CN1798731A - Ionic liquid comprising uronium cations or thiouronium cations - Google Patents
Ionic liquid comprising uronium cations or thiouronium cations Download PDFInfo
- Publication number
- CN1798731A CN1798731A CN 200480015435 CN200480015435A CN1798731A CN 1798731 A CN1798731 A CN 1798731A CN 200480015435 CN200480015435 CN 200480015435 CN 200480015435 A CN200480015435 A CN 200480015435A CN 1798731 A CN1798731 A CN 1798731A
- Authority
- CN
- China
- Prior art keywords
- carbon atom
- salt
- replace
- substituent
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 uronium cations Chemical class 0.000 title abstract description 45
- 239000002608 ionic liquid Substances 0.000 title abstract description 10
- 150000001768 cations Chemical class 0.000 title abstract 2
- 150000003839 salts Chemical class 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 84
- 150000001721 carbon Chemical group 0.000 claims description 75
- 125000001424 substituent group Chemical group 0.000 claims description 44
- 229910052731 fluorine Inorganic materials 0.000 claims description 41
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 27
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- 229920006395 saturated elastomer Polymers 0.000 claims description 20
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910004013 NO 2 Inorganic materials 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910016467 AlCl 4 Inorganic materials 0.000 claims description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 238000005804 alkylation reaction Methods 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 230000026030 halogenation Effects 0.000 claims description 3
- 238000005658 halogenation reaction Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical group 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 150000003672 ureas Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 229910052757 nitrogen Inorganic materials 0.000 description 72
- 239000002904 solvent Substances 0.000 description 31
- 229910052698 phosphorus Inorganic materials 0.000 description 20
- 239000011541 reaction mixture Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 16
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 15
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 238000004293 19F NMR spectroscopy Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 125000005500 uronium group Chemical group 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- UVECLJDRPFNRRQ-UHFFFAOYSA-N ethyl trifluoromethanesulfonate Chemical compound CCOS(=O)(=O)C(F)(F)F UVECLJDRPFNRRQ-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- KDDQRKBRJSGMQE-UHFFFAOYSA-N 4-thiazolyl Chemical compound [C]1=CSC=N1 KDDQRKBRJSGMQE-UHFFFAOYSA-N 0.000 description 1
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000006117 Diels-Alder cycloaddition reaction Methods 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002618 bicyclic heterocycle group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- YVXHZKKCZYLQOP-UHFFFAOYSA-N hept-1-yne Chemical compound CCCCCC#C YVXHZKKCZYLQOP-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical class COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 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 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- VFIZBHJTOHUOEK-UHFFFAOYSA-N s-ethylisothiourea Chemical compound CCSC(N)=N VFIZBHJTOHUOEK-UHFFFAOYSA-N 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a ionic liquid comprising salts of uronium cations or thiouronium cations, a preparing method and usage thereof.
Description
The present invention relates to contain urea (uronium) or thiocarbamide (thiouronium) positively charged ion and various anionic salt, relate to the preparation method of these salts and as ion liquid purposes.
Ionic liquid or liquid salt are the ionic species that contains organic cation and general inorganic anion.They do not contain neutral molecule and have the fusing point that is lower than 373K usually.Known in the state of the art have multiple as ion liquid compound.For example, Hurley and Wier disclose solvent-free ionic liquid first in a series of United States Patent (USP)s (US2,446,331, US 2,446,339 and US 2,446,350).These " room temperature fused salts " are based on AlCl
3Halid with multiple positive alkyl pyridine.
In recent years, some comments (R.Sheldon " Catalyticreations in ionic liquids ", Chem.Commun., 2001,2399-2407 have been delivered about this theme; M.J.Earle, K.R.Seddon " Ionic Liquids.Green solvent for the future ", Pure Appl.Chem., 72 (2000), 1391-1398; P.Wasserscheid, W.Keim " IonischeFl ü ssigkeiten-neue L sungen f ü r die Ubergangsmetall-katalyse " [IonicLiquids-Novel Solutions for Transition-Metal Catalysis], Angew.Chem., 112 (2000), 3926-3945; T.Welton " Room temperature ionic liquids, Solvents for synthesis and catalysis ", Chem.Rev., 92 (1999), 2071-2083; R.Hagiwara, Ya.Ito " Room temperature ionic liquids of alkylimidazoliumcations and fluoroanions ", Journal of fluorine Chem., 105 (2000), 221-227).
Ion liquid character, for example fusing point, thermal and electrochemical stability, viscosity greatly are subjected to the influence of anionic type.On the contrary, can be by suitable selection anionic/cationic to changing polarity and wetting ability or lipophilicity.Therefore need have different properties is beneficial to have more possibilities aspect purposes novel ion liquid.
The purpose of this invention is to provide and can be used as ion liquid novel stabilising class salt compound and preparation method thereof with useful quality.Especially, the purpose of this invention is to provide and contain highly stable cationic ionic compound.
This purpose of following realization: provide according to general formula (1) contain urea or the cationic salt of thiocarbamide, positive charge delocalization (delocalise) on many heteroatomss wherein,
Wherein
X represents O or S,
Wherein substituent R and R
0Representative independently of each other separately
The straight or branched alkyl that contains 1-20 carbon atom,
The straight or branched alkenyl that contains 2-20 carbon atom and one or more pairs of keys,
Contain 2-20 carbon atom and one or more triple-linked straight or branched alkynyl,
Saturated, the partially or completely unsaturated cycloalkyl that contains 3-7 carbon atom,
Its alkyl that can be contained 1-6 carbon atom replaces,
R also can represent hydrogen,
Wherein one or more substituent R or R
0Can partially or completely be replaced by halogen or the part by CN or NO
2Replace, but do not comprise that halogenation is at R
0The situation of α position, and
Halogen is represented F, Cl, Br or I,
Wherein substituent R and R
0Can be interconnection in pairs by singly-bound or two key,
And wherein not direct one or more substituent R or the R adjacent with heteroatoms
0Carbon atom or two non-conterminous carbon atoms can be selected from-O-,-C (O)-,-C (O) O-,-S-,-S (O)-,-SO
2-,-SO
3-,-N=,-N=N-,-NH-,-NR '-,-PR '-,-P (O) R '-,-P (O) R '-O-,-O-P (O) R '-O-and-P (R ')
2The atom of=N-and/or atomic group replace, wherein R ' contains not the fluoridizing of 1-6 carbon atom, partially fluorinated or fluoridized alkyl, the unsaturated cycloalkyl of saturated or part that contains 3-7 carbon atom, phenyl that does not replace or replace or the heterocycle that does not replace or replace
And
A-is selected from:
[R
1SO
3]
-, [R
F 'SO
3]
-, [(R
FSO
2)
2N]
-, [(R
FSO
2)
3C]
-, [(FSO
2)
3C]
-, [R
1CH
2OSO
3]
-, [R
1C (O) O]
-, [R
F 'C (O) O]
-, [CCl
3C (O) O]
-, [(CN)
3C]
-, [(CN)
2CR
1]
-, [(R
1O (O) C)
2CR
1]
-, [P (C
nF
2n+1-mH
m)
yF
6-y]
-, [P (C
6F
5)
yF
6-y]
-, [R
1 2P (O) O]
-, [R
1P (O) O
2]
2-, [(R
1O)
2P (O) O]
-, [(R
1O) P (O) O
2]
2-, [(R
1O) (R
1) P (O) O]
-, [R
F 2P (O) O]
-, [R
FP (O) O
2]
2-, [BF
zR
F 4-z]
-, [BF
z(CN)
4-z]
-, [B (CN)
4]
-, [B (C
6F
5)
4]
-, [B (OR
1)
4]
-, [N (CF
3)
2]
-, [N (CN)
2]
-, [AlCl
4]
-Or [SiF
6]
2-,
Substituent R wherein
FAnd R
F 'Representative independently of each other separately
Contain the perfluorination of 1-20 carbon atom and the alkyl of straight or branched, wherein R
F 'Do not comprise trifluoromethyl,
Contain the perfluorination of 2-20 carbon atom and one or more pairs of keys and the alkenyl of straight or branched,
Perfluorophenyl and saturated, the partially or completely unsaturated cycloalkyl that contains 3-7 carbon atom, it can be replaced by perfluoroalkyl, wherein substituent R
FOr R
F 'Can be interconnection in pairs by singly-bound or two key, and
Substituent R wherein
FOr R
F 'In can be selected from carbon atom of heteroatomic α position or two non-conterminous carbon atoms-O-,-C (O)-,-S-,-S (O)-,-SO
2-,-N=,-N=N-,-NR '-,-PR '-and-P (O) R '-atom and/or atomic group replace, perhaps can contain end group R '-O-SO
2-or R '-O-C (O)-, wherein R ' representative contains not the fluoridizing of 1-6 carbon atom, partially fluorinated or fluoridized alkyl, contains the undersaturated cycloalkyl of saturated or part of 3-7 carbon atom, the phenyl that does not replace or replace or the heterocycle of replacement or replacement not,
And
Substituent R wherein
1Representative independently of each other separately
Work as A
-=[(CN)
2CR
1]
-Or [(R
1O (O) C)
2CR
1]
-And when X=O or S, be hydrogen, or
Work as A
-=[R
1CH
2OSO
3]
-, X=S or O and substituent R and R
0=when containing the alkyl of 1 to 20 carbon atom, be hydrogen,
The straight or branched alkyl that contains 1-20 carbon atom,
The straight or branched alkenyl that contains 2-20 carbon atom and one or more pairs of keys,
Contain 2-20 carbon atom and one or more triple-linked straight or branched alkynyl,
Saturated, the partially or completely undersaturated cycloalkyl that contains 3-7 carbon atom,
Its alkyl that can be contained 1-6 carbon atom replaces,
Substituent R wherein
1Can be partly by CN, NO
2Or the halogen replacement, and
Halogen is represented F, Cl, Br or I,
Substituent R wherein
1Can be interconnection in pairs by singly-bound or two key, and
Substituent R wherein
1In can be selected from carbon atom of heteroatomic α position or two non-conterminous carbon atoms-O-,-C (O)-,-C (O) O-,-S-,-S (O)-,-SO
2-,-SO
3-,-N=,-N=N-,-NH-,-NR '-,-PR ' and-P (O) R ', P (O) R ' O-, OP (O) R ' O-,-PR '
2=N-,-C (O) NH-,-C (O) NR '-,-SO
2NH-or-SO
2NR '-atom and/or atomic group replace, wherein R ' representative contains not the fluoridizing of 1-6 carbon atom, partially fluorinated or fluoridized alkyl, the unsaturated cycloalkyl of saturated or part that contains 3-7 carbon atom, phenyl that does not replace or replace or the heterocycle that does not replace or replace
And variable
N represents 1 to 20,
M represents 0,1,2 or 3,
Y represents 0,1,2,3 or 4,
Z represents 0,1,2 or 3,
Condition is
As X=S and R and R
0=when containing the alkyl of 1 to 20 carbon atom, negatively charged ion A
-Can=[BF
4]
-, CF
3COO
-, [B (C
6H
5)
4]
-Or [CH
3C
6H
4SO
3]
-,
And when X=O, negatively charged ion A
-Can=CF
3COO
-[B (C
6H
5)
4]
-, and
As X=O and R
0During=ethyl, get rid of negatively charged ion A
-=CH
3CH
2OSO
3 -
For the present invention, complete undersaturated substituting group also can refer to aromatic substituent.
Compound of the present invention is a feature with highly stable positively charged ion.
Therefore, compound of the present invention is to contain the optional thiocarbamide that replaces or the salt of uronium.
Except hydrogen, suitable substituents R according to the present invention is: C
1To C
20, C particularly
1To C
12Alkyl, C
2To C
20, C particularly
2To C
12Alkenyl or alkynyl and saturated or undersaturated promptly also comprise the C of aromatics
3To C
7Cycloalkyl, it can be by C
1To C
6Alkyl replaces, particularly phenyl.
Four substituent R of salt of the present invention can be identical or different.
Be fit to do substituent R according to the present invention
0Be: C
1To C
20, C particularly
1To C
12Alkyl, C
2To C
20, C particularly
2To C
12Alkenyl or alkynyl and saturated or undersaturated promptly also comprise the C of aromatics
3To C
7Cycloalkyl, it can be by C
1To C
6Alkyl replaces, particularly phenyl.
C
1-C
12Alkyl is, for example, methyl, ethyl, sec.-propyl, propyl group, butyl, sec-butyl or the tertiary butyl, comprise amyl group, 1-, 2-or 3-methyl butyl, 1 in addition, 1-, 1,2-or 2,2-dimethyl propyl, 1-ethyl propyl, hexyl, heptyl, octyl group, nonyl, decyl, undecyl or dodecyl.Optional partially or completely replaced, for example difluoromethyl, trifluoromethyl, trifluoroethyl, pentafluoroethyl group, five fluoropropyls, seven fluoropropyls, seven fluorine butyl, nine fluorine butyl or nine fluorine hexyls by F.
Preferred abovementioned alkyl contains 1 to 6 carbon atom.
Therefore, contain not replacing of 3-7 carbon atom saturated or partially or completely undersaturated cycloalkyl be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, cyclopentenyl, ring penta-1,3-dialkylene, cyclohexenyl, hexamethylene-1,3-dialkylene, hexamethylene-1,4-dialkylene, phenyl, cycloheptenyl, ring heptan-butadienyl, ring heptan-1,4-dialkylene or ring heptan-1, the 5-dialkylene, they can be by C
1To C
6Alkyl replaces, wherein cycloalkyl or by C
1To C
6The cycloalkyl that alkyl replaces again can be by halogen atom (for example F, Cl, Br or I, particularly F or Cl), CN or NO
2Replace.
Substituent R and R
0Can be partially or completely by halogen atom particularly F and/or Cl replace, or part is by CN or NO
2Replace, wherein get rid of R
0α-CH
2The halogenation of group.In addition, substituent R and R
0Can contain one or two to be selected from-O-,-C (O)-,-C (O) O-,-S-,-S (O)-,-SO
2-,-SO
2O-,-N=,-N=N-,-NH-,-NR '-,-PR '-,-P (O) R '-,-P (O) R '-O-,-O-P (O) R '-O-,-P (O) (NR '
2)-NR '-and-P (R ')
2Mutual non-conterminous heteroatoms or the atomic group of=N-, wherein R ' can be do not fluoridize, partially fluorinated or fluoridized C
1To C
6Alkyl, C
3To C
7Cycloalkyl, phenyl that does not replace or replace or the heterocycle that does not replace or replace.
In R ', C
3To C
7Cycloalkyl is, for example, and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl.
In R ', the phenyl of replacement is meant the phenyl that is replaced by following groups: C
1To C
6Alkyl, C
1To C
6Alkenyl, NO
2, F, Cl, Br, I, OH, C
1-C
6Alkoxyl group, CN, SCN, SCF
3, SO
2CF
3, C (O) O-C
1-C
6Alkyl, NH
2, C
1-C
6Alkylamino or C
1-C
6-dialkyl amido, COOH, C (O) NR "
2, SO
2OR ", SO
2X ', SO
2NR "
2, SO
3H or NHC (O) R ", wherein X ' represents F, Cl or Br, and R " representative as to not the fluoridizing of R ' definition, part or fluoridized C
1To C
6Alkyl or C
3-C
7-cycloalkyl; for example; adjacent-; between-or right-aminomethyl phenyl; adjacent-; between-or right-ethylphenyl; adjacent-; between-or right-propyl group phenyl; adjacent-; between-or right-isopropyl phenyl; adjacent-; between-or right-tert-butyl-phenyl; adjacent-; between-or right-aminophenyl; adjacent-; between-or right-(N; the N-dimethylamino) phenyl; adjacent-; between-or right-nitrophenyl; adjacent-; between-or right-hydroxy phenyl; adjacent-; between-or right-p-methoxy-phenyl; adjacent-; between-or right-ethoxyl phenenyl; adjacent-; between-or right-(trifluoromethyl) phenyl; adjacent-; between-or right-(trifluoromethoxy) phenyl; adjacent-; between-or right-(trifluoromethyl sulfonyl) phenyl; adjacent-; between-or right-fluorophenyl; adjacent-; between-or right-chloro-phenyl-; adjacent-; between-or right-bromophenyl; adjacent-; between-or right-iodophenyl; also preferred 2; 3-; 2; 4-; 2; 5-; 2; 6-; 3,4-or 3,5-3,5-dimethylphenyl; 2; 3-; 2; 4-; 2,5-; 2,6-; 3; 4-or 3; the 5-dihydroxy phenyl; 2,3-; 2,4-; 2; 5-; 2; 6-; 3,4-or 3,5-difluorophenyl; 2; 3-; 2; 4-; 2,5-; 2,6-; 3; 4-or 3; the 5-dichlorophenyl; 2,3-; 2,4-; 2; 5-; 2; 6-; 3,4-or 3,5-dibromo phenyl; 2; 3-; 2; 4-; 2,5-; 2,6-; 3; 4-or 3; the 5-Dimethoxyphenyl; 5-fluoro-2-aminomethyl phenyl; 3,4,5-trimethoxyphenyl or 2; 4, the 5-trimethylphenyl.
In R ', heterocycle is meant saturated or undersaturated monocycle or the bicyclic heterocyclic group that contains 5 to 13 ring memberses, wherein can have 1,2 or 3 N and/or 1 or 2 S or O atom, and heterocyclic group can be by C
1To C
6Alkyl, C
1To C
6Alkenyl, NO
2, F, Cl, Br, I, OH, C
1-C
6Alkoxyl group, CN, SCN, SCF
3, SO
2CF
3, C (O) O-C
1-C
6Alkyl, NH
2, C
1-C
6Alkylamino or C
1-C
6Dialkyl amido, COOH, C (O) NR "
2, SO
2OR ", SO
2X ', SO
2NR "
2, SO
3H or NHC (O) R " replace wherein X ' and R " have an above-mentioned implication.
Heterocyclic group preferably replaces or unsubstituted 2-or 3-furyl, 2-or 3-thienyl, 1-, 2-or 3-pyrryl, 1-, 2-, 4-or 5-imidazolyl, 3-, 4-or 5-pyrazolyl, 2-, 4-or 5-oxazolyl, 3-, 4-or 5-isoxazolyl, 2-, 4-or 5-thiazolyl, 3-, 4-or 5-isothiazolyl, 2-, 3-or 4-pyridyl, 2-, 4-, 5-or 6-pyrimidyl, also be preferably 1,2,3-triazole-1-,-4-or-the 5-base, 1,2,4-triazole-1-,-4-or-the 5-base, 1-or 5-tetrazyl, 1,2,3-oxadiazole-4-or-the 5-base, 1,2,4-oxadiazole-3-or-the 5-base, 1,3,4-thiadiazoles-2-or-the 5-base, 1,2,4-thiadiazoles-3-or-the 5-base, 1,2,3-thiadiazoles-4-or-the 5-base, 2-, 3-, 4-, 5-or 6-2H-sulfo-pyranyl, 2-, 3-or 4-4H-sulfo-pyranyl, 3-or 4-pyridazinyl, pyrazinyl, 2-, 3-, 4-, 5-, 6-or 7-benzofuryl, 2-, 3-, 4-, 5-, 6-or 7-benzothienyl, 1-, 2-, 3-, 4-, 5-, 6-or 7-1H-indyl, 1-, 2-, 4-or 5-benzimidazolyl-, 1-, 3-, 4-, 5-, 6-or 7-benzopyrazoles base, 2-, 4-, 5-, 6-or 7-benzoxazolyl, 3-, 4-, 5-, 6-or 7-benzoisoxazole base, 2-, 4-, 5-, 6-or 7-benzothiazolyl, 2-, 4-, 5-, 6-or 7-benzisothiazole base, 4-, 5-, 6-or 7-benzo-2,1,3-oxadiazole base, 1-, 2-, 3-, 4-, 5-, 6-, 7-or 8-quinolyl, 1-, 3-, 4-, 5-, 6-, 7-or 8-isoquinolyl, 1-, 2-, 3-, 4-or 9-carbazyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-or 9-acridyl, 3-, 4-, 5-, 6-, 7-or 8-cinnolines base, 2-, 4-, 5-, 6-, 7-or 8-quinazolyl or 1-, 2-or 3-pyrrolidyl.
Without limitation, the substituent R of thiocarbamide or uronium and R
0Example be:
-CH
3，-C
2H
5，-C
3H
7，-CH(CH
3)
2，-C
4H
9，-C(CH
3)
3，-C
5H
11，-C
6H
13，-C
7H
15，
-C
8H
17，-C
9H
19，-C
10H
21，-C
12H
25，-C
20H
41，-OCH
3，-OCH(CH
3)
2，-CH
2OCH
3，
-C
2H
4OCH(CH
3)
2，-C
2H
4SC
2H
5，-C
2H
4SCH(CH
3)
2，-S(O)CH
3，-SO
2CH
3，
-SO
2C
6H
5，-SO
2C
3H
7，-SO
2CH(CH
3)
2，-SO
2CH
2CF
3，-CH
2SO
2CH
3，
-CH
2N(H)C
2H
5，-C
2H
4N(H)C
2H
5，-CH
2N(CH
3)CH
3，-CN，-C
2H
4N(CH
3)CH
3，
-CF
3，-C
2F
5，-C
3F
7，-C
4F
9，-C(CF
3)
3，-CF
2SO
2CF
3，-C
2F
4N(C
2F
5)C
2F
5，-CHF
2，
-CH
2CF
3，-C
2F
2H
3，-C
3FH
6，-CH
2C
3F
7，-C(CFH
2)
3，-CH
2C(O)OH，-CH
2C
6H
5，
-CH
2C(O)CH
3，-CH
2C(O)C
2H
5，-CH
2C(O)OCH
3，CH
2C(O)OC
2H
5，-C(O)CH
3，
-C(O)C
6H
5，-C(O)OCH
3，-C(O)OC
2H
5，P(O)(C
2H
5)
2，P(O)[N(C
2H
5)
2]
2，
The most nearly four substituent R also can with form monocycle, two rings or encircle more cationic mode connect into right.
Without limitation, this cationic example is:
Or
Wherein substituent R and R
0Can have above-mentioned implication or particularly preferred implication.Above-mentioned cationic carbocyclic ring or heterocycle also can randomly be replaced by following groups: C
1To C
6Alkyl, C
1To C
6Alkenyl, NO
2, F, Cl, Br, I, OH, C
1-C
6Alkoxyl group, CN, SCN, SCF
3, SO
2CF
3, C (O) O-C
1-C
6Alkyl, NH
2, C
1-C
6Alkylamino or C
1-C
6Dialkyl amido, COOH, C (O) NR "
2, SO
2OR ", SO
2NR "
2, SO
2X ', SO
3H or NHC (O) R " or replacement or unsubstituted phenyl or the heterocycle that do not replace or replace, wherein X ' and R " an above-mentioned implication had.
The negatively charged ion A of salt of the present invention
-Be selected from:
[R
1SO
3]
-, [R
F 'SO
3]
-, [(R
FSO
2)
2N]
-, [(R
FSO
2)
3C]
-, [(FSO
2)
3C]
-, [R
1CH
2OSO
3]
-, [R
1C (O) O]
-, [R
F 'C (O) O]
-, [CCl
3C (O) O]
-, [(CN)
3C]
-, [(CN)
2CR
1]
-, [(R
1O (O) C)
2CR
1]
-, [P (C
nF
2n+1-mH
m)
yF
6-y]
-, [P (C
6F
5)
yF
6-y]
-, [R
1 2P (O) O]
-, [R
1P (O) O
2]
2 -, [(R
1O)
2P (O) O]
-, [(R
1O) P (O) O
2]
2-, [(R
1O) (R
1) P (O) O]
-, [R
F 2P (O) O]
-, [R
FP (O) O
2]
2-, [BF
zR
F 4-z]
-, [BF
z(CN)
4-z]
-, [B (CN)
4]
-, [B (C
6F
5)
4]
-, [B (OR
1)
4]
-, [N (CF
3)
2]
-, [N (CN)
2]
-, [AlCl
4]
-Or [SiF
6]
2-,
Substituent R wherein
FAnd R
F 'Representative independently of each other separately
The perfluorination and straight or branched alkyl, the wherein R that contain 1-20 carbon atom
F 'Do not comprise trifluoromethyl,
The perfluorination and the straight or branched alkenyl that contain 2-20 carbon atom and one or more pairs of keys,
Perfluorophenyl and saturated, the partially or completely unsaturated cycloalkyl that contains 3-7 carbon atom, it can be replaced by fluoridized alkyl, wherein substituent R
FOr R
F 'Can be interconnection in pairs by singly-bound or two key, and
Substituent R wherein
FOr R
F 'In can be selected from carbon atom of heteroatomic α position or two non-conterminous carbon atoms-O-,-C (O)-,-S-,-S (O)-,-SO
2-,-N=,-N=N-,-NR '-,-PR '-and-P (O) R '-atom and/or atomic group replace, wherein R ' representative contains not the fluoridizing of 1-6 carbon atom, partially fluorinated or fluoridized alkyl, the unsaturated cycloalkyl of saturated or part that contains 3-7 carbon atom, phenyl that does not replace or replace or the heterocycle that does not replace or replace
And
Substituent R wherein
1Representative independently of each other separately
Work as A
-=[(CN)
2CR
1]
-Or [(R
1O (O) C)
2CR
1]
-And when X=O or S, be hydrogen, or
Work as A
-=[R
1CH
2OSO
3]
-, X=S or O and substituent R and R
0=when containing the alkyl of 1 to 20 carbon atom, be hydrogen,
The straight or branched alkyl that contains 1-20 carbon atom,
The straight or branched alkenyl that contains 2-20 carbon atom and one or more pairs of keys,
Contain 2-20 carbon atom and one or more triple-linked straight or branched alkynyl,
Saturated, the partially or completely unsaturated cycloalkyl that contains 3-7 carbon atom,
Its alkyl that can be contained 1-6 carbon atom replaces,
Substituent R wherein
1Can be partly by CN, NO
2Or the halogen replacement, and
Halogen is represented F, Cl, Br or I,
Substituent R wherein
1Can be interconnection in pairs by singly-bound or two key, and
Substituent R wherein
1In can be selected from carbon atom of heteroatomic α position or two non-conterminous carbon atoms-O-,-C (O)-,-C (O) O-,-S-,-S (O)-,-SO
2-,-SO
3-,-N=,-N=N-,-NH-,-NR '-,-PR ' and-P (O) R ', P (O) R ' O-, OP (O) R ' O-,-PR '
2=N-,-C (O) NH-,-C (O) NR '-,-SO
2NH-or-SO
2NR '-atom and/or atomic group replace, wherein R ' representative contains not the fluoridizing of 1-6 carbon atom, partially fluorinated or fluoridized alkyl, the unsaturated cycloalkyl of saturated or part that contains 3-7 carbon atom, not replacement or substituted-phenyl or not replacement or substituted heterocycle
And variable
N represents 1 to 20,
M represents 0,1,2 or 3,
Y represents 0,1,2,3 or 4,
Z represents 0,1,2 or 3,
Condition is
As X=S and R and R
0=when containing the alkyl of 1 to 20 carbon atom, negatively charged ion A
-Can=[BF
4]
-, CF
3COO
-, [B (C
6H
5)
4]
-Or [CH
3C
6H
4SO
3]
-,
And when X=O, negatively charged ion A
-Can=CF
3COO
-[B (C
6H
5)
4]
-, and
As X=O and R
0During=ethyl, get rid of negatively charged ion A
-=CH
3CH
2OSO
3 -
The straight or branched alkenyl (wherein can also have a plurality of pairs of keys) that contains 2 to 20 carbon atoms is, for example, allyl group, 2-or 3-butenyl, isobutenyl, secondary butenyl, also have in addition 4-pentenyl, isopentene group, hexenyl, heptenyl, octenyl ,-C
9H
17,-C
10H
19To-C
20H
39Preferred allyl group, 2-or 3-butenyl, isobutenyl, secondary butenyl, further preferred 4-pentenyl, isopentene group or hexenyl.
The straight or branched alkynyl (wherein can also have a plurality of triple bonds) that contains 2 to 20 carbon atoms is, for example, ethynyl, 1-or 2-propynyl, 2-or 3-butynyl, in addition also have 4-pentynyl, 3-pentynyl, hexin base, heptyne base, octyne base ,-C
9H
15,-C
10H
17To-C
20H
37Preferred ethynyl, 1-or 2-propynyl, 2-or 3-butynyl, 4-pentynyl, 3-pentynyl or hexin base.
In negatively charged ion, there are a plurality of R
FOr R
F 'Situation under, these also can with form dicyclo or encircle more anionic mode connect into by singly-bound or two key right.
In addition, substituent R
FOr R
F 'Can contain one or two to be selected from-O-,-SO
2-and-NR '-not at mutual non-conterminous atom or the atomic group or the end group-SO of heteroatomic α position
2X ', wherein R ' can be do not fluoridize, partially fluorinated or fluoridized C
1-to C
6Alkyl, C
3To C
7Cycloalkyl does not replace or substituted-phenyl, comprises-C
6F
5, or do not replace or substituted heterocycle, and X '=F, Cl or Br.
Without limitation, anionic substituent R
FAnd R
F 'Example be:
-CF
3，-C
2F
5，-C
3F
7，-C
4F
9，-C(CF
3)
3，-CF
2N(CF
3)CF
3，-CF
2OCF
3，
-CF
2S(O)CF
3，-CF
2SO
2CF
3，-C
2F
4N(C
2F
5)C
2F
5，CF＝CF
2，-C(CF
3)＝CFCF
3，
-CF
2CF=CFCF
3,-CF=CFN (CF
3) CF
3Or-CF
2SO
2F,
-C (CF
3)=CFCF
3,-CF
2CF=CFCF
3Or-CF=CFN (CF
3) CF
3
R
F 'Be preferably pentafluoroethyl group, hexafluoro propyl group or nine fluorine butyl.
R
FBe preferably trifluoromethyl, pentafluoroethyl group, seven fluoropropyls or nine fluorine butyl.
Be subject to abandoning of claim 1, more anionic examples of the present invention are as follows:
[CF
3SO
3]
-，[CF
3CF
2SO
3]
-，[CH
3CH
2SO
3]
-，[(CF
3SO
2)
2N]
-，[(C
2F
5SO
2)
2N]
-，
[(CF
3SO
2)
3C]
-，[(C
2F
5SO
2)
3C]
-，[CH
3CH
2OSO
3]
-，[(FSO
2)
3C]
-，
[CF
3C(O)O]
-，[CF
3CF
2C(O)O]
-，[CH
3CH
2C(O)O]
-，[CH
3C(O)O]
-，
[P(C
2F
5)
3F
3]
-，[P(CF
3)
3F
3]
-，[P(C
2F
4H)(CF
3)
2F
3]
-，[P(C
2F
3H
2)
3F
3]
-，
[P(C
2F
5)(CF
3)
2F
3]
-，[P(C
6F
5)
3F
3]
-，[P(C
3F
7)
3F
3]
-，[P(C
4F
9)
3F
3]
-，
[P(C
2F
5)
2F
4]
-，[(C
2F
5)
2P(O)O]
-，[(C
2F
5)P(O)O
2]
2-，[P(C
6F
5)
2F
4]
-，
[(CF
3)
2P(O)O]
-，[(CH
3)
2P(O)O]
-，[(C
4F
9)
2P(O)O]
-，[CF
3P(O)O
2]
2-，
[CH
3P(O)O
2]
2-，[(CH
3O)
2P(O)O]
-，[BF
3(CF
3)]
-，[BF
2(C
2F
5)
2]
-，[BF
3(C
2F
5)]
-，
[BF
2(CF
3)
2]
-，[B(C
2F
5)
4]
-，[BF
3(CN)]
-，[BF
2(CN)
2]
-，[B(CN)
4]
-，[B(CF
3)
4]
-，
[BF
4]
-，[B(OCH
3)
4]
-，[B(OCH
3)
2(OC
2H
5)]
-，[B(O
2C
2H
4)
2]
-，[B(O
2C
2H
2)
2]
-，
[B (O
2CH
4)
2]
-, [N (CF
3)
2]
-, [N (CN
2)
2]
-, [C (CN)
3]
-, [AlCl
4]
-Or [SiF
6]
2-
Consider that this abandons, particularly preferred negatively charged ion is [R in the above-mentioned example
F 'SO
3]
-, [P (C
nF
2n+1-mH
m)
yF
6-y]
-, [R
F 2P (O) O]
-, [BF
zR
F 4-z]
-Or [BF
z(CN)
4-z]
-, wherein n, m, y and z have one of above-mentioned implication, for example [B (CN)
4]
-, [(C
2F
5)
3PF
3]
-, [(C
2F
5)
2PF
4]
-, [(C
4F
9)
3PF
3]
-, [(C
3F
7)
3PF
3]
-, [B (C
2F
5) F
3]
-, [(CF
3)
2P (O) O]
-, [(C
2F
5)
2P (O) O]
-Or [B (CF
3)
4]
-Consider that this abandons, very particularly preferably negatively charged ion is [BF in the above-mentioned example
4]
-, [(C
2F
5)
3PF
3]
-, [(C
2F
5)
2P (O) O]
-Or [CF
3SO
3]
-
In particularly preferred negatively charged ion, formula [P (C
nF
2n+1-mH
m)
yF
6-y]
-Phosphate radical have special significance because this anionic selection causes the salt of formula (1) to have low especially viscosity.
According to the present invention, preferably meet the salt of one group of formula (1) of following condition: wherein cationic substituent R is represented hydrogen or is contained the straight or branched alkyl of 1-12 carbon atom (particularly 1-6 carbon atom), and A
-Have the preferred or particularly preferred implication of the described implication of formula (1).
According to the present invention, preferably meet the salt of one group of formula (1) of following condition: wherein cationic substituent R is selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, sec-butyl, phenyl, cyclohexyl, and A
-Have the preferred or particularly preferred implication of the described implication of formula (1).
According to the present invention, preferably meet the salt of one group of formula (1) of following condition: wherein X represents sulphur, and A
-Have the preferred or particularly preferred implication of the described implication of formula (1).
According to the present invention, preferably meet the salt of one group of formula (1) of following condition: wherein X represents oxygen, and A
-Have the preferred or particularly preferred implication of the described implication of formula (1).
According to the present invention, preferably meet the salt of one group of formula (1) of following condition: R wherein
0Representative contains the straight or branched alkyl of 1-20 carbon atom, and it can partially or completely be fluoridized, but wherein gets rid of R
0α-CH
2Fluoridizing of group, X represents sulphur or R wherein
0Straight or branched alkyl and X that representative contains 1-20 carbon atom represent oxygen, and A
-Have the preferred or particularly preferred implication of the described implication of formula (1).
According to the present invention, preferably meet the salt of one group of formula (1) of following condition: R wherein
0Representative contains the straight or branched alkyl of 1-20 carbon atom, and it can partially or completely be fluoridized, X=S, and substituent R represents the straight or branched alkyl that contains 1-20 carbon atom separately independently of each other, and A
-Have the preferred or particularly preferred implication of the described implication of formula (1).
According to the present invention, preferably meet the salt of one group of formula (1) of following condition: R wherein
0Representative contains the straight or branched alkyl of 1-20 carbon atom, X=O, and substituent R represents the straight or branched alkyl that contains 1-20 carbon atom separately independently of each other, and A
-Have the preferred or particularly preferred implication of the described implication of formula (1).
Secondly, the present invention relates to preparation method according to the salt that contains thiocarbamide or uronium of formula of the present invention (1).For this reason, use ester AR
0Or use oxonium salt (R
0)
3O
+A
-With thiocarbamide C (S) (NR
2)
2Or urea C (O) (NR
2)
2Alkylation.
Group or substituent R
0With R herein definition and general formula (1) in similar or have an implication of pointing out specially.With the situation of ester reaction under, A can be selected from [R
1CH
2OSO
3], [R
1SO
3], [R
FSO
3], [R
FC (O) O] and [CCl
3C (O) O], and with the situation of oxonium salt reaction under, A
-Can be selected from [(FSO
2)
3C]
-[BF
4]
-
This reaction is preferably carried out under the temperature that at least a described component is a liquid.This reaction is to carry out in the temperature range of liquid particularly preferably in reaction mixture.
The reaction of thiocarbamide or urea and ester or oxonium salt can be in polar organic solvent (for example, 1,2-ethylene dichloride or methylene dichloride), carry out in non-polar organic solvent (for example hexane or pentane) or without solvent (for example in salt-melting).According to the present invention, solvent mixture also can replace neat solvent to use.
According to the present invention, reagent can react with the excessive ratio of mixture that is up to five times of one of reactant.Yet reactant preferably uses with equimolar amount.
Salt of the present invention can separate with extraordinary yield (usually above 80%, preferably being higher than 90%).
The invention further relates to another kind of method by salt exchange preparation salt of the present invention.Wherein, contain the thiocarbamide of general formula (1) or uronium and be selected from [BF
4]
-, Br
-, Cl
-, I
-Or [ClO
4]
-Negatively charged ion A
-Salt and salt Kt
+A
-Or with sour AH reaction, wherein Kt is basic metal or alkaline-earth metal, A defines according to general formula (1).
This reaction is preferably carried out under at least a component is the temperature of liquid.This reaction is to carry out in the temperature range of liquid particularly preferably in reaction mixture.
The exchange of the salt of thiocarbamide or urea salt can be in polar solvent (for example, water, acetonitrile, glycol dimethyl ether, dimethyl formamide, methyl alcohol or propionitrile), carry out in non-polar organic solvent (for example methylene dichloride) or without solvent (for example in salt-melting).According to the present invention, solvent mixture also can replace neat solvent to use.
According to the present invention, reagent can react with excessive 10% the ratio of mixture of being up to of one of reactant.Yet reactant preferably uses with equimolar amount.
Perhaps, negatively charged ion A
-=[R
F 2P (O) O]
-The time the salt of formula of the present invention (1) can pass through three (perfluoroalkyl) phosphine oxides and pure and mild thiocarbamide C (S) (NR
2)
2Or urea C (O) (NR
2)
2Reaction be prepared, wherein radicals R definition as above and also alkalescence stronger than alcohol.
Select suitable alcohol, make after alkylation, to form required positively charged ion at used alkali.
Used three (perfluoroalkyl) phosphine oxide can be by traditional method preparation well known by persons skilled in the art.These compounds preferably by with the prepared in reaction of hexamethyldisiloxane (V.YaSememii etc., J.Gen.Chem.USSR (Engl.Trans.) 55, No.12 (1985), 2415-2417).
All compounds of the present invention all have salt like feature, relatively low fusing point (being usually less than 100 ℃) and can be used as ionic liquid.
Salt of the present invention can be as the solvent of many synthetic or catalyzed reactions, for example friedel-crafts acidylate and alkylation, Diels-Alder cycloaddition, hydrogenation and oxidizing reaction, Heck reaction.In addition, can synthesize, for example the fluorated solvent used of secondary cell and galvanic cell.
Also can use compound of the present invention as nonaqueous electrolyte, if desired, can be used in combination with other ionogen well known by persons skilled in the art.
In addition, salt of the present invention can be used as non-aqueous polar material in suitable reaction, be used as phase-transfer catalyst, as tensio-active agent or as the medium of heterogeneous or homogeneous catalyst.
Above and whole disclosures of all applications, patents and publications of hereinafter mentioning all incorporated herein by reference.
Even without further note, can utilize above-mentioned explanation in the scope the most widely but infer those skilled in the art.Therefore, preferred embodiment and embodiment only are considered as descriptive disclosing, and it is construed as limiting never by any way.
(have 5 millimeters that the band deuterium is locked at Bruker Avance DRX spectrometer
1H/BB broadband head) goes up spectrum in the NMR of the solution of 20 ℃ of measurements in deuterated solvent.The survey frequency of various nucleons is:
1H:300.13MHz,
11B:96.92MHz,
19F:282.41MHz and
31P:121.49MHz.For each spectrum or each data set, reference method has been described separately.
Embodiment 1: trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--S-ethyl isothiourea
With 15.0 gram (113.4 mmole) N, N, N ', N '-tetramethyl thiourea are dissolved in 50 cubic centimetres of methylene dichloride, and use 30 fens clock times slow (dropwise) adding, 20.6 gram (115.6 mmole) trifluoromethanesulfonic acid ethyl ester CF simultaneously with the ice bath refrigerative
3SO
2OC
2H
5, use magnetic stirrer vigorous stirring reaction mixture simultaneously.With reaction mixture restir 10 minutes at room temperature.Solvent is removed in decompression.With resistates with 30 cubic centimetres of pentanes washing three times, and under 7.0 handkerchief vacuum in 40-50 ℃ of drying 1 hour, produce the 35.0 grams crystalline material of fusing easily.Based on N, N, N ', N '-tetramethyl thiourea, trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--N "-yield of ethyl isothiourea be 99.5%.
19F NMR (reference: CCl
3Mark in the F-; Solvent: CD
3CN) :-77.84s (CF
3).
1H NMR (reference: TMS; Solvent: CD
3CN): 1.30t (CH
3); 3.02q (CH
2); 3.25s (4CH
3);
3J
H, H=7.4Hz.
Ultimate analysis
Measured value, %:C 30.82 H 5.49 N 9.07
C
8H
17F
3N
2O
3S
2Calculated value, %:C 30.96 H 5.52 N 9.03
Embodiment 2: three (pentafluoroethyl group) three hexafluorophosphoric acid N, N, N ', N '-tetramethyl--S-ethyl isothiourea
With 17.1 gram (55.1 mmole) trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--S-ethyl isothiourea is dissolved in 70 cubic centimetres of water, and at room temperature add 31.0 gram (57.8 mmole) five hydrations three (pentafluoroethyl group), three hexafluorophosphoric acid, use magnetic stirrer vigorous stirring reaction mixture simultaneously.Separate the low layer water also with 30 cubic centimetres of water washings four times.With resistates under 7.0 handkerchief vacuum in oil bath in 60 ℃ of dryings 3 hours, produce 30.0 gram fluent materials.Based on trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--S-ethyl isothiourea, three (pentafluoroethyl group) three hexafluorophosphoric acid N, N, N ', the yield of N '-tetramethyl--S-ethyl isothiourea is 89.8%.
19F NMR (reference: CCl
3Mark in the F-; Solvent: CD
3CN) :-43.56dm (PF);-79.58m (CF
3);-81.27m (2CF
3);-86.92dm (PF
2);-114.93m (CF
2);-115.52m (2CF
2);
1J
P, F=890Hz;
1J
P, F=904Hz;
2J
P, F=86Hz;
2J
P, F=97Hz.
1H NMR (reference: TMS; Solvent: CD
3CN): 1.34t (CH
3); 3.03q (CH
2); 3.25s (4CH
3);
3J
H, H=7.4Hz.
31P NMR (reference: 85%H
3PO
4Solvent: CD
3CN) :-148.55dtm;
1J
P, F=890Hz;
1J
P, F=902Hz.
Ultimate analysis
Measured value, %:C 25.63 H 2.87 N 4.59
C
13H
17F
18N
2The calculated value of PS, %:C 25.75 H 2.83 N 4.62
Embodiment 3: trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--S-(2,2, the 2-trifluoroethyl) isothiourea
With 1.0 gram (7.56 mmole) N, N, N ', N '-tetramethyl thiourea are dissolved in 20 cubic centimetres of hexanes, and 1.84 gram (7.93 mmole) trifluoromethanesulfonic acids 2,2 of slow (dropwise) adding at room temperature, 2-trifluoro ethyl ester CF
3SO
2OCH
2CF
3, use magnetic stirrer vigorous stirring reaction mixture simultaneously.With reaction mixture restir 6 hours at room temperature.From hexane, isolate low layer mutually and with twice of 10 cubic centimetres of hexane wash.With resistates under 1.3 handkerchief vacuum in 50 ℃ of dryings 2 hours, produce 2.74 gram oily materials (fusing point 67-70 ℃).Trifluoromethanesulfonic acid N, N, N ', the yield of N '-tetramethyl--S-(2,2, the 2-trifluoroethyl) isothiourea is N, N, N ', 99.4% of N '-tetramethyl thiourea.
19F NMR (reference: CCl
3Mark in the F-; Solvent: CD
3CN) :-65.98t (CF
3);-77.92t (CF
3);
3J
H, F=9.6Hz.
1H NMR (reference: TMS; Solvent: CD
3CN): 3.30s (4CH
3); 3.75q (CH
2);
3J
H, F=9.6Hz.
Embodiment 4: Tetrafluoroboric acid N, N, N ', N '-tetramethyl--S-ethyl isothiourea
The 70 cubic centimetre 1M solution (69.6 mmole) of Tetrafluoroboric acid triethyl oxygen in methylene dichloride are joined 4.6 gram (34.8 mmole) N, N, N ' in N '-tetramethyl thiourea, cools off reaction mixture simultaneously with the magnetic stirrer vigorous stirring and with ice bath.Reaction mixture was at room temperature stirred 6 hours, and all volatile constituents are removed in decompression.With resistates with 40 cubic centimetres of heat (60 ℃) hexane wash three times, and under the vacuum of 1.3 handkerchiefs in drying at room temperature 1 hour, produce 6.8 gram solid materials.Based on N, N, N ', N '-tetramethyl thiourea, Tetrafluoroboric acid N, N, N ', the yield of N '-tetramethyl--S-ethyl isothiourea is 78.8%.
19F NMR (reference: CCl
3Mark in the F-; Solvent: CD
3CN) :-150.34s; 150.40s (BF
4 -).
1H NMR (reference: TMS; Solvent: CD
3CN): 1.29t (CH
3); 2.99q (CH
2); 3.22s (4CH
3);
3J
H, H=7.4Hz.
Embodiment 5: trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--O-methyl-isourea
With 30.0 gram (258.3 mmole) N, N, N ', N '-tetramethyl-urea are dissolved in 150 cubic centimetres of pentanes, and restrain (263.3 mmole) trifluoromethanesulfonic acid methyl esters CF with 30 fens clock times slow (dropwise) adding 43.2
3SO
2OCH
3, simultaneously with reaction mixture with ice bath cooling and use the magnetic stirrer vigorous stirring.With reaction mixture restir 10 minutes at room temperature.Separate the low layer liquid phase also with 50 cubic centimetres of pentane washed twice.With resistates under 7.0 handkerchief vacuum in 60 ℃ of dryings 1 hour, produce 71.0 gram fluent materials.Based on N, N, N ', N '-tetramethyl-urea, trifluoromethanesulfonic acid N, N, N ', the yield of N '-tetramethyl--O-methyl-isourea is 98.1%.
19F NMR (reference: CCl
3Mark in the F-; Solvent: CD
3CN) :-77.88s (CF
3).
1H NMR (reference: TMS; Solvent: CD
3CN): 3.05s (4CH
3); 4.04s (CH
3).
Embodiment 6: three (pentafluoroethyl group) three hexafluorophosphoric acid N, N, N ', N '-tetramethyl--O-methyl-isourea
With 31.5 gram (112.4 mmole) trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--O-methyl-isourea are dissolved in 300 cubic centimetres of water, and at room temperature add 63.3 gram (118.7 mmole) five hydrations three (pentafluoroethyl group), three hexafluorophosphoric acid, use magnetic stirrer vigorous stirring reaction mixture simultaneously.Leach throw out also with 30 cubic centimetres of water washings three times.With resistates under 7.0 handkerchief vacuum in oil bath in 50-60 ℃ of drying 3 hours, produce 62.7 gram solid white materials (fusing point 69-70 ℃).Based on trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--O-methyl-isourea, three (pentafluoroethyl group) three hexafluorophosphoric acid N, N, N ', the yield of N '-tetramethyl--O-methyl-isourea is 96.8%.
19F NMR (reference: CCl
3Mark in the F-; Solvent: CD
3CN) :-43.51dm (PF);-79.54m (CF
3);-81.23m (2CF
3);-86.90dm (PF
2);-114.90m (CF
2);-115.48m (2CF
2);
1J
P, F=889Hz;
1J
P, F=901Hz;
2J
P, F=86Hz;
2J
P, F=98Hz.
1H NMR (reference: TMS; Solvent: CD
3CN): 3.05s (4CH
3); 4.04s (CH
3).
31P NMR (reference: 85%H
3PO
4Solvent: CD
3CN) :-148.57dtm;
1J
P, F=890Hz;
1J
P, F=902Hz.
Ultimate analysis
Measured value, %:C 24.94 H 2.64 N 4.89
C
12H
15F
18N
2The calculated value of OP, %:C 25.01 H 2.62 N 4.86
Embodiment 7: trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--O-ethyl isourea
With 15.0 gram (129.1 mmole) N, N, N ', N '-tetramethyl-urea are dissolved in 70 cubic centimetres of pentanes, and restrain (131.9 mmole) trifluoromethanesulfonic acid ethyl esters, CF with 30 fens clock times slow (dropwise) adding 23.5
3SO
2OC
2H
5, simultaneously with reaction mixture with ice bath cooling and use the magnetic stirrer vigorous stirring.With reaction mixture restir 10 minutes at room temperature.Separate the low layer liquid phase also with 30 cubic centimetres of pentanes washings three times.With resistates under 7.0 handkerchief vacuum in 50 ℃ of dryings 1 hour, produce 37.9 gram fluent materials.Based on N, N, N ', N '-tetramethyl-urea, trifluoromethanesulfonic acid N, N, N ', the yield of N '-tetramethyl--O-ethyl isourea is 99.8%.
19F NMR (reference: CCl
3Mark in the F-; Solvent: CD
3CN) :-77.86s (CF
3).
1H NMR (reference: TMS; Solvent: CD
3CN): 1.40t (CH
3); 3.05s (4CH
3); 4.38q (CH
2);
3J
H, H=7.1Hz.
Embodiment 8: three (pentafluoroethyl group) three hexafluorophosphoric acid N, N, N ', N '-tetramethyl--O-ethyl isourea
With 18.8 gram (63.9 mmole) trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--O-ethyl isothiourea is dissolved in 70 cubic centimetres of water, and at room temperature add 36.0 gram (67.2 mmole) five hydrations three (pentafluoroethyl group), three hexafluorophosphoric acid, use magnetic stirrer vigorous stirring reaction mixture simultaneously.Leach throw out also with 30 cubic centimetres of water washings four times.With resistates under 7.0 handkerchief vacuum in oil bath in 60 ℃ of dryings 3 hours, produce 36.7 gram solid white materials (fusing point 32-34 ℃).Based on trifluoromethanesulfonic acid N, N, N ', N '-tetramethyl--O-methyl-isourea, three (pentafluoroethyl group) three hexafluorophosphoric acid N, N, N ', the yield of N '-tetramethyl--O-ethyl isourea is 97.3%.
19F NMR (reference: CCl
3Mark in the F-; Solvent: CD
3CN) :-43.50dm (PF);-79.52m (CF
3);-81.21m (2CF
3);-86.88dm (PF
2);-114.90m (CF
2);-115.48m (2CF
2);
1J
P, F=889Hz;
1J
P, F=900Hz;
2J
P, F=84Hz;
2J
P, F=98Hz.
1H NMR (reference: TMS; Solvent: CD
3CN): 1.42t (CH
3); 3.05s (4CH
3); 4.37q (CH
2);
3J
H, H=7.0Hz.
31P NMR (reference: 85%H
3PO
4Solvent: CD
3CN) :-148.60dtm;
1J
P, F=888Hz;
1J
P, F=902Hz.
Ultimate analysis
Measured value, %:C 26.50 H 2.95 N 4.78
C
13H
17F
18N
2The calculated value of OP, %:C 26.45 H 2.90 N 4.75
9: two (pentafluoroethyl group) phospho acid of embodiment 2-methyl isophthalic acid, 1,3,3-tetramethyl-isourea
In being furnished with 25 ml flasks of reflux exchanger, restrain (16.6 mmole) oxidation three (pentafluoroethyl group) phosphine (C with 6.72
2F
5)
3P=O mixes with 15 cubic centimetres of glycol dimethyl ethers and 1.93 gram (16.6 mmole) tetramethyl-ureas.In this mixture, add 0.532 gram (16.6 mmole) methyl alcohol, use the magnetic stirrer stirred reaction mixture simultaneously.Make reaction mixture boiling 5 hours, under high vacuum (1.4 handkerchief), remove all volatile products, generation 6.59 gram viscous liquids in 50 ℃.Two (pentafluoroethyl group) phospho acid 2-methyl isophthalic acid, 1,3, the yield of 3-tetramethyl-isourea is 91.9%.
19F NMR (reference: CCl
3Mark in the F-; Solvent: CD
3CN) :-80.21m (2CF
3);-124.91dm (2CF
2);
2J
P, F=67Hz.
1H NMR (reference: TMS; Solvent: CD
3CN): 3.05s (4CH
3); 4.05s (OCH
3).
31P NMR (reference: 85%H
3PO
4Solvent: CD
3CN) :-2.12quin.;
2J
P, F=67Hz.
Claims (15)
1. the thiocarbamide of general formula (1) or urea salt:
Wherein
X represents O or S,
Wherein substituent R and R
0Representative independently of each other separately
The straight or branched alkyl that contains 1-20 carbon atom,
The straight or branched alkenyl that contains 2-20 carbon atom and one or more pairs of keys,
Contain 2-20 carbon atom and one or more triple-linked straight or branched alkynyl,
Saturated, the partially or completely undersaturated cycloalkyl that contains 3-7 carbon atom,
Its alkyl that can be contained 1-6 carbon atom replaces,
R also can represent hydrogen,
Wherein one or more substituent R or R
0Can partially or completely be replaced by halogen or the part by CN or NO
2Replace, but do not comprise that halogenation is at R
0The situation of α position, and
Halogen is represented F, Cl, Br or I,
Wherein substituent R and R
0Can be interconnection in pairs by singly-bound or two key,
And wherein not direct one or more substituent R or the R adjacent with heteroatoms
0Carbon atom or two non-conterminous carbon atoms can be selected from-O-,-C (O)-,-C (O) O-,-S-,-S (O)-,-SO
2-,-SO
3-,-N=,-N=N-,-NH-,-NR '-,-PR '-,-P (O) R '-,-P (O) R '-O-,-O-P (O) R '-O-and-P (R ')
2The atom of=N-and/or atomic group replace, wherein R ' contains not the fluoridizing of 1-6 carbon atom, partially fluorinated or fluoridized alkyl, the undersaturated cycloalkyl of saturated or part that contains 3-7 carbon atom, phenyl that does not replace or replace or the heterocycle that does not replace or replace
And
A
-Be selected from:
[R
1SO
3]
-, [R
F 'SO
3]
-, [(R
FSO
2)
2N]
-, [(R
FSO
2)
3C]
-, [(FSO
2)
3C]
-, [R
1CH
2OSO
3]
-, [R
1C (O) O]
-, [R
F 'C (O) O]
-, [CCl
3C (O) O]
-, [(CN)
3C]
-, [(CN)
2CR
1]
-, [(R
1O (O) C)
2CR
1]
-, [P (C
nF
2n+1-mH
m)
yF
6-y]
-, [P (C
6F
5)
yF
6-y]
-, [R
1 2P (O) O]
-, [R
1P (O) O
2]
2-, [(R
1O)
2P (O) O]
-, [(R
1O) P (O) O
2]
2-, [(R
1O) (R
1) P (O) O]
-, [R
F 2P (O) O]
-, [R
FP (O) O
2]
2-, [BF
zR
F 4-z]
-, [BF
z(CN)
4-z]
-, [B (CN)
4]
-, [B (C
6F
5)
4]
-, [B (OR
1)
4]
-, [N (CF
3)
2]
-, [N (CN)
2]
-, [AlCl
4]
-Or [SiF
6]
2-,
Substituent R wherein
FAnd R
F 'Representative independently of each other separately
Contain the perfluorination of 1-20 carbon atom and the alkyl of straight or branched, wherein R
F 'Do not comprise trifluoromethyl,
Contain the perfluorination of 2-20 carbon atom and one or more pairs of keys and the alkenyl of straight or branched,
Fluoridized phenyl and saturated, the partially or completely unsaturated cycloalkyl that contains 3-7 carbon atom, it can be replaced by perfluoroalkyl,
Substituent R wherein
FOr R
F 'Can be interconnection in pairs by singly-bound or two key, and
Substituent R wherein
FOr R
F 'In can be selected from carbon atom of heteroatomic α position or two non-conterminous carbon atoms-O-,-C (O)-,-S-,-S (O)-,-SO
2-,-N=,-N=N-,-NR '-,-PR '-and-P (O) R '-atom and/or atomic group replace, perhaps can contain end group R '-O-SO
2-or R '-O-C (O)-, wherein R ' representative contains not the fluoridizing of 1-6 carbon atom, partially fluorinated or fluoridized alkyl, contains the undersaturated cycloalkyl of saturated or part of 3-7 carbon atom, the phenyl that does not replace or replace or the heterocycle of replacement or replacement not,
And
Substituent R wherein
1Representative independently of each other separately
Work as A
-=[(CN)
2CR
1]
-Or [(R
1O (O) C)
2CR
1]
-And when X=O or S, be hydrogen, or
Work as A
-=[R
1CH
2OSO
3]
-, X=S or O and substituent R and R
0=when containing the alkyl of 1 to 20 carbon atom, be hydrogen,
The straight or branched alkyl that contains 1-20 carbon atom,
The straight or branched alkenyl that contains 2-20 carbon atom and one or more pairs of keys,
Contain 2-20 carbon atom and one or more triple-linked straight or branched alkynyl,
Saturated, the partially or completely undersaturated cycloalkyl that contains 3-7 carbon atom,
Its alkyl that can be contained 1-6 carbon atom replaces,
Substituent R wherein
1Can be partly by CN, NO
2Or the halogen replacement, and
Halogen is represented F, Cl, Br or I,
Substituent R wherein
1Can be interconnection in pairs by singly-bound or two key, and
Substituent R wherein
1In can be selected from carbon atom of heteroatomic α position or two non-conterminous carbon atoms-O-,-C (O)-,-C (O) O-,-S-,-S (O)-,-SO
2-,-SO
3-,-N=,-N=N-,-NH-,-NR '-,-PR ' and-P (O) R ', P (O) R ' O-, OP (O) R ' O-,-PR '
2=N-,-C (O) NH-,-C (O) NR '-,-SO
2NH-or-SO
2NR '-atom and/or atomic group replace, wherein R ' representative contains not the fluoridizing of 1-6 carbon atom, partially fluorinated or fluoridized alkyl, the undersaturated cycloalkyl of saturated or part that contains 3-7 carbon atom, phenyl that does not replace or replace or the heterocycle that does not replace or replace
And variable
N represents 1 to 20,
M represents 0,1,2 or 3,
Y represents 0,1,2,3 or 4,
Z represents 0,1,2 or 3,
Condition is
As X=S and R and R
0=when containing the alkyl of 1 to 20 carbon atom, negatively charged ion A
-Can=[BF
4]
-, CF
3COO
-, [B (C
6H
5)
4]
-Or [CH
3C
6H
4SO
3]
-,
And when X=O, negatively charged ion A
-Can=CF
3COO
-[B (C
6H
5)
4]
-, and
As X=O and R
0During=ethyl, get rid of negatively charged ion A
-=CH
3CH
2OSO
3 -
2. according to the salt of claim 1, it is characterized in that R is hydrogen and/or the straight or branched alkyl that contains 1 to 12 carbon atom.
3. according to the salt of claim 1 or 2, it is characterized in that R is selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, sec-butyl, phenyl and cyclohexyl.
4. according to the salt of one of claim 1 to 3, it is characterized in that X=S.
5. according to the salt of one of claim 1 to 4, it is characterized in that R
0Representative contains the straight or branched alkyl of 1 to 12 carbon atom, and it can partially or completely be replaced by F, but wherein gets rid of R
0α-CH
2Fluoridizing of group, and X=S.
6. according to the salt of one of claim 1 to 3, it is characterized in that X=O.
7. according to the salt of one of claim 1 to 3 or 6, it is characterized in that R
0Representative contains the straight or branched alkyl of 1 to 12 carbon atom, and X=O.
8. according to the salt of one of claim 1 to 7, it is characterized in that described negatively charged ion is selected from:
[CF
3SO
3]
-, [CF
3CF
2SO
3]
-, [CH
3CH
2SO
3]
-, [(CF
3SO
2)
2N]
-, [(C
2F
5SO
2)
2N]
-, [(CF
3SO
2)
3C]
-, [(C
2F
5SO
2)
3C]
-, [CH
3CH
2OSO
3]
-, [(FSO
2)
3C]
-, [CF
3C (O) O]
-, [CF
3CF
2C (O) O]
-, [CH
3CH
2C (O) O]
-, [CH
3C (O) O]
-, [P (C
2F
5)
3F
3]
-, [P (CF
3)
3F
3]
-, [P (C
2F
4H) (CF
3)
2F
3]
-, [P (C
2F
3H
2)
3F
3]
-, [P (C
2F
5) (CF
3)
2F
3]
-, [P (C
6F
5)
3F
3]
-, [P (C
3F
7)
3F
3]
-, [P (C
4F
9)
3F
3]
-, [P (C
2F
5)
2F
4]
-, [(C
2F
5)
2P (O) O]
-, [(C
2F
5) P (O) O
2]
2-, [P (C
6F
5)
2F
4]
-, [(CF
3)
2P (O) O]
-, [(CH
3)
2P (O) O]
-, [(C
4F
9)
2P (O) O]
-, [CF
3P (O) O
2]
2-, [CH
3P (O) O
2]
2-, [(CH
3O)
2P (O) O]
-, [BF
3(CF
3)]
-, [BF
2(C
2F
5)
2]
-, [BF
3(C
2F
5)]
-, [BF
2(CF
3)
2]
-, [B (C
2F
5)
4]
-, [BF
3(CN)]
-, [BF
2(CN)
2]
-, [B (CN)
4]
-, [B (CF
3)
4]
-, [BF
4]
-, [B (OCH
3)
4]
-, [B (OCH
3)
2(OC
2H
5)]
-, [B (O
2C
2H
4)
2]
-, [B (O
2C
2H
2)
2]
-, [B (O
2CH
4)
2]
-, [N (CF
3)
2]
-, [N (CN)
2]
-, [C (CN)
2]
-, [AlCl
4]
-Or [SiF
6]]
2-
9. according to the preparation method of the salt of one of claim 1 to 8, it is characterized in that using ester AR
0Or use oxonium salt (R
0)
3O
+A
-With thiocarbamide C (S) (NR
2)
2Or urea C (O) (NR
2)
2Alkylation, wherein R such as one of claim 1 to 8 definition, R wherein
0Such as one of claim 1 to 8 definition and A be selected from [R
1CH
2OSO
3], [R
1SO
3], [R
FSO
3], [R
FC (O) O] and [CCl
3C (O) O], radicals R wherein
1Or R
FSuch as one of claim 1 to 8 definition and A
-Be selected from [(FSO
2)
3C]
-[BF
4]
-
10. according to the method for claim 9, it is characterized in that this is reflected under the temperature that at least a component is a liquid carries out.
11., it is characterized in that the salt and the salt Kt of general formula (1) according to the preparation method of the salt of one of claim 1 to 8
+A
-Or with sour AH reaction,
Wherein radicals R and R
0Such as one of claim 1 to 8 definition, negatively charged ion A
-Be selected from [BF
4]
-, Br
-, Cl
-, I
-Or [ClO
4]
-, wherein Kt is basic metal or alkaline-earth metal, A such as one of claim 1 to 8 definition.
12. as the salt of one of claim 1 to 8 or multinomial defined formula (1) as ion liquid purposes.
13. as the salt of one of claim 1 to 8 or multinomial defined formula (1) purposes as nonaqueous electrolyte.
14. as the salt of one of claim 1 to 8 or multinomial defined formula (1) purposes as phase-transfer catalyst.
15. as the salt of one of claim 1 to 8 or multinomial defined formula (1) purposes as tensio-active agent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10325050.6 | 2003-06-02 | ||
| DE2003124891 DE10324891A1 (en) | 2003-06-02 | 2003-06-02 | Thiouronium or uronium salts with various anions, e.g. triflate or tetrakis-pentafluorophenyl-borate, used as ionic liquids, non-aqueous electrolytes, phase-transfer catalysts and surfactants |
| DE10324891.9 | 2003-06-02 | ||
| DE10353758.9 | 2003-11-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1798731A true CN1798731A (en) | 2006-07-05 |
Family
ID=33482371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480015435 Pending CN1798731A (en) | 2003-06-02 | 2004-05-28 | Ionic liquid comprising uronium cations or thiouronium cations |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1798731A (en) |
| DE (1) | DE10324891A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391166A (en) * | 2011-07-20 | 2012-03-28 | 彩虹集团公司 | Preparation method of ionic liquid for dye-sensitized solar cell |
| CN104926782A (en) * | 2015-05-13 | 2015-09-23 | 南昌航空大学 | Method for preparing cyclic carbonate using isothiourea salt ionic liquid |
| CN106588728A (en) * | 2016-12-15 | 2017-04-26 | 山东省医学科学院药物研究所 | Ionic liquid containing thiourea structure, and synthesis method and application thereof |
| US10450264B2 (en) | 2015-07-10 | 2019-10-22 | Uop Llc | Synthesis of non-cyclic amide and thioamide based ionic liquids |
| US10550049B2 (en) | 2015-07-10 | 2020-02-04 | Uop Llc | Hydrocarbon conversion processes using non-cyclic amide and thioamide based ionic liquids |
-
2003
- 2003-06-02 DE DE2003124891 patent/DE10324891A1/en not_active Withdrawn
-
2004
- 2004-05-28 CN CN 200480015435 patent/CN1798731A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391166A (en) * | 2011-07-20 | 2012-03-28 | 彩虹集团公司 | Preparation method of ionic liquid for dye-sensitized solar cell |
| CN104926782A (en) * | 2015-05-13 | 2015-09-23 | 南昌航空大学 | Method for preparing cyclic carbonate using isothiourea salt ionic liquid |
| US10450264B2 (en) | 2015-07-10 | 2019-10-22 | Uop Llc | Synthesis of non-cyclic amide and thioamide based ionic liquids |
| US10550049B2 (en) | 2015-07-10 | 2020-02-04 | Uop Llc | Hydrocarbon conversion processes using non-cyclic amide and thioamide based ionic liquids |
| CN106588728A (en) * | 2016-12-15 | 2017-04-26 | 山东省医学科学院药物研究所 | Ionic liquid containing thiourea structure, and synthesis method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10324891A1 (en) | 2004-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1167405C (en) | Keratin fibre dyeing composition containing pyrazolo-(1,5-alpha)-pyrimidine derivatives, dyeing method, pyrazolo-(1,5-alpha) pyrimidine new-type derivatives and preparation method thereof | |
| CN1160817C (en) | Electrolytes containing mixed fluorocarbon/hydrocarbon imide and methide salts | |
| CN1279046C (en) | Fluoroalkyl phosphate for electrochemical cells | |
| CN1330567A (en) | Microemulsions containing water and hydrofluoroethers | |
| JP5172667B2 (en) | Ionic liquid with low viscosity | |
| CN100335967C (en) | Polyoxyalkylene ammonium salts and their use as antistatic agents | |
| CN1327986A (en) | Ion type liquid | |
| CN1358726A (en) | Tetrafluoalkylborate and use as conductive salt | |
| US8859813B2 (en) | Ionic liquids having uronium cations and a process for making same | |
| CN1013198B (en) | Anti-tumour sulfonylurea deriv. preparing process | |
| CN1974547A (en) | Ionic liquid of alkyl guanidine salt and its prepn process | |
| CN1283645C (en) | Novel strong acids, process for the preparation thereof, and uses thereof | |
| CN1974550A (en) | Process for the preparation of compounds having a CF2O bridge | |
| CN1227253C (en) | Method for producing sulfonamide-substituted imidazotriazinones | |
| CN1798731A (en) | Ionic liquid comprising uronium cations or thiouronium cations | |
| CN1353134A (en) | Electrolyte | |
| CN1492898A (en) | Diepisulfide based prepolymers and their use in the optical field | |
| CN1874844A (en) | Method for the production of nickel(0)-phosphorous ligand complexes | |
| CN1070222A (en) | Preparation contains the method for the detergent composition of alkyl sulfate particles and basic granules | |
| CN1202163A (en) | Benzothiazolone derivatives | |
| CN1318546A (en) | Lithium salt, its prep., anhydrous electrolyte and electrochemical cell | |
| CN1712395A (en) | Nitrogen containing fluoride paraffin sulfonate | |
| CN1726200A (en) | Ionic liquids comprising [N(CF3)2] anions | |
| CN1441702A (en) | Composition and compound based on metal and acid salts having sulphonyl group borne by perhalogenated carbon and their use as Lewis acid | |
| CN101068791A (en) | Method for preparing salt with tetrafluoroborate anion and reducing the content of hologenate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |