧化硅物质,而该三嗪前驱物中的-Si(OR6)3会转变成-Si(O-)3,并通过-Si(O-)3而键结至该二氧化硅物质上,使得该二氧化硅微米复合粒子具有多个表示为的基团。再者,由于该三嗪系前驱物不易产生自聚现象,使得所获得的二氧化硅微米复合粒子的粒径均一、粒径分布集中,且纯度高。
由于该二氧化硅微米复合粒子具有放射红外线功能,特别是远红外线,而可应用于医疗用品、保健用品或生活用品中。该医疗用品例如但不限于医疗级照射灯。该保健用品例如但不限于护膝用具或热敷垫等。该生活用品例如但不限于化妆品或织物等。
具体实施方式
本发明将就以下实施例来作进一步说明,但应了解的是,该实施例仅为例示说明用,而不应被解释为本发明实施限制。
实施例1(C8H17O)((C8H17)2N)-Tz-Si(OEt)3
步骤a:将容置有30mL的干燥二氯甲烷的100mL的单口反应瓶置于0℃的冰水浴中。将1.84克(10mmol)的三聚氰氯加入至该反应瓶中,并使该三聚氰氯溶解。然后,将2.41克(10mmol)的二辛胺缓慢滴入该反应瓶中。待反应10分钟后,缓慢加入1.01克(10mmol)的三乙基胺。待反应20分钟后,使用30mL的0.5M的氢氧化钠水溶液进行两次萃取处理,收集有机层。将50mL的清水加入有机层中进行萃取处理,再次收集有机层。接着,将无水硫酸镁加入有机层中除水,然后过滤,可得滤液。使用减压浓缩机将该滤液中的二氯甲烷移除,得到3.69克(9.5mmol)的2,4-二氯-6-二辛基胺基-1,3,5-三嗪。
步骤b:将含有20mL干燥二氯甲烷及3.88克(10mmol)2,4-二氯-6-二辛基胺基-1,3,5-三嗪的50mL的单口反应瓶置于0℃的冰水浴中。将0.4克(10mmol)的60%氢化钠与1.3克(10mmol)的1-辛醇混合并反应2分钟,形成混合溶液,接着将该混合溶液缓慢加入至该反应瓶中,反应10分钟后,移置室温环境下反应12小时。接着,加入30mL的0.5M氢氧化钠水溶液进行两次萃取处理,收集有机层。将50mL的清水加入有机层中进行萃取处理,再次收集有机层。然后,将无水硫酸镁加入有机层中除水过滤,可得滤液。使用减压浓缩机将该滤液中的二氯甲烷移除,得到4.54克(9.4mmol)的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪。
步骤c:将4.83克(10mmol)的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪溶于50ml的四氢呋喃中,加入2.44克(11mmol)的3-(三乙氧基硅烷基)丙基胺及2.6克(20mmol)的N,N-二异丙基乙基胺。将温度升至65℃进行48小时的反应。然后,使用减压浓缩机将四氢呋喃移除。加入30mL的二氯甲烷及30mL的0.5M氢氧化钠水溶液进行两次萃取处理,并收集有机层。接着,将50mL的清水加入有机层中进行萃取处理,再次收集有机层。将无水硫酸镁加入有机层中进行除水及过滤,可得滤液。使用减压浓缩机将该滤液中的二氯甲烷移除,可得浓缩物。将该浓缩物利用硅胶管柱(管径为2.6cm且长度为15cm)进行纯化处理,且该纯化处理是利用己烷与四氢呋喃作为冲提液,而该己烷与该四氢呋喃的体积比为5:1。得到4.48克(6.7mmol)的2-二辛基胺基-4-辛基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪,且总产率为59.8%。
该2-二辛基胺基-4-辛基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.64(t,J=8.4Hz,2H,CH2-Si),0.86(t,J=6.3Hz,9H,3×CH3),1.20(t,J=6.9Hz,9H,3×CH3-COSi),1.26(s,broad,30H,15×CH2),1.55(s,broad,4H,2×CH2-CN),1.60~1.78(m,4H,CH2-CSi+CH2-CO),3.33~3.51(m,6H,3×CH2-N),3.80(q,J=6.9Hz,6H,3×CH2-OSi),4.21(s,broad,2H,CH2-O),5.05(t,J=5.7Hz,1H,N-H)。MS:m/z 668.51(M+H)+。化学结构为
实施例2(C2H5O)((C8H17)2N)-Tz-Si(OEt)3
该实施例2与该实施例1不同处在于:将实施例1的步骤b中的1-辛醇置换成乙醇,而于步骤b完成后形成化合物为2-氯-4-二辛基胺基-6-乙基氧基-1,3,5-三嗪。且将步骤c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置换成2-氯-4-二辛基胺基-6-乙基氧基-1,3,5-三嗪,而于步骤c完成后形成化合物为2-二辛基胺基-4-乙基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪。该实施例2的总产率为47.0%。
该2-二辛基胺基-4-乙基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3,δ(ppm):0.62(t,J=8.1Hz,2H,CH2-Si),0.86(t,J=6.3Hz,6H,2×CH3),1.20(t,J=6.9Hz,9H,3×CH3-COSi),1.27(s,broad,23H,10×CH2+CH3),1.55(s,broad,4H,2×CH2-CN),1.60~1.78(m,2H,CH2-CSi),3.33~3.51(m,6H,3×CH2-N),3.80(q,J=6.9Hz,6H,3×CH2-OSi),4.25(s,broad,2H,CH2-O),5.05(t,J=5.7Hz,1H,N-H)。MS:m/z 584.79(M+H)+。化学结构为
实施例3((CH3)2CHO)((C8H17)2N)-Tz-Si(OEt)3
该实施例3与该实施例1不同处在于:将实施例1的步骤b中的1-辛醇置换成异丙醇,而于步骤b完成后形成化合物为2-氯-4-二辛基胺基-6-异丙基氧基-1,3,5-三嗪。且将步骤c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置换成2-氯-4-二辛基胺基-6-异丙基氧基-1,3,5-三嗪,而于步骤c完成后形成化合物为2-二辛基胺基-4-异丙基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪。该实施例3的总产率为38.3%。
该2-二辛基胺基-4-异丙基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.61(t,J=8.1Hz,2H,CH2-Si),0.85(t,J=6.3Hz,6H,2×CH3),1.19(t,J=6.9Hz,9H,3×CH3-COSi),1.31(s,broad,26H,13×CH2),1.55(s,broad,4H,2×CH2-CN),1.69(m,J=6.6Hz,2H,CH2-CSi),3.35(q,J=6.3Hz,2H,3×CH2-N),3.45(q,J=6.3Hz,4H,2×CH2-N),3.77(q,J=6.9Hz,6H,3×CH2-OSi),5.37(s,broad,1H,CH-O),6.323(s,1H,N-H);MS:m/z 598.83(M+H)+。
化学结构为
实施例4(C2H5O)((2-(C2H5)(C6H12))2N)-Tz-Si(OEt)3
该实施例4与该实施例1不同处在于:将实施例1的步骤a中的二辛胺置换成二(2-乙基己基)胺,而于步骤a完成后形成化合物为2,4-二氯-6-二(2-乙基己基)胺基-1,3,5-三嗪。将实施例1步骤b中的1-辛醇置换成乙醇,而于步骤b完成后形成化合物为2-氯-4-二(2-乙基己基)胺基-6-乙基氧基-1,3,5-三嗪。且将步骤c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置换成2-氯-4-二(2-乙基己基)胺基-6-乙基氧基-1,3,5-三嗪,而于步骤c完成后形成化合物为2-二(2-乙基己基)胺基-4-乙基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪。该实施例4的总产率为41.0%。
该2-二(2-乙基己基)胺基-4-乙基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.66(t,J=8.1Hz,2H,CH2-Si),0.86(t,J=6.9Hz,12H,4×CH3),1.22(t,J=6.9Hz,9H,3×CH3-COSi),1.26(s,broad,16H,8×CH2),1.34(t,J=7.5Hz,3H,1×CH3),1.64~1.80(m,4H,CH2-CSi+2×CH),3.37~3.44(m,6H,3×CH2-N),3.81(q,J=6.9Hz,6H,3×CH2-OSi),4.31(t,J=6.6Hz,2H,CH2-O),4.95(s,broad,1H,H-N)。MS:m/z 584.92(M+H)+。
化学结构为
实施例5(C8H17NH)((C8H17)2N)-Tz-Si(OEt)3
该实施例5与该实施例1不同处在于:将实施例1的步骤b中的1-辛醇置换成1-辛胺,而于步骤b完成后形成化合物为2-氯-4-辛基胺基-6-二辛基胺基-1,3,5-三嗪。将步骤c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置换成2-氯-4-辛基胺基-6-二辛基胺基-1,3,5-三嗪,于步骤c完成后形成化合物为2-辛基胺基-4-二辛基胺基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪。该实施例5的总产率为49.3%。
该2-辛基胺基-4-二辛基胺基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.68(t,J=8.7Hz,2H,CH2-Si),0.88(t,J=6.3Hz,9H,3×CH3),1.21(t,J=6.9Hz,9H,3×CH3-COSi),1.26(s,broad,30H,15×CH2),1.51~1.80(m,8H,CH2-CSi+3×CH2-CN),3.33~3.51(m,8H,4×CH2-N),3.81(q,J=6.9Hz,6H,3×CH2-OSi),5.01(s,broad,1H,H-N),5.35(t,J=4.8Hz,1H,H-N)。MS:m/z 667.35(M+H)+。化学结构为
实施例6(C8H17S)((C8H17)2N)-Tz-Si(OEt)3
该实施例6与该实施例1不同处在于:将实施例1步骤b中的1-辛醇置换成1-辛硫醇,而于步骤b完成后形成化合物为2-氯-4-二辛基胺基-6-辛基硫基-1,3,5-三嗪。将步骤c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置换成2-氯-4-二辛基胺基-6-辛基硫基-1,3,5-三嗪,于步骤c完成后形成化合物为2-二辛基胺基-4-辛基硫基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪。该实施例6的总产率为53.3%。
该2-二辛基胺基-4-辛基硫基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.65(t,J=8.4Hz,2H,CH2-Si),0.88(t,J=6.3Hz,9H,3×CH3),1.22(t,J=6.9Hz,9H,3×CH3-COSi),1.27(s,broad,30H,15×CH2),1.42(s,broad,4H,2×CH2-CN),1.60~1.78(m,4H,CH2-CSi+CH2-CO),3.01(t,J=7.2Hz,2H,CH2-S),3.36~3.51(m,6H,3×CH2-N),3.81(q,J=6.9Hz,6H,3×CH2-OSi),5.01(t,J=5.7Hz,1H,H-N)。MS:m/z 683.78(M)+。化学结构为
实施例7(C8H17S)(C8H17NH)-Tz-Si(OEt)3
该实施例7与该实施例1不同处在于:将实施例1步骤a中的二辛胺置换成1-辛胺,而于步骤a完成后形成化合物为2,4-二氯-6-辛基胺基-1,3,5-三嗪。将实施例1步骤b中的1-辛醇置换成1-辛硫醇,而于步骤b完成后形成化合物为2-氯-4-辛基胺基-6-辛基硫基-1,3,5-三嗪。将步骤c中2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置换成2-氯-4-辛基胺基-6-辛基硫基-1,3,5-三嗪,于步骤c完成后形成化合物为2-辛基胺基-4-辛基硫基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪。该实施例7的总产率为43.1%。
该2-辛基胺基-4-辛基硫基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.66(t,J=8.4Hz,2H,CH2-Si),0.88(t,J=6.3Hz,6H,2×CH3),1.23(t,J=7.2Hz,9H,3×CH3-COSi),1.26(s,broad,20H,10×CH2),1.48~1.78(m,6H,CH2-CSi+CH2-CN+CH2-CS),3.03(t,J=7.2Hz,2H,CH2-S),3.34~3.51(m,4H,2×CH2-N),3.82(q,J=6.6Hz,6H,3×CH2-OSi),5.03(s,broad,1H,H-N),5.35(t,J=5.1,1H,H-N)。MS:m/z 571.83(M)+。化学结构为
实施例8(C8H17O)(C8H17NH)-Tz-Si(OEt)3
该实施例8与该实施例1不同处在于:将实施例1的步骤a中的二辛胺置换成1-辛胺,而于步骤a完成后形成化合物为2,4-二氯-6-辛基胺基-1,3,5-三嗪。将步骤b中的2,4-二氯-6-二辛基胺基-1,3,5-三嗪置换成2,4-二氯-6-辛基胺基-1,3,5-三嗪,于步骤b完成后形成2-氯-4-辛基胺基-6-辛基氧基-1,3,5-三嗪。将步骤c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置换成2-氯-4-辛基胺基-6-辛基氧基-1,3,5-三嗪,而于步骤c完成后形成2-辛基胺基-4-辛基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪。该实施例8的总产率为35.2%。
该2-辛基胺基-4-辛基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.69(t,J=7.2Hz,2H,CH2-Si),0.88(t,J=6.6Hz,6H,2×CH3),1.22(t,J=6.9Hz,9H,3×CH3-COSi),1.26(s,broad,20H,10×CH2),1.49~1.8.(m,6H,CH2-CSi+2×CH2-CO),3.22~3.51(m,4H,2×CH2-N),3.81(q,J=6.9Hz,6H,3×CH2-OSi),4.16~4.39(m,2H,CH2-O),5.01(s,broad,1H,H-N),5.35(t,J=5.1,1H,H-N)。MS:m/z 556.54(M+H)+。化学结构为
实施例9(C16H33O)((C4H9)2N)-Tz-Si(OEt)3
该实施例9与该实施例1不同处在于:将实施例1步骤a中的二辛胺置换成二丁胺,而于步骤a完成后形成化合物为2,4-二氯-6-二丁基胺基-1,3,5-三嗪。将实施例1步骤b中的1-辛醇置换成1-十六醇,而于步骤b完成后形成化合物为2-氯-4-二丁基胺基-6-十六基氧基-1,3,5-三嗪。将步骤c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置换成2-氯-4-二丁基胺基-6-十六基氧基-1,3,5-三嗪,于步骤c完成后形成化合物为2-二丁基胺基-4-十六基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪。该实施例9的总产率为38.3%。
该2-二丁基胺基-4-十六基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.64(t,J=8.4Hz,2H,CH2-Si),0.88(t,J=6.9Hz,9H,3×CH3),1.22(t,J=6.9Hz,9H,3×CH3-COSi),1.31(s,broad,30H,15×CH2),1.51~1.73(m,8H,2×CH2-CN)+CH2-CSi+CH2-CO),3.33~3.58(m,6H,3×CH2-N),3.81(q,J=6.9Hz,6H,3×CH2-OSi),4.21(s,broad,2H,CH2-O),5.7(t,J=5.1Hz,1H,H-N)。MS:m/z568.71(M+H)+。化学结构为
实施例10Bis-((C4H9)2N)-Tz-Si(OEt)3
步骤a:将容置有50mL的干燥二氯甲烷的100mL的单口反应瓶置于0℃的冰水浴中。将1.84克(10mmol)三聚氰氯加入至该反应瓶中,并使该三聚氰氯溶解。然后,将2.81克(22mmol)的二丁胺缓慢滴入该反应瓶中。待反应20分钟后,缓慢加入2.53克(25mmol)的三乙基胺,并持续反应20分钟。
步骤b:然后,移置室温环境(约27度)下再反应12小时。接着,使用60mL的0.5M的氢氧化钠水溶液进行两次萃取处理,收集有机层。将50mL的清水加入有机层中进行萃取处理,再次收集有机层。接着,将无水硫酸镁加入有机层中进行除水及过滤,可得滤液。使用减压浓缩机将该滤液中的二氯甲烷移除,得到3.37克(9.2mmol)的2-氯-4,6-双(二丁基胺基)-1,3,5-三嗪。
步骤c:将3.67克(10mmol)的2-氯-4,6-双(二丁基胺基)-1,3,5-三嗪溶于50ml四氢呋喃中,接着,加入2.44克(11mmol)的3-(三乙氧基硅烷基)丙基胺及2.6克(20mmol)的N,N-二异丙基乙基胺。将温度升至50℃进行24小时的反应。然后,使用减压浓缩机将四氢呋喃移除。加入30mL的二氯甲烷并使用30mL的0.5M氢氧化钠水溶液进行两次的萃取处理,并收集有机层。接着,将50mL的清水加入有机层中进行萃取处理,再次收集有机层。然后,将无水硫酸镁加入有机层中进行除水及过滤,可得一滤液。使用减压浓缩机将该滤液中的二氯甲烷移除,可得浓缩物。将该浓缩物利用硅胶管柱(管径为2.6cm且长度为15cm)进行纯化处理,且该纯化处理是利用己烷与四氢呋喃作为冲提液,而该己烷与该四氢呋喃的体积比为5:1,得到1.99克(3.6mmol)的2,4-双(二丁基胺基)-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪,且总产率为33.1%。
该2,4-双(二丁基胺基)-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.67(t,J=6.3Hz,2H,CH2-Si),0.92(t,J=7.2Hz,12H,4×CH3),1.21(t,J=6.9Hz,9H,3×CH3-COSi),1.30(q,J=7.5Hz,8H,4×CH2-CN),1.60~1.71(m,10H,CH2-CSi+4×CH2-CN),3.30(q,J=6.6Hz,2H,CH2-N),3.43(t,J=7.8Hz,8H,4×CH2-N),3.81(q,J=6.9Hz,6H,3×CH2-OSi),4.73(t,J=6.0Hz,1H,H-N)。MS:m/z 555.79(M+H)+。化学结构为
实施例11Bis-(C8H17S)-Tz-Si(OEt)3
该实施例11与该实施例10不同处在于:将实施例10的步骤a中的二丁胺置换成1-辛硫醇、三乙基胺换成N,N-二异丙基乙基胺,且于步骤b完成后形成化合物为2-氯-4,6-二(辛基硫基)-1,3,5-三嗪。将步骤b中的2-氯-4,6-双(二丁基胺基)-1,3,5-三嗪置换成2-氯-4,6-二(辛基硫基)-1,3,5-三嗪,而于步骤c完成后形成化合物为2,4-二(辛基硫基)-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪,该实施例11的总产率为58.3%。
该2,4-二(辛基硫基)-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.65(t,J=8.4Hz,2H,CH2-Si),0.87(t,J=7.2Hz,6H,2×CH3),1.22(t,J=7.2Hz,9H,3×CH3-COSi),1.271(s,broad,16H,8×CH2),1.34~1.49(m,4H,2×CH2),1.67~1.79(m,6H,CH2-CSi+2×CH2-CS),3.05(t,J=6.6Hz,4H,2×CH2-S),3.41(q,J=6.3Hz,2H,CH2-N),3.82(q,J=6.6Hz,6H,3×CH2-OSi),5.46(s,broad,1H,H-N)。MS:m/z 589.90(M+H)+。化学结构为
实施例12Bis-(C8H17O)-Tz-Si(OEt)3
该实施例12与该实施例10不同处在于:将实施例10步骤a中的二丁胺置换成1-辛醇、三乙基胺换成氢化钠,且于步骤b完成后形成化合物为2-氯-4,6-二(辛基氧基)-1,3,5-三嗪。将步骤c中的2-氯-4,6-双(二丁基胺基)-1,3,5-三嗪置换成2-氯-4,6-二(辛基氧基)-1,3,5-三嗪,于步骤c完成后形成2,4-二(辛基氧基)-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪,该实施例12的总产率为68.4%。
该2,4-二(辛基氧基)-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3,298K),δ(ppm):0.66(t,J=8.4Hz,2H,CH2-Si),0.88(t,J=8.4Hz,6H,2×CH3),1.23(t,J=6.9Hz,9H,3×CH3-COSi),1.28(s,broad,16H,8×CH2),1.34~1.49(m,4H,2×CH2),1.67~1.79(m,6H,CH2-CSi+2×CH2-CO),3.44(q,J=6.3Hz,2H,CH2-N),3.82(q,J=6.6Hz,6H,3×CH2-OSi),4.3(t,J=8.1Hz,4H,2×CH2-O),5.42(t,J=5.1,1H,H-N)。MS:m/z 557.83(M+H)+。化学结构为
实施例13Bis-(C8H17NH)-Tz-Si(OEt)3
该实施例13与该实施例10不同处在于:将实施例10步骤a中的二丁胺置换成1-辛胺,而于步骤a完成后形成化合物为2-氯-4,6-二(辛基胺基)-1,3,5-三嗪化合物。将步骤b中的2-氯-4,6-双(二丁基胺基)-1,3,5-三嗪置换成2-氯-4,6-二(辛基胺基)-1,3,5-三嗪,于步骤b完成后形成化合物为2,4-二(辛基胺基)-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪,该实施例13的总产率为52.3%。
该2,4-二(辛基胺基)-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.66(t,J=8.4Hz,2H,CH2-Si),0.87(t,J=6.3Hz,6H,2×CH3),1.21(t,J=6.9Hz,9H,3×CH3-COSi),1.28(s,broad,20H,10×CH2),1.41~1.79(m,6H,CH2-CSi+2×CH2-CN),3.32(s,broad,6H,3×CH2-N),3.81(q,J=6.9Hz,6H,3×CH2-OSi),4.84(s,broad,3H,3×H-N)。MS:m/z 555.44(M+H)+。
化学结构为
实施例14((CH3)2CHO)((C6H13)2N)-Tz-Si(OEt)3
该实施例14与该实施例1不同处在于:将实施例1的步骤a中的二辛胺置换成二己胺,而于步骤a完成后形成化合物为2,4-二氯-6-二己基胺基-1,3,5-三嗪。将实施例1的步骤b中的1-辛醇置换成异丙醇,而于步骤b完成后形成化合物为2-氯-4-二己基胺基-6-异丙基氧基-1,3,5-三嗪。且将步骤c中的2-氯-4-二辛基胺基-6-辛基氧基-1,3,5-三嗪置换成2-氯-4-二己基胺基-6-异丙基氧基-1,3,5-三嗪,而于步骤c完成后形成化合物为2-二己基胺基-4-异丙基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪。该实施例14的总产率为38.3%。
该2-二己基胺基-4-异丙基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪的光谱分析:1H NMR(300MHz,CDCl3),δ(ppm):0.65(t,J=8.4Hz,2H,CH2-Si),0.88(t,J=6.0Hz,6H,2×CH3),1.21(t,J=6.9Hz,9H,3×CH3-COSi),1.31(s,broad,18H,9×CH2),1.56(s,broad,4H,2×CH2-CN),1.60~1.75(m,2H,CH2-CSi),3.33~3.51(m,6H,3×CH2-N),3.81(q,J=6.9Hz,6H,3×CH2-OSi),5.19(s,broad,1H,CH-O),5.01(t,J=4.5Hz,1H,N-H)。MS:m/z 542.83(M+H)+。化学结构为
应用例1
将6.68克(10mmol)的实施例1的2-二辛基胺基-4-辛基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪、20.8克(100mmol)的四乙氧基硅烷及30mL的乙醇均匀搅拌3分钟,然后,缓慢加入22mL的35%的氨水水溶液,并反应24小时。待反应24小时后,进行过滤处理,获得滤饼,接着,以热水清洗该滤饼两次并进行干燥处理,得到6.5克的包含多个二氧化硅微米复合粒子的产物,且产率为58.6%。
应用例2
该应用例2与该应用例1不同处在于:将2-二辛基胺基-4-辛基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪置换成实施例2的2-二辛基胺基-4-乙基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪,而形成6.3克的包含多个二氧化硅微米复合粒子的产物,且产率为57.4%。
应用例3
该应用例3与该应用例1不同处在于:将2-二辛基胺基-4-辛基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪置换成实施例3的2-二辛基胺基-4-异丙基氧基-6-(3-三乙氧基硅烷基丙基)胺基-1,3,5-三嗪,而形成5.9克的包含多个二氧化硅微米复合粒子的产物,且产率为53.9%。
比较应用例1
将20.8克(100mmol)的四乙氧基硅烷及30mL的乙醇均匀搅拌3分钟,然后,缓慢加入22mL的35%的氨水水溶液,并反应24小时。待反应后,进行过滤处理,获得滤饼,接着,以热水清洗该滤饼两次并进行干燥处理,得到5.1克的包含多个二氧化硅粒子的产物,且产率为85%。
评价项目
粒径(单位:μm)量测:将应用例1的产物、应用例2的产物、应用例3的产物及比较应用例1的产物分散于乙醇中,并使用粒径及界面电位分析仪(particle size and zetapotential analyzer;厂牌:Otsuka Electronics;型号:NanoPlus)进行量测。
远红外线放射率(单位:%):将应用例1的产物、应用例2的产物、应用例3的产物及比较应用例1的产物制备成长约13mm、宽约13mm且厚度小于2mm的片状检测样品。使用傅里叶变换红外光光谱仪(厂牌:Bruker Optics;型号:VERTEX 70)对所述检测样品进行量测。该量测条件:量测温度为40℃;环境温度为25±3℃且相对湿度为60±10%;量测波长范围4μm至14μm。
皮肤刺激性测试:依据ASTM F719-81及ISO 10993-10的规范。先剃除纽西兰白兔背部毛发,并检查背部皮表是否完整,若背部皮表有刮痕或皮肤病,则不予使用。为方便描述测试过程,以应用例1的产物进行说明,而应用例2的产物、应用例3的产物及比较应用例1的产物也依照该方式进行测试。将2克的应用例1的产物与10毫升的生理食盐水(normalsaline)混合,形成浓度为0.2克/mL的检测样品。将两片纱布分别浸入0.5mL的检测样品与作为对照组的0.5mL的生理食盐水中72小时,形成两片浸湿的纱布。接着,将所述浸湿的纱布间隔设置并覆盖在已剔除毛发的背部皮表上,然后以透气绷带固定。4小时后,移除所述浸湿的纱布,接着,于1、24、48及72小时后,观察并纪录测背部皮表是否存在有红斑或水肿等的现象。
细胞毒性测试A:利用琼脂扩散试验法(Agar Diffusion Test)进行细胞毒性测试(Cytotoxicity test)。将小鼠纤维母细胞(L929,mouse fibroblast cells,CCRC60091NCTN Clone 929,of strain L)植入6孔培养盘(6-well plate)的各孔中,并分别在各孔中加入含有10%的血清及1%的抗生素的最低必需培养基(minimum essentialmedium,简称MEM)培养,待细胞长至八分满(sub-confluent cell monolayer),再加入2mL的1.5%的琼脂(Agar)。待琼脂凝固后,再将检测样品置于其中一个孔中,而剩余的孔不放置该检测样品并作为对照组。接着,放置于37℃且含有5%的二氧化碳的培养箱中培养24小时,以中性红(Neutral Red)染色并计数活细胞的数目。该检测样品共进行3次测试,定性的结果依据ISO10993-5及ASTM F895-11。评估三重复中个别的等级重复的等级平均后,即为定性评分。测试结果R.I.>1/1即样品具细胞毒性。依据细胞死亡比例与细胞变形比例获得反应指数(Response Index,简称RI),且RI值愈低,表示细胞毒性愈低。为清楚描述该检测样品的配置过程,以应用例1的产物进行说明,而应用例2的产物、应用例3的产物及比较应用例1的产物也依照该方式进行配置。将0.2克的应用例1的产物与含有10%的血清及1%的抗生素的最低必需培养基混合,形成浓度为0.2g/mL的检测样品。在测试应用例1时的对照组的反应指数为0/0。在测试应用例2时的对照组的反应指数为0/0。在测试应用例3时的对照组的反应指数为0/0。在测试比较应用例1时的对照组的反应指数为5/5。
细胞毒性测试B:利用MTT分析法进行细胞毒性测试(Cytotoxicity test)。将小鼠纤维母细胞(L929,mouse fibroblast cells,CCRC 60091NCTN Clone 929,of strain L)植入96孔培养盘(96-well plate)的各孔中,并分别在各孔中加入含有10%的血清及1%的抗生素的最低必需培养基培养。待细胞长满(sub-confluent monolayer),则将0.1mL的检测样品加入96孔培养盘的部分孔中,而剩余的孔不放置检测样品并作为对照组。接着,放置于37℃且含有5%的二氧化碳的培养箱中培养24小时,再以MTT法进行细胞存活率(CellViability)分析。该检测样品共进行3次测试,并取其平均值。为清楚描述检测样品的配置过程,以应用例1的产物进行说明,而应用例2的产物、应用例3的产物及比较应用例1的产物也依照该方式进行配置。将0.2克的应用例1的产物与含有10%的血清及1%的抗生素的最低必需培养基混合,形成浓度为0.2g/mL的检测样品。在测试应用例1时的对照组的细胞存活率为73.3±5.7%。在测试应用例2时的对照组的细胞存活率为102.9±6.8%。在测试应用例3时的对照组的细胞存活率为70.64±3.54%。在测试比较应用例1时的对照组的细胞存活率为35.4±4.9%。
由下表1可知,应用例1、2、3制得该二氧化硅微米复合粒子具有对细胞无毒害且对皮肤无刺激的效果。
表1
Claims (6)
1.一种三嗪系前驱物,其特征在于由式(I)所示:
X及Y各自选自于-NR1R2、-OR3或-SR4;
R1选自于氢、未经取代的C1至C22的直链烷基,或未经取代的C1至C22的支链烷基;
R2、R3及R4各自选自于未经取代的C1至C22的直链烷基,或未经取代的C1至C22的支链烷基;且
Z表示-NH-R5-Si(OR6)3,R5表示C2至C4的亚烷基,且每一个R6各自表示C1至C2的烷基。
2.一种制备权利要求1所述的三嗪系前驱物的方法,其特征在于包含以下步骤:
步骤(a),使2,4,6-三氯-1,3,5-三嗪与表示为H-X的第一亲核化合物在第一溶剂的存在下且在第一温度范围为0℃至25℃下进行第一置换反应,形成式(i)所示的第一中间物,
步骤(b)使该第一中间物与表示为H-Y的第二亲核化合物在第二溶剂的存在下且在第二温度范围为15℃至40℃下进行第二置换反应,形成式(ii)所示的第二中间物,
步骤(c)使该第二中间物与表示为H-Z的第三亲核化合物在第三溶剂的存在下且在第三温度范围为35℃至75℃下进行第三置换反应,形成该三嗪系前驱物。
3.根据权利要求2所述的制备权利要求1所述的三嗪系前驱物的方法,其特征在于:在该步骤(b)中,该第一亲核化合物与该第二亲核化合物为相同,且该第一溶剂与第二溶剂为相同。
4.一种制备二氧化硅微米复合粒子的方法,其特征在于包含:使权利要求1所述的三嗪系前驱物与四烷基硅酸酯进行水解及缩聚合反应。
5.根据权利要求4所述的制备二氧化硅微米复合粒子的方法,其特征在于:该四烷基硅酸酯是四乙氧基硅烷。
6.一种二氧化硅微米复合粒子,其特征在于:由权利要求4所述的制备二氧化硅微米复合粒子的方法所形成。
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