CN102229579B - A kind of cation is the preparation method of the Br φ nsted acidic ion liquid of 1,3-thiazoles-2-thiones - Google Patents
A kind of cation is the preparation method of the Br φ nsted acidic ion liquid of 1,3-thiazoles-2-thiones Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000002500 ions Chemical class 0.000 title claims abstract description 5
- 239000007788 liquid Substances 0.000 title claims description 15
- 230000002378 acidificating effect Effects 0.000 title claims 2
- 150000001768 cations Chemical class 0.000 title abstract description 7
- -1 1,3-thiazole-2-thione cation Chemical class 0.000 claims abstract description 43
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 6
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims 3
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 claims 2
- 239000012429 reaction media Substances 0.000 claims 2
- 229950004288 tosilate Drugs 0.000 claims 2
- 238000000034 method Methods 0.000 claims 1
- 238000006561 solvent free reaction Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 62
- 239000002608 ionic liquid Substances 0.000 abstract description 47
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 6
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical class SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011831 acidic ionic liquid Substances 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- FMNLAYRURATQMB-UHFFFAOYSA-N 1-sulfanylidene-1,3-thiazole Chemical compound S=S1C=CN=C1 FMNLAYRURATQMB-UHFFFAOYSA-N 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 abstract description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 abstract description 2
- 229940089960 chloroacetate Drugs 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 abstract description 2
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 125000002560 nitrile group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 35
- 238000005481 NMR spectroscopy Methods 0.000 description 24
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- HTYWMMZQCZGEJQ-UHFFFAOYSA-N 3-butyl-1,3-thiazole-2-thione Chemical compound CCCCN1C=CSC1=S HTYWMMZQCZGEJQ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- KYBPVHHFIHFPOZ-UHFFFAOYSA-N propane-1-sulfonic acid;3h-1,3-thiazole-2-thione Chemical compound S=C1NC=CS1.CCCS(O)(=O)=O KYBPVHHFIHFPOZ-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
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- Thiazole And Isothizaole Compounds (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
本发明涉及一种基于1，3‑噻唑‑2‑硫酮类阳离子的酸性离子液体的制备方法。该离子液体的阳离子为1，3‑噻唑‑2‑硫酮衍生物，阴离子为 酸根离子。阳离子噻唑硫酮3位被碳原子数1‑16的所有直链或支链烷基、碳原子数1‑16的部分氟化或全氟化的所有直链或支链烷基、碳原子数3‑4的烷基磺酸以及所有含有醚基、羟基、羧基、腈基官能团且碳原子数为2‑10的直链或支链烷基中的其中之一所取代。阴离子为氯、溴、碘、氟硼酸根、氟磷酸根、硫酸根、硫酸氢根、磷酸二氢根、磷酸根、硝酸根、对甲苯磺酸根、三氟乙酸根、三氟甲磺酸根、乳酸根、氯乙酸根、甲酸根、乙酸根、丙酸根、甲磺酸根中的其中之一。The present invention relates to a kind of based on 1,3-thiazole-2-thione cation Preparation method of acidic ionic liquid. The cation of the ionic liquid is 1,3-thiazole-2-thione derivative, and the anion is Acid ion. The 3-position of cationic thiazolethione is all linear or branched alkyl groups with 1-16 carbon atoms, all linear or branched alkyl groups with 1-16 carbon atoms partially fluorinated or perfluorinated, the number of carbon atoms 3-4 alkyl sulfonic acid and all linear or branched alkyl groups containing ether, hydroxyl, carboxyl, and nitrile functional groups and carbon atoms of 2-10 are substituted. Anions are chlorine, bromine, iodine, fluoroborate, fluorophosphate, sulfate, hydrogensulfate, dihydrogenphosphate, phosphate, nitrate, p-toluenesulfonate, trifluoroacetate, trifluoromethanesulfonate, One of lactate, chloroacetate, formate, acetate, propionate, and methanesulfonate.
Description
技术领域 technical field
本发明涉及一种基于1，3-噻唑-2-硫酮类阳离子的新型酸性离子液体的制备方法。 The present invention relates to a novel based on 1,3-thiazole-2-thione cations Preparation method of acidic ionic liquid.
技术背景 technical background
离子液体(ILs)是指全部由离子组成的液体。离子液体又称为室温离子液体、室温熔融盐、有机离子液体等。离子液体一般是由特定的体积相对较大的结构不对称的有机阳离子和体积相对较小的无机或有机阴离子构成的、在室温或近于室温下呈液态的物质。近年来，离子液体作为一种“绿色”溶剂或催化剂在有机合成中发挥了独特的作用。首先，离子液体作为溶剂为化学反应提供了不同于传统分子溶剂的环境，它可以改变反应的机理，使催化剂的活性和稳定性更好、选择性和转化率更高；其次，溶解在离子液体中的催化剂，具有均相催化效率高，多相催化易分离的优点，产物的分离可以用倾析、萃取和蒸馏等方法；再者因离子液体无蒸气压，液相温度范围宽，使得分离易于进行。因此，有关离子液体的应用研究正在越来越多地受到人们的关注。 Ionic liquids (ILs) are liquids composed entirely of ions. Ionic liquids are also called room temperature ionic liquids, room temperature molten salts, organic ionic liquids, etc. Ionic liquids are generally composed of specific relatively large organic cations with asymmetric structure and relatively small inorganic or organic anions, and are liquid substances at room temperature or near room temperature. In recent years, ionic liquids have played a unique role in organic synthesis as a "green" solvent or catalyst. First of all, as a solvent, ionic liquid provides an environment different from traditional molecular solvents for chemical reactions. It can change the mechanism of the reaction, making the catalyst more active and stable, with higher selectivity and conversion; The catalyst in the catalyst has the advantages of high homogeneous catalysis efficiency and easy separation of heterogeneous catalysis. The separation of products can be done by decantation, extraction and distillation. Furthermore, because the ionic liquid has no vapor pressure and the temperature range of the liquid phase is wide, the separation Easy to do. Therefore, the research on the application of ionic liquids is attracting more and more attention.
近年来人们关于离子液体的研究主要集中于阳离子为季铵盐离子、季鏻盐离子、咪唑盐离子和吡啶盐离子等的离子液体。1914年，Walden等人在The Journal of Organic Chemistry(1929，1291)上报道了第一个离子液体。此后离子液体的合成及应用如雨后春笋，尤其是功能化离子液体，在很多领域应用广泛。2002年Cole等人在Journal of the American Chemical Society(2002，124：5962-5963)首次报道了具有较强Bronsted酸性的离子液体的合成。何鸣元等在Green Chemistry(2003，5：38-39)报道了[HMIM]BF4([HMIM]为1-甲基咪唑阳离子)离子液体的合成及应用。2003年，邓有全等人在Catalysis Communications(2003，4：597-601)报道了两种磺酸基功能化的咪唑类酸性离子液体，发现在烯烃的聚合反应中有很好的反应活性和选择性。至今，尚未见阳离子为1，3-噻唑-2-硫酮的离子液体的合成研究报道。鉴于噻唑硫酮环具有结构可调、稳定性好等优点，本发明涉及一种基于1，3-噻唑-2-硫酮类阳离子的新型酸性离子液体的合成方法。 In recent years, people's research on ionic liquids mainly focuses on ionic liquids whose cations are quaternary ammonium salt ions, quaternary phosphonium salt ions, imidazolium salt ions and pyridinium salt ions. In 1914, Walden et al. reported the first ionic liquid in The Journal of Organic Chemistry (1929, 1291). Since then, the synthesis and application of ionic liquids have sprung up, especially functionalized ionic liquids, which are widely used in many fields. In 2002, Cole et al first reported the synthesis of ionic liquids with strong Bronsted acidity in Journal of the American Chemical Society (2002, 124:5962-5963). He Mingyuan et al reported the synthesis and application of [HMIM]BF 4 ([HMIM] is 1-methylimidazolium cation) ionic liquid in Green Chemistry (2003, 5:38-39). In 2003, Deng Youquan and others reported two kinds of imidazole acidic ionic liquids functionalized with sulfonic acid groups in Catalysis Communications (2003, 4:597-601), and found that they have good reactivity and selectivity in the polymerization reaction of olefins . So far, there is no report on the synthesis of ionic liquids whose cation is 1,3-thiazole-2-thione. In view of the thiazolethione ring having the advantages of adjustable structure and good stability, the present invention relates to a novel compound based on 1,3-thiazole-2-thione cations Synthetic method of acidic ionic liquid.
发明内容 Contents of the invention
现有技术中的离子液体主要集中于阳离子为季铵盐离子、季鏻盐离子、咪唑盐离子和吡啶盐离子等的离子液体，未见有基于1，3-噻唑-2-硫酮类阳离子的离子液体的研究报道。针对现有离子液体阳离子种类尚不丰富的问题，本发明提供了一种具有结构可调、稳定性好等优点的基于1，3-噻唑-2-硫酮类阳离子的新型离子液体的制备方法。 The ionic liquids in the prior art mainly focus on the ionic liquids whose cations are quaternary ammonium salt ions, quaternary phosphonium salt ions, imidazolium salt ions and pyridinium salt ions, etc., and there are no cations based on 1,3-thiazole-2-thione Research reports on ionic liquids. Aiming at the problem that the types of cations in the existing ionic liquids are not abundant, the present invention provides a preparation method of a novel ionic liquid based on 1,3-thiazole-2-thione cations with the advantages of adjustable structure and good stability .
本发明采用的技术方案：一种结构通式为(I)的基于1，3-噻唑-2-硫酮类阳离子的新型酸性离子液体的制备方法，其中R1基为代表碳原子数1-16的所有直链或支链烷基、碳原子数1-16的部分氟化或全氟化的所有直链或支链烷基、碳原子数3-4的烷基磺酸以及所有含有醚基、羟基、羧基、腈基官能团且碳原子数为2-10的直链或支链烷基的其中之一；X- 为氯、溴、碘、氟硼酸根、氟磷酸根、硫酸根、硫酸氢根、磷酸二氢根、磷酸根、硝酸根、对甲苯磺酸根、三氟乙酸根、三氟甲磺酸根、乳酸根、氯乙酸根、甲酸根、乙酸根、丙酸根、甲磺酸根中的其中之一，其特征在于包括如下步骤： The technical scheme adopted in the present invention: a novel compound based on 1,3-thiazole-2-thione cations with general structural formula (I) The preparation method of acidic ionic liquid, wherein R 1 group represents all linear or branched chain alkyls with 1-16 carbon atoms, all linear or branched chains with partial fluorination or perfluorination with 1-16 carbon atoms Alkyl, alkyl sulfonic acid with 3-4 carbon atoms, and one of all straight-chain or branched-chain alkyl groups with 2-10 carbon atoms containing ether, hydroxyl, carboxyl, and nitrile functional groups; X - Chlorine, bromine, iodine, fluoroborate, fluorophosphate, sulfate, hydrogensulfate, dihydrogenphosphate, phosphate, nitrate, p-toluenesulfonate, trifluoroacetate, trifluoromethanesulfonate, lactic acid One of them in root, chloroacetate, formate, acetate, propionate, methanesulfonate, it is characterized in that comprising the steps:
(1)将1，3-噻唑-2-硫酮和卤代烷按照摩尔比1∶1的比例加入反应器中，然后加入相转移催化剂四丁基溴化铵和30％NaOH溶液，搅拌，加热至80℃-90℃，反应8-12h，冷却分层后，分出有机相，用蒸馏水洗涤至水相中加入硝酸银溶液后无沉淀生成，减压蒸去溶剂，真空干燥得到3-烷基-1，3-噻唑-2-硫酮。 (1) 1,3-thiazole-2-thione and alkyl halide are added in the reactor according to the molar ratio of 1:1, then phase transfer catalyst tetrabutylammonium bromide and 30% NaOH solution are added, stirred, heated to 80°C-90°C, react for 8-12h, after cooling and layering, separate the organic phase, wash with distilled water until no precipitation is formed after adding silver nitrate solution to the water phase, evaporate the solvent under reduced pressure, and dry in vacuo to obtain 3-alkyl -1,3-thiazole-2-thione.
(2)将(1)中1，3-噻唑-2-硫酮分别与1，3-丙烷磺酸内酯、1，4-丁烷磺酸内酯按照摩尔比1∶1的比例加入反应器中，加入乙酸乙酯为溶剂，加热至80℃-90℃，反应8-12h固化，滤出固体，用乙醚和乙酸乙酯洗涤滤饼，干燥，用玛瑙研钵研细，然后加入适量乙腈和乙酸乙酯混合液加热，趁热过滤除去残留的原料，滤饼干燥得到纯净的3-烷基磺酸-1，3-噻唑-2-硫酮内盐，白色粉末。 (2) Add 1,3-thiazole-2-thione in (1) to 1,3-propane sultone and 1,4-butane sultone in a molar ratio of 1:1. In the container, add ethyl acetate as a solvent, heat to 80°C-90°C, react for 8-12h to solidify, filter out the solid, wash the filter cake with ether and ethyl acetate, dry, grind finely with an agate mortar, and then add an appropriate amount of The mixture of acetonitrile and ethyl acetate was heated, filtered while hot to remove the residual raw material, and the filter cake was dried to obtain pure 3-alkylsulfonic acid-1,3-thiazole-2-thione inner salt, white powder.
(3)将(2)、(3)中的3-烷基-1，3-噻唑-2-硫酮和3-烷基磺酸-1，3-噻唑-2-硫酮内盐和酸按照摩尔比1∶1的比例加入反应瓶中，无溶剂下加热至80℃-90℃，反应12-24h至反应液均一停止反应，冷却后将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得相应的离子液体。 (3) 3-alkyl-1,3-thiazole-2-thione and 3-alkylsulfonic acid-1,3-thiazole-2-thione inner salt in (2), (3) and Add the acid into the reaction flask according to the molar ratio of 1:1, heat to 80°C-90°C without solvent, react for 12-24h until the reaction solution is uniform and stop the reaction, after cooling, wash the product with ether three times, evaporate the ether under reduced pressure and a small amount of water, and then vacuum-dried at 100°C for 10 hours to obtain the corresponding ionic liquid.
附图说明 Description of drawings
图1为3-丁基-1，3-噻唑-2-硫酮硫酸氢盐离子液体的核磁氢谱谱图。 Fig. 1 is the proton nuclear magnetic spectrogram of 3-butyl-1,3-thiazole-2-thione bisulfate ionic liquid.
图2为3-丁基-1，3-噻唑-2-硫酮对甲苯磺酸盐离子液体的核磁氢谱谱图。 Fig. 2 is the H NMR spectrogram of 3-butyl-1,3-thiazole-2-thione p-toluenesulfonate ionic liquid.
图3为3-丁基-1，3-噻唑-2-硫酮三氟甲磺酸盐离子液体的核磁氢谱谱图。 Fig. 3 is the H NMR spectrogram of 3-butyl-1,3-thiazole-2-thione trifluoromethanesulfonate ionic liquid.
图4为3-丁基-1，3-噻唑-2-硫酮三氟乙酸盐离子液体的核磁氢谱谱图。 Figure 4 is the H NMR spectrum of 3-butyl-1,3-thiazole-2-thione trifluoroacetate ionic liquid.
图5为3-丁基磺酸-1，3-噻唑-2-硫酮硫酸氢盐离子液体核磁氢谱谱图。 Fig. 5 is the H NMR spectrum of 3-butylsulfonic acid-1,3-thiazole-2-thione bisulfate ionic liquid.
图6为3-丁基磺酸-1，3-噻唑-2-硫酮三氟甲磺酸盐离子液体核磁氢谱谱图。 Fig. 6 is a hydrogen nuclear magnetic spectrum spectrogram of 3-butylsulfonic acid-1,3-thiazole-2-thione trifluoromethanesulfonate ionic liquid.
图7为3-丁基磺酸-1，3-噻唑-2-硫酮三氟乙酸盐离子液体核磁氢谱谱图。 Fig. 7 is the H NMR spectrum of 3-butylsulfonic acid-1,3-thiazole-2-thione trifluoroacetate ionic liquid.
图8为3-丙基磺酸-1，3-噻唑-2-硫酮对甲苯磺酸盐离子液体核磁氢谱谱图。 Fig. 8 is the H NMR spectrum of 3-propylsulfonic acid-1,3-thiazole-2-thione p-toluenesulfonate ionic liquid.
图9为3-丙基磺酸-1，3-噻唑-2-硫酮磷酸二氢盐离子液体核磁氢谱谱图。 Fig. 9 is a hydrogen nuclear magnetic spectrum spectrum of 3-propylsulfonic acid-1,3-thiazole-2-thione phosphate dihydrogen salt ionic liquid.
图10为3-丙基磺酸-1，3-噻唑-2-硫酮三氟甲磺酸盐离子液体核磁氢谱谱图。 Fig. 10 is the H NMR spectrum of 3-propylsulfonic acid-1,3-thiazole-2-thione trifluoromethanesulfonate ionic liquid.
图11为3-丙基磺酸-1，3-噻唑-2-硫酮三氟乙酸盐离子液体核磁氢谱谱图。 Figure 11 is the H NMR spectrum of 3-propylsulfonic acid-1,3-thiazole-2-thione trifluoroacetate ionic liquid.
具体实施方式 detailed description
为了使本发明的技术手段、创作特征、达成目的与功效易于明白理解，下面通过具体的实施例对本发明进行进一步详细描述： In order to make the technical means, creative features, goals and effects of the present invention easy to understand, the present invention will be further described in detail below through specific examples:
实施例1：3-丁基-1，3-噻唑-2-硫酮硫酸氢盐离子液体的制备 Example 1: Preparation of 3-butyl-1,3-thiazole-2-thione bisulfate ionic liquid
25mL圆底烧瓶中，加入3-丁基-1，3-噻唑-2-硫酮(20mmol)，滴加95-98％H2SO4(20mmol)，升温至90℃，保持此温度反应12h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品，棕黄色液体。采用核磁共振仪和质谱仪检测，所得产品的参数为1H NMR(400MHz，CDCl3)：δ0.90(t，3H，CH3)，1.27-1.37(m，2H，CH2)，1.59-1.68(m，2H，CH2)，3.09(s，2H，CH2)，3.35(t，2H，CH2)，4.42(t，2H，CH2)；ESI-MS：m/z＝176[M+]，m/z＝97[M-]。 In a 25mL round bottom flask, add 3-butyl-1,3-thiazole-2-thione (20mmol), add 95-98% H 2 SO 4 (20mmol) dropwise, raise the temperature to 90°C, and keep the temperature for 12h . After the reaction, the product was washed three times with diethyl ether, the diethyl ether and a small amount of water were evaporated under reduced pressure, and then vacuum-dried at 100°C for 10 h to obtain the product as a brown-yellow liquid. Using nuclear magnetic resonance and mass spectrometer detection, the parameters of the product obtained are 1 H NMR (400MHz, CDCl 3 ): δ0.90 (t, 3H, CH 3 ), 1.27-1.37 (m, 2H, CH 2 ), 1.59- 1.68 (m, 2H, CH 2 ), 3.09 (s, 2H, CH 2 ), 3.35 (t, 2H, CH 2 ), 4.42 (t, 2H, CH 2 ); ESI-MS: m/z=176[ M + ], m/z = 97 [M - ].
实施例2：3-丁基-1，3-噻唑-2-硫酮对甲苯磺酸盐离子液体的制备 Example 2: Preparation of 3-butyl-1,3-thiazole-2-thione p-toluenesulfonate ionic liquid
25mL圆底烧瓶中，加入3-丁基-1，3-噻唑-2-硫酮(20mmol)，加入对甲苯磺酸(20mmol)，升温至90℃，保持此温度24h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品，棕黄色液体。采用核磁共振仪和质谱检测，所得产品的参数为1H NMR(400MHz，D2O)：δ0.90(t，3H，CH3)，1.18-1.76(m，4H，2×CH2)，2.37(s，3H，CH3)，3.07(t，2H，CH2)，3.71(t，2H，CH2)，4.25(t，2H，CH2)，7.33-7.68(dd，4H，Ar)；ESI-MS：m/z＝176[M+]，m/z＝171[M-]。 Add 3-butyl-1,3-thiazole-2-thione (20mmol) and p-toluenesulfonic acid (20mmol) into a 25mL round-bottomed flask, heat up to 90°C, and keep this temperature for 24h. After the reaction, the product was washed three times with diethyl ether, the diethyl ether and a small amount of water were evaporated under reduced pressure, and then vacuum-dried at 100°C for 10 h to obtain the product as a brown-yellow liquid. Using nuclear magnetic resonance and mass spectrometry detection, the parameters of the obtained product are 1 H NMR (400MHz, D 2 O): δ0.90 (t, 3H, CH 3 ), 1.18-1.76 (m, 4H, 2×CH 2 ), 2.37(s, 3H, CH 3 ), 3.07(t, 2H, CH 2 ), 3.71(t, 2H, CH 2 ), 4.25(t, 2H, CH 2 ), 7.33-7.68(dd, 4H, Ar) ; ESI-MS: m/z = 176 [M + ], m/z = 171 [M − ].
实施例3：3-丁基-1，3-噻唑-2-硫酮三氟甲磺酸盐离子液体的制备 Example 3: Preparation of 3-butyl-1,3-thiazole-2-thione trifluoromethanesulfonate ionic liquid
25mL圆底烧瓶中，加入3-丁基-1，3-噻唑-2-硫酮(20mmol)，加入三氟甲磺酸(20mmol)，升温至85℃，保持此温度12h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品，棕黄色液体。采用核磁共振仪和质谱检测，所得产品的参数为1H NMR(400MHz，CDCl3)：δ0.97(t，3H，CH3)，1.44-1.53(m，2H，CH2)，1.74-1.82(m，2H，CH2)，3.35(t，2H，CH2)，3.82(t，2H，CH2)，4.48(t，2H，CH2)；ESI-MS：m/z＝176[M+]，m/z＝149[M-]。 Add 3-butyl-1,3-thiazole-2-thione (20mmol) and trifluoromethanesulfonic acid (20mmol) into a 25mL round-bottomed flask, raise the temperature to 85°C, and keep this temperature for 12h. After the reaction, the product was washed three times with diethyl ether, the diethyl ether and a small amount of water were evaporated under reduced pressure, and then vacuum-dried at 100°C for 10 h to obtain the product as a brown-yellow liquid. Using nuclear magnetic resonance and mass spectrometry detection, the parameters of the obtained product are 1 H NMR (400MHz, CDCl 3 ): δ0.97 (t, 3H, CH 3 ), 1.44-1.53 (m, 2H, CH 2 ), 1.74-1.82 (m, 2H, CH 2 ), 3.35 (t, 2H, CH 2 ), 3.82 (t, 2H, CH 2 ), 4.48 (t, 2H, CH 2 ); ESI-MS: m/z=176 [M + ], m/z = 149 [M - ].
实施例4：3-丁基-1，3-噻唑-2-硫酮三氟乙酸盐离子液体的制备 Example 4: Preparation of 3-butyl-1,3-thiazole-2-thione trifluoroacetate ionic liquid
25mL圆底烧瓶中，加入3-丁基-1，3-噻唑-2-硫酮(10mmol)，滴加三氟乙酸(10mmol)，升温至85℃，保持此温度反应12h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品，棕黄色液体。采用核磁共振仪检测，所得产品的参数为1H NMR(400MHz，DMSO-d6)：δ0.87(t，3H，CH3)，1.25-1.40(m，2H，CH2)，1.53-1.66(m，2H，CH2)，3.13(t，2H，CH2)，3.46(t，2H，CH2)，4.16(t，2H，CH2)，(b，1H，NH)；ESI-MS：m/z＝176[M+]，m/z＝113[M-]。 3-Butyl-1,3-thiazole-2-thione (10 mmol) was added to a 25 mL round bottom flask, trifluoroacetic acid (10 mmol) was added dropwise, the temperature was raised to 85° C., and the temperature was maintained for 12 h. After the reaction, the product was washed three times with diethyl ether, the diethyl ether and a small amount of water were evaporated under reduced pressure, and then vacuum-dried at 100°C for 10 h to obtain the product as a brown-yellow liquid. Detected by nuclear magnetic resonance, the parameters of the obtained product are 1 H NMR (400MHz, DMSO-d 6 ): δ0.87 (t, 3H, CH 3 ), 1.25-1.40 (m, 2H, CH 2 ), 1.53-1.66 (m, 2H, CH 2 ), 3.13 (t, 2H, CH 2 ), 3.46 (t, 2H, CH 2 ), 4.16 (t, 2H, CH 2 ), (b, 1H, NH); ESI-MS : m/z=176[M + ], m/z = 113[M-].
实施例5：3-丁基磺酸-1，3-噻唑-2-硫酮硫酸氢盐离子液体的制备 Example 5: Preparation of 3-butylsulfonic acid-1,3-thiazole-2-thione bisulfate ionic liquid
25mL圆底烧瓶中，加入3-丁基磺酸-1，3-噻唑-2-硫酮内盐(10mmol)，滴加95-98％H2SO4 (20mmol)，升温至90℃，保持此温度24h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品。采用核磁共振仪和质谱仪检测，所得产品的参数为1H NMR(400MHz，D2O)：1.69-2.01(m，4H，2CH2)，2.80(t，2H，CH2)，3.22(t，2H，CH2)，3.65(t，2H，CH2)，4.20(t，2H，CH2)；ESI-MS：m/z＝256[M+]，m/z＝97[M-]。 In a 25mL round bottom flask, add 3-butylsulfonic acid-1,3-thiazole-2-thione inner salt (10mmol), add 95-98% H 2 SO 4 (20mmol) dropwise, raise the temperature to 90°C, keep This temperature is 24h. After the reaction, the product was washed three times with ether, the ether and a small amount of water were evaporated under reduced pressure, and then dried in vacuum at 100°C for 10 hours to obtain the product. Adopt nuclear magnetic resonance instrument and mass spectrometer to detect, the parameter of obtained product is 1 H NMR (400MHz, D 2 O): 1.69-2.01 (m, 4H, 2CH 2 ), 2.80 (t, 2H, CH 2 ), 3.22 (t , 2H, CH 2 ), 3.65 (t, 2H, CH 2 ), 4.20 (t, 2H, CH 2 ); ESI-MS: m/z=256[M + ], m/z=97[M − ] .
实施例6：3-丁基磺酸-1，3-噻唑-2-硫酮三氟甲磺酸盐离子液体的制备 Example 6: Preparation of 3-butylsulfonic acid-1,3-thiazole-2-thione trifluoromethanesulfonate ionic liquid
25mL圆底烧瓶中，加入3-丁基磺酸基-1，3-噻唑-2-硫酮(20mmol)，加入三氟甲磺酸(20mmol)，升温至80℃，保持此温度12h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品，淡黄色液体。采用核磁共振仪和质谱仪检测，所得产品的参数为1H NMR(400MHz，D2O)：δ1.70-1.86(m，4H，2CH2)，2.81(t，2H，CH2)，3.23(t，2H，CH2)，3.67(t，2H，CH2)，4.21(t，2H，CH2)；ESI-MS：m/z＝256[M+]，m/z＝149[M-]。 Add 3-butylsulfonate-1,3-thiazole-2-thione (20mmol) and trifluoromethanesulfonic acid (20mmol) into a 25mL round-bottomed flask, heat up to 80°C, and keep this temperature for 12h. After the reaction, the product was washed three times with ether, and the ether and a small amount of water were evaporated under reduced pressure, and then dried in vacuum at 100°C for 10 hours to obtain the product as a light yellow liquid. Using nuclear magnetic resonance and mass spectrometer detection, the parameters of the product obtained are 1 H NMR (400MHz, D 2 O): δ1.70-1.86 (m, 4H, 2CH 2 ), 2.81 (t, 2H, CH 2 ), 3.23 (t, 2H, CH 2 ), 3.67 (t, 2H, CH 2 ), 4.21 (t, 2H, CH 2 ); ESI-MS: m/z=256[M + ], m/z=149[M - ].
实施例7：3-丁基磺酸-1，3-噻唑-2-硫酮三氟乙酸盐离子液体的制备 Example 7: Preparation of 3-butylsulfonic acid-1,3-thiazole-2-thione trifluoroacetate ionic liquid
25mL圆底烧瓶中，加入3-丁基磺酸-1，3-噻唑-2-硫酮内盐(10mmol)，滴加三氟乙酸(10mmol)，升温至90℃，保持此温度反应24h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品，淡黄色液体。采用核磁共振仪和质谱仪检测，所得产品的参数为1H NMR(400MHz，D2O)：δ1.70-1.85(m，4H，2CH2)，2.79(t，2H，CH2)，3.23(t，2H，CH2)，3.66(t，2H，CH2)，4.20(t，2H，CH2)；质谱ESI-MS：m/z＝256[M+]，m/z＝113[M-]。 In a 25mL round bottom flask, add 3-butylsulfonic acid-1,3-thiazole-2-thione internal salt (10mmol), drop trifluoroacetic acid (10mmol), raise the temperature to 90°C, and keep this temperature for 24h. After the reaction, the product was washed three times with ether, the ether and a small amount of water were evaporated under reduced pressure, and then dried in vacuum at 100°C for 10 hours to obtain the product as a light yellow liquid. Using nuclear magnetic resonance and mass spectrometer detection, the parameters of the product obtained are 1 H NMR (400MHz, D 2 O): δ1.70-1.85 (m, 4H, 2CH 2 ), 2.79 (t, 2H, CH 2 ), 3.23 (t, 2H, CH 2 ), 3.66 (t, 2H, CH 2 ), 4.20 (t, 2H, CH 2 ); mass spectrum ESI-MS: m/z=256[M + ], m/z=113[ M-] .
实施例8：3-丙基磺酸-1，3-噻唑-2-硫酮对甲苯磺酸盐离子液体的制备 Example 8: Preparation of 3-propylsulfonic acid-1,3-thiazole-2-thione p-toluenesulfonate ionic liquid
25mL圆底烧瓶中，加入3-丙基磺酸-1，3-噻唑-2-硫酮内盐(10mmol)，加入对甲苯磺酸(10mmol)，升温至90℃，保持此温度24h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品，淡黄色液体。采用核磁共振仪和质谱仪检测，所得产品的参数为1H NMR(400MHz，D2O)：δ2.10-2.17(m，2H，CH2)，2.29(s，3H，CH3)，2.94(t，2H，CH2)，3.33(t，2H，CH2)，3.66(t，2H，CH2)，4.20(t，2H，CH2)，7.25-7.60(dd， J＝8.2Hz，4H，ArH)；ESI-MS：m/z＝242[M+]，m/z＝171[M-]。 In a 25mL round bottom flask, add 3-propylsulfonic acid-1,3-thiazole-2-thione inner salt (10mmol), add p-toluenesulfonic acid (10mmol), heat up to 90°C, and keep this temperature for 24h. After the reaction, the product was washed three times with ether, the ether and a small amount of water were evaporated under reduced pressure, and then dried in vacuum at 100°C for 10 hours to obtain the product as a light yellow liquid. Using nuclear magnetic resonance and mass spectrometer detection, the parameters of the product obtained are 1 H NMR (400MHz, D 2 O): δ2.10-2.17 (m, 2H, CH 2 ), 2.29 (s, 3H, CH 3 ), 2.94 (t, 2H, CH 2 ), 3.33 (t, 2H, CH 2 ), 3.66 (t, 2H, CH 2 ), 4.20 (t, 2H, CH 2 ), 7.25-7.60 (dd, J=8.2Hz, 4H, ArH); ESI-MS: m/z = 242 [M + ], m/z = 171 [M − ].
实施例9：3-丙基磺酸-1，3-噻唑-2-硫酮磷酸二氢盐离子液体的制备 Example 9: Preparation of 3-propylsulfonic acid-1,3-thiazole-2-thione dihydrogen phosphate ionic liquid
25mL圆底烧瓶中，加入3-丙基磺酸-1，3-噻唑-2-硫酮(10mmol)，加入磷酸(10mmol)，升温至90℃，保持此温度回流24h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品，淡黄色液体。采用核磁共振仪和质谱仪检测，所得产品的参数为1H NMR(400MHz，D2O)：δ2.16-2.23(m，2H，CH2)，2.93(t，2H，CH2)，3.42(t，2H，CH2)，3.76(t，2H，CH2)，4.30(t，2H，CH2)；ESI-MS：m/z＝242[M+]，m/z＝97[M-]。 Add 3-propylsulfonic acid-1,3-thiazole-2-thione (10mmol) and phosphoric acid (10mmol) into a 25mL round-bottomed flask, raise the temperature to 90°C, and keep the temperature under reflux for 24h. After the reaction, the product was washed three times with ether, the ether and a small amount of water were evaporated under reduced pressure, and then dried in vacuum at 100°C for 10 hours to obtain the product as a light yellow liquid. Adopt nuclear magnetic resonance instrument and mass spectrometer detection, the parameter of obtained product is 1 H NMR (400MHz, D 2 O): δ2.16-2.23 (m, 2H, CH 2 ), 2.93 (t, 2H, CH 2 ), 3.42 (t, 2H, CH 2 ), 3.76 (t, 2H, CH 2 ), 4.30 (t, 2H, CH 2 ); ESI-MS: m/z=242[M + ], m/z=97[M - ].
实施例10：3-丙磺酸基-1，3-噻唑-2-硫酮三氟甲磺酸盐离子液体的制备 Example 10: Preparation of 3-propanesulfonate-1,3-thiazole-2-thione trifluoromethanesulfonate ionic liquid
25mL圆底烧瓶中，加入3-丙基磺酸-1，3-噻唑-2-硫酮(20mmol)，加入三氟甲磺酸(20mmol)，升温至90℃，保持此温度12h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品，淡黄色液体。采用核磁共振仪和质谱仪检测，所得产品的参数为1H NMR(400MHz，D2O)：δ2.12-2.18(m，2H，CH2)，2.94(t，2H，CH2)，3.37(t，2H，CH2)，3.71(t，2H，CH2)，4.24(t，2H，CH2)；ESI-MS：m/z＝242[M+]，m/z＝149[M-]。 Add 3-propylsulfonic acid-1,3-thiazole-2-thione (20mmol) to a 25mL round bottom flask, add trifluoromethanesulfonic acid (20mmol), heat up to 90°C, and keep this temperature for 12h. After the reaction, the product was washed three times with ether, the ether and a small amount of water were evaporated under reduced pressure, and then dried in vacuum at 100°C for 10 hours to obtain the product as a light yellow liquid. Adopt NMR and mass spectrometer detection, the parameters of the product obtained are 1 H NMR (400MHz, D 2 O): δ2.12-2.18 (m, 2H, CH 2 ), 2.94 (t, 2H, CH 2 ), 3.37 (t, 2H, CH 2 ), 3.71 (t, 2H, CH 2 ), 4.24 (t, 2H, CH 2 ); ESI-MS: m/z=242[M + ], m/z=149[M - ].
实施例11：3-丙基磺酸-1，3-噻唑-2-硫酮三氟乙酸盐离子液体的制备 Example 11: Preparation of 3-propylsulfonic acid-1,3-thiazole-2-thione trifluoroacetate ionic liquid
25mL圆底烧瓶中，加入3-丙磺酸基-1，3-噻唑-2-硫酮内盐(10mmol)，滴加三氟乙酸(10mmol)，升温至90℃，保持此温度反应12h。反应完将产物用乙醚洗涤三次，减压蒸去乙醚和少量的水分，然后真空100℃干燥10h，即得到产品，淡黄色液体。采用核磁共振仪和质谱仪检测，所得产品的参数为1H NMR(400MHz，D2O)：δ2.12-2.27(m，2H，CH2)，3.03(t，2H，CH2)，3.46(t，2H，CH2)，3.79(t，2H，CH2)，4.33(t，2H，CH2)；质谱ESI-MS：m/z＝242[M+]，m/z＝149[M-]。 In a 25mL round bottom flask, add 3-propanesulfonate-1,3-thiazole-2-thione internal salt (10mmol), drop trifluoroacetic acid (10mmol), raise the temperature to 90°C, and keep this temperature for 12h. After the reaction, the product was washed three times with ether, the ether and a small amount of water were evaporated under reduced pressure, and then dried in vacuum at 100°C for 10 hours to obtain the product as a light yellow liquid. Adopt NMR and mass spectrometer detection, the parameters of the product obtained are 1 H NMR (400MHz, D 2 O): δ2.12-2.27 (m, 2H, CH 2 ), 3.03 (t, 2H, CH 2 ), 3.46 (t, 2H, CH 2 ), 3.79 (t, 2H, CH 2 ), 4.33 (t, 2H, CH 2 ); mass spectrum ESI-MS: m/z=242[M + ], m/z=149[ M-] .
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