CN108675986A - 一种1,2,4-三氮唑吡啶盐化合物、制备方法及应用 - Google Patents
一种1,2,4-三氮唑吡啶盐化合物、制备方法及应用 Download PDFInfo
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- -1 1,2,4- triazoles pyridinium compound Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 15
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 12
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- RSSYZIDIBGZMCM-UHFFFAOYSA-N pyridine;1h-1,2,4-triazole Chemical class C=1N=CNN=1.C1=CC=NC=C1 RSSYZIDIBGZMCM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000001953 recrystallisation Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000012043 crude product Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 235000010290 biphenyl Nutrition 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 125000001814 trioxo-lambda(7)-chloranyloxy group Chemical group *OCl(=O)(=O)=O 0.000 claims description 2
- VCBVJJDJKPNJEG-UHFFFAOYSA-N 2,4,5-triphenyl-2H-pyran Chemical class C1=CC=C(C=C1)C2C=C(C(=CO2)C3=CC=CC=C3)C4=CC=CC=C4 VCBVJJDJKPNJEG-UHFFFAOYSA-N 0.000 claims 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 abstract description 15
- 241000588724 Escherichia coli Species 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005292 vacuum distillation Methods 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 30
- 239000007787 solid Substances 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 9
- JLKXXDAJGKKSNK-UHFFFAOYSA-N perchloric acid;pyridine Chemical compound OCl(=O)(=O)=O.C1=CC=NC=C1 JLKXXDAJGKKSNK-UHFFFAOYSA-N 0.000 description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 150000001243 acetic acids Chemical class 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000012453 solvate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- 241001478240 Coccus Species 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 241000219095 Vitis Species 0.000 description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 description 2
- 235000014787 Vitis vinifera Nutrition 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 210000002429 large intestine Anatomy 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- URJCERJZIWLFOJ-UHFFFAOYSA-N phenyl perchlorate Chemical compound O=Cl(=O)(=O)OC1=CC=CC=C1 URJCERJZIWLFOJ-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical class C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 238000006751 Mitsunobu reaction Methods 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229940006477 nitrate ion Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003285 pharmacodynamic effect Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- 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
- C07D401/02—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 two hetero rings
- C07D401/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
本发明提供了一种1,2,4‑三氮唑吡啶盐化合物、制备方法及应用，即将不同取代基吡喃盐化合物溶于有机溶剂后，加入3‑氨基‑1,2,4‑三氮唑溶液和碱助剂，在一定温度下搅拌反应后，滴加适量酸助剂，继续反应，减压蒸馏除去溶剂，得到粗产品；再经过重结晶、洗涤纯化、真空干燥后得到产品；发明的1,2,4‑三氮唑吡啶盐对大肠杆菌、金黄色葡萄球菌、黑曲霉菌具有优异的抗菌活性，同时，发明的化合物具有蓝色或蓝绿色发光，可以应用发光材料领域。
Description
技术领域
本发明属于精细化工技术领域，具体涉及一种1,2,4-三氮唑吡啶盐化合物、 制备方法及应用。
背景技术
吡啶盐是一类重要的六元氮杂环化合物，不仅是重要的有机合成中间体， 而且在化学传感、催化剂、光敏剂、离子液体、非线性光学材料、抗菌材料等 领域具有广阔的应用前景。SN2反应、Mitsunobu反应、Zincke’s反应等都被用 于吡啶盐及其衍生物的合成，但是很多合成方法存在副产物多，分离纯化难度 大，产物较难满足有机光电材料和生物材料的要求，且已知的一些分子结构可 修饰性低，从而限制了吡啶盐化合物的功能性应用。
三氮唑是一类代表性的多氮五元环分子，由于其独特的结构和化学性质， 在药物化学、有机合成中间体、光稳定剂等领域具有广阔应用。近年来，研究 发现三氮唑及其衍生物具有良好的稳定性和药理活性，在抗菌、抗癌、抗病毒 药物开发领域得到广泛应用。与其它抗菌剂相比，三氮唑类化合物在药效学、 药物代谢动力学等方面具有明显优势，但是报道的合成产物结构缺乏，且存在 作用机制和作用位点单一、抗菌性能不高的局限。目前尚未见共轭结构的1,2,4- 三氮唑吡啶盐化合物的报道。
本发明提出一种新型的1,2,4-三氮唑吡啶盐化合物及其制备方法，并可将其 应用于抗菌和阴离子传感领域。
发明内容
本发明的目的是提供一种1,2,4-三氮唑吡啶盐化合物的制备方法，合成1,2,4-三氮唑吡啶盐可用于抗菌和发光材料领域。
本发明的技术方案：
一种1,2,4-三氮唑吡啶盐化合物，其结构式如(I)所示：
式(Ⅰ)中，R为H或OMe或Me；X为ClO4。
一种1,2,4-三氮唑吡啶盐化合物的制备方法，步骤如下：
将不同取代基吡喃盐溶于有机溶剂，再加入3-氨基-1,2,4-三氮唑溶液和碱助剂，在10～40℃温度条件下搅拌反应2～20分钟后，滴加适量酸助剂，继续搅拌 反应0.5～10h后，减压蒸馏除去溶剂，得到粗产品；再经过重结晶、洗涤纯化 后，40～80℃真空干燥后得到产品；其中，吡喃盐、3-氨基-1,2,4-三氮唑、碱助 剂、酸助剂的摩尔比为1：1：0.05～2：0.5～3；
所述的不同取代基吡喃盐为2-甲基-3,4,5,6-四苯基吡喃盐、2,3,4,5,6-五苯基吡喃盐、2,4,5-三苯基吡喃盐、2-(4-甲氧基苯基)-4,5-二苯基吡喃盐，2-(4-甲 基苯基)-4,5-二苯基吡喃盐、2-萘基-4,5-二苯基吡喃盐和2-(4,4’-联苯基)-4,5- 二苯基吡喃盐中的一种；
所述的有机溶剂为二氯甲烷、三氯甲烷、甲醇、乙醇中的一种或两种以上 混合；
所述的碱助剂为C4以下的有机胺、碱金属碳酸盐、碱金属氢氧化物中的一 种或两种以上混合；
所述的酸助剂为C4以下的有机酸中的一种或两种以上混合。
一种1,2,4-三氮唑吡啶盐化合物，可用于抗菌和发光材料领域。抗菌实验研 究表明所述1,2,4-三氮唑吡啶盐化合物对大肠杆菌、金黄色葡萄球菌、黑曲霉菌 具有优异的抗菌活性(见附图1)。同时，所述的化合物在溶液中具有蓝色或蓝 绿色发光，可以应用发光材料领域。其发射峰强度随着溶液中氟离子和醋酸根 离子浓度的增加而逐渐降低，然而氯离子、溴离子、碘离子、硝酸根离子则没 有明显淬灭或者增强作用(见附图2)；当有上述离子共存时，仍可以实现对氟 离子和醋酸根离子的快速响应(见附图3)，这说明所述化合物对阴离子检测具 有优异的选择性和抗干扰能力。
本发明的有益效果：以多苯基取代吡喃盐和3-氨基-1,2,4-三氮唑反应合成 1,2,4-三氮唑吡啶盐，是一种简便、温和、高收率制备具有共轭结构的三氮唑吡 啶盐化合物的方法；通过叠加三氮唑分子和吡啶盐分子的生物活性，增加了所 述化合物的抗菌效力和广谱性，所述化合物可应用于抗菌材料领域。同时，由 于识别位点的增加，所述化合物可以通过荧光淬灭实现对氟离子和醋酸根离子 的高效识别，在环境、生物、医药检测等领域具有良好的应用前景。
附图说明
图1是1-(1H-1,2,4-三氮唑)-2,4,5-三苯基吡啶高氯酸盐晶体结构。
图2是大肠杆菌的荧光双染色照片，图2(a)为大肠杆菌，图2(b)为2-甲基 -3,4,5,6-四苯基-1-(1H-1,2,4-三氮唑)吡啶高氯酸盐处理后的大肠杆菌。
图3是2-甲基-3,4,5,6-四苯基-1-(1H-1,2,4-三氮唑)吡啶高氯酸盐溶液中滴 加不同阴离子四丁基铵盐(1×10-2mol/L)的荧光光谱，其中，(a)F-,(b)Cl-,(c) Br-,(d)I-,(e)AcO-,(f)NO3 -。
图4是含有不同阴离子的2-甲基-3,4,5,6-四苯基-1-(1H-1,2,4-三氮唑)吡啶 高氯酸盐溶液中加入(a)F-和(b)AcO-后的荧光强度变化。
具体实施方式
以下结合技术方案和附图叙述本发明的具体实施方式，但不限定本发明的范 围。
实施例1
向200mL的圆底烧瓶中加入50mL甲醇溶剂、0.50mmol 2-甲基-3,4,5,6- 四苯基高氯酸吡喃盐和0.50mmol 3-氨基-1,2,4-三氮唑，30℃下搅拌至完全溶 解，然后加入0.50mmol三乙胺，室温下搅拌反应10分钟后，加入0.80mmol 冰乙酸，持续搅拌反应6h；之后旋蒸掉溶剂，得到浅黄色固体，再利用乙醇重 结晶两次，50℃真空干燥后，得到白色产品，产率80％。表征数据：1H NMR(400 MHz,DMSO)δ(ppm):14.90(s,1H),8.80(s,1H),7.33(s,3H),7.21(s,2H),7.14(s, 3H),7.05(s,2H),7.01-6.94(m,9H),2.27(s,3H).13C NMR(126MHz,DMSO)δ (ppm):160.19,155.44,154.32,154.21,146.28,140.28,139.51,135.54,134.51, 134.15,130.67,130.21,129.54,128.62,128.49,127.84,127.58,127.28,127.26, 127.16,20.10.MS(ESI)m/z:465.3330(M+)。产物为2-甲基-3,4,5,6-四苯基-1-(1H-1,2,4-三氮唑)吡啶高氯酸盐，结构式为：
通过细菌生长曲线法、菌落计数法、荧光染色法对2-甲基-3,4,5,6-四苯基-1-(1H-1,2,4-三氮唑)吡啶高氯酸盐的抗菌性能研究，其对大肠杆菌的杀菌率达到 97％以上，对金黄色葡萄球菌的杀菌率达到95％，黑曲霉菌的杀菌率达到93％。 2-甲基-3,4,5,6-四苯基-1-(1H-1,2,4-三氮唑)吡啶高氯酸盐的固体荧光发射波长 为428nm，在乙醇溶液中发射波长为462nm；加入AcO-或F-后荧光强度明显减 低，荧光淬灭效率分别为86％、95％，说明化合物可以识别微量的F-和AcO-； 而加入Cl-、Br-、I-、和NO3 -其它阴离子后荧光强度没有明显变化(附图2)， 有其他干扰阴离子存在时也可以对F-和AcO-具有高的识别灵敏性(附图3)。
实施例2
向200mL的圆底烧瓶中加入50mL甲醇溶剂、0.50mmol 2,3,4,5,6-五苯基 高氯酸吡喃盐和0.50mmol 3-氨基-1,2,4-三氮唑，30℃下搅拌至完全溶解，然后 加入0.50mmol乙二胺，室温下搅拌反应10分钟后，加入1.00mmol冰乙酸， 持续搅拌反应6h；之后蒸掉溶剂，得到固体，乙醇重结晶两次，50℃真空干燥 后，得到产品，产率89％。表征数据：1H NMR(400MHz,DMSO)δ(ppm):14.47 (s,1H),8.39(s,1H),7.24(m,4H),7.11(m,10H),7.01(s,5H),6.99(m,6H).13C NMR(126MHz,DMSO)δ(ppm):163.71,156.88,155.98,154.73,145.42,132.07, 131.57,130.61,129.41,128.27,125.03,123.77,115.19,55.83,40.02,39.98,39.93, 39.85,39.81,39.69,39.64,39.48,39.31,39.14,38.98.MS(ESI)m/z:527.4152 (M+)。产物为2,3,4,5,6-五苯基-1-(1H-1,2,4-三氮唑)吡啶高氯酸盐，分子式为：
2,3,4,5,6-五苯基-1-(1H-1,2,4-三氮唑)吡啶高氯酸盐对大肠杆菌、金黄色葡萄球菌、黑曲霉菌展现了优异的抗菌活性，杀菌率达到95％以上；其固体荧光 发射为426nm，在乙醇溶液中发射波长为467nm；加入AcO-或F-后荧光强度明 显减低，荧光淬灭效率分别为70％、94％；而加入Cl-、Br-、I-、和NO3 -其它阴 离子后荧光强度没有明显变化，说明化合物可以识别微量的F-和AcO-。
实施例3
向100mL的圆底烧瓶中加入30mL甲醇溶剂、0.40mmol 2,4,5-三苯基高氯 酸吡喃盐和0.40mmol 3-氨基-1,2,4-三氮唑，室温下搅拌至完全溶解，然后加入 0.50mmol三乙胺，室温下搅拌反应10分钟后，加入0.8mmol冰乙酸，持续搅 拌反应3h；之后蒸掉溶剂，得到浅黄色固体，再利用乙醇重结晶两次，40℃真 空干燥后，得到白色产品，产率86％。表征数据：1H NMR(400MHz,DMSO)δ (ppm):14.93(s,1H),9.40(s,1H),8.81(s,1H),8.47(s,1H),7.53(s,1H),7.51(s, 2H),7.48(s,1H),7.46(s,2H),7.44(s,2H),7.41(d,J＝7.2Hz,5H),7.35(s,2H). 13C NMR(126MHz,DMSO)δ(ppm):158.69,156.98,153.05,146.33,145.85,137.88,134.95,133.24,131.24,131.15,130.74,130.55,129.78,129.76,129.31,129.21,128.80,128.77,128.71.MS(ESI)m/z:375.1278(M+).产物为1-(1H-1,2,4- 三氮唑)-2,4,5-三苯基吡啶高氯酸盐，结构式为：
通过菌落计数得出1-(1H-1,2,4-三氮唑)-2,4,5-三苯基吡啶高氯酸盐对大肠 杆菌、金黄色葡萄球菌、黑曲霉菌都具有优异抗菌活性，杀菌率达到95％以上。 化合物固体荧光发射为438nm，在乙醇溶液中发射波长为480nm，对不同阴离 子具有不同的荧光识别性能。
实施例4
向200mL的圆底烧瓶中加入50mL甲醇溶剂、0.60mmol 2-萘基-4,5-二苯 基高氯酸吡喃盐和0.60mmol 3-氨基-1,2,4-三氮唑，室温下搅拌至完全溶解，然 后加入0.70mmol三乙胺，室温下搅拌反应15分钟后，加入1.5mmol冰乙酸， 持续搅拌反应5h；之后蒸掉溶剂，得到固体，再利用乙醇重结晶两次，50℃真 空干燥后，得到产品，产率88％。表征数据：1H NMR(400MHz,DMSO)δ(ppm): 14.68(s,1H),9.55(s,1H),8.58(m,2H),8.12(m,1H),8.06-8.01(m,2H),7.87 (m,1H),7.69(m,1H),7.63-7.58(m,3H),7.49-7.40(m,11H).13C NMR(126MHz,DMSO)δ(ppm):158.50,156.85,151.97,146.42,145.36,138.48,134.87,133.55, 132.61,131.81,131.26,130.56,129.87,129.24,129.09,128.85,128.67,128.39, 127.51,126.77,124.95.MS(ESI)m/z:425.1799(M+)。产物为2-萘基-4,5-二苯基-1- (1H-1,2,4-三氮唑)吡啶高氯酸盐，结构式为：
2-萘基-4,5-二苯基-1-(1H-1,2,4-三氮唑)吡啶高氯酸盐对大肠杆菌、金黄色 葡萄球菌、黑曲霉菌展现了优异的抗菌活性。其固体荧光发射为470nm，在乙 醇溶液中发射波长为460nm，对不同阴离子具有不同的荧光识别性能。
实施例5
向100mL的圆底烧瓶中加入30mL乙醇溶剂、0.40mmol 2-(4,4’-联苯基) -4,5-二苯基高氯酸吡喃盐和0.40mmol 3-氨基-1,2,4-三氮唑，室温下搅拌至完全 溶解，然后加入0.50mmol三乙胺，室温下搅拌反应10分钟后，加入1.0mmol 甲酸，持续搅拌反应6h；之后旋蒸掉溶剂，得到固体，再利用乙醇重结晶两次， 40℃真空干燥后，得到产品，产率83％。表征数据：：1H NMR(400MHz,DMSO) δ(ppm):14.99(s,1H),9.43(s,1H),8.87(s,1H),8.56(s,1H),7.83(m,2H),7.74(m, 2H),7.64(m,2H),7.53-7.48(m,5H),7.45(m,6H),7.40-7.37(m,2H).13C NMR (126MHz,DMSO)δ(ppm):158.58,157.06,152.77,146.36,145.98,142.56,138.34, 137.80,134.98,133.26,130.78,130.55,130.20,130.03,129.76,129.21,129.13, 128.81,128.72,128.47,126.87.MS(ESI)m/z:451.1924(M+)。产物为1-(1H-1,2,4- 三氮唑)-2-(4,4’-联苯基)-4,5-二苯基吡啶高氯酸盐，结构式为：
产率44％。表征数据
1-(1H-1,2,4-三氮唑)-2-(4,4’-联苯基)-4,5-二苯基吡啶高氯酸盐对大肠杆菌、金黄色葡萄球菌、黑曲霉菌展现了抗菌活性；其固体荧光发射为454nm， 在乙醇溶液中发射波长为545nm，加入AcO-或F-后荧光强度明显减低，荧光淬 灭效率分别为81％、92％；而加入Cl-、Br-、I-、和NO3 -其它阴离子后荧光强度 没有明显变化，说明对不同阴离子具有不同的荧光识别性能。
Claims (10)
1.一种1,2,4-三氮唑吡啶盐化合物，其特征在于，所述的1,2,4-三氮唑吡啶盐化合物的结构式如(I)所示：
式(Ⅰ)中，R为H或OMe或Me；X为ClO4。
2.一种1,2,4-三氮唑吡啶盐化合物的制备方法，其特征在于，步骤如下：
将不同取代基吡喃盐溶于有机溶剂，再加入3-氨基-1,2,4-三氮唑溶液和碱助剂，在10～40℃温度条件下搅拌反应2～20分钟后，滴加适量酸助剂，继续搅拌反应0.5～10h后，减压蒸馏除去溶剂，得到粗产品；再经过重结晶、洗涤纯化后，40～80℃真空干燥后得到产品；其中，吡喃盐、3-氨基-1,2,4-三氮唑、碱助剂、酸助剂的摩尔比为1：1：0.05～2：0.5～3。
3.根据权利要求2所述的1,2,4-三氮唑吡啶盐化合物的制备方法，其特征在于，所述的不同取代基吡喃盐为2-甲基-3,4,5,6-四苯基吡喃盐、2,3,4,5,6-五苯基吡喃盐、2,4,5-三苯基吡喃盐、2-(4-甲氧基苯基)-4,5-二苯基吡喃盐，2-(4-甲基苯基)-4,5-二苯基吡喃盐、2-萘基-4,5-二苯基吡喃盐和2-(4,4’-联苯基)-4,5-二苯基吡喃盐中的一种。
4.根据权利要求2或3所述的1,2,4-三氮唑吡啶盐化合物的制备方法，其特征在于，所述的有机溶剂为二氯甲烷、三氯甲烷、甲醇、乙醇中的一种或两种以上混合。
5.根据权利要求2或3所述的1,2,4-三氮唑吡啶盐化合物的制备方法，其特征在于，所述的碱助剂为C4以下的有机胺、碱金属碳酸盐、碱金属氢氧化物中的一种或两种以上混合。
6.根据权利要求4所述的1,2,4-三氮唑吡啶盐化合物的制备方法，其特征在于，所述的碱助剂为C4以下的有机胺、碱金属碳酸盐、碱金属氢氧化物中的一种或两种以上混合。
7.根据权利要求2、3或6所述的1,2,4-三氮唑吡啶盐化合物的制备方法，其特征在于，所述的酸助剂为C4以下的有机酸中的一种或两种以上混合。
8.根据权利要求4所述的1,2,4-三氮唑吡啶盐化合物的制备方法，其特征在于，所述的酸助剂为C4以下的有机酸中的一种或两种以上混合。
9.根据权利要求5所述的1,2,4-三氮唑吡啶盐化合物的制备方法，其特征在于，所述的酸助剂为C4以下的有机酸中的一种或两种以上混合。
10.一种1,2,4-三氮唑吡啶盐化合物，用于抗菌和发光材料领域。
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| WO1992009595A1 (de) * | 1990-11-29 | 1992-06-11 | Byk Gulden Lomberg Chemische Fabrik Gmbh | Neue und bekannte disulfide und ihre verwendung |
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