US20090130767A1 - Organosilanes and substrates covalently bonded with same and methods for synthesis and use - Google Patents
Organosilanes and substrates covalently bonded with same and methods for synthesis and use Download PDFInfo
- Publication number
- US20090130767A1 US20090130767A1 US12/275,117 US27511708A US2009130767A1 US 20090130767 A1 US20090130767 A1 US 20090130767A1 US 27511708 A US27511708 A US 27511708A US 2009130767 A1 US2009130767 A1 US 2009130767A1
- Authority
- US
- United States
- Prior art keywords
- alkyl
- optionally substituted
- aryl
- compound
- hydroxy
- 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.)
- Abandoned
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 title description 13
- 230000015572 biosynthetic process Effects 0.000 title description 9
- 150000001282 organosilanes Chemical class 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims description 88
- 125000003118 aryl group Chemical group 0.000 claims description 66
- 125000000217 alkyl group Chemical group 0.000 claims description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 36
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 35
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 125000003545 alkoxy group Chemical group 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 15
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 claims description 15
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 15
- 125000005279 aryl sulfonyloxy group Chemical group 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000004458 analytical method Methods 0.000 claims description 11
- 238000004587 chromatography analysis Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000004677 hydrates Chemical class 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000012453 solvate Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 238000013375 chromatographic separation Methods 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- 125000005001 aminoaryl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 3
- 125000005372 silanol group Chemical group 0.000 claims description 3
- 125000001475 halogen functional group Chemical group 0.000 claims 10
- 150000003377 silicon compounds Chemical class 0.000 abstract description 14
- -1 cyano, phenyl Chemical group 0.000 description 86
- 125000001424 substituent group Chemical group 0.000 description 22
- 0 [1*]C([2*])[3*] Chemical compound [1*]C([2*])[3*] 0.000 description 19
- 125000001072 heteroaryl group Chemical group 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- 150000001412 amines Chemical class 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- 150000001408 amides Chemical class 0.000 description 11
- 125000000753 cycloalkyl group Chemical group 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 10
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000003093 cationic surfactant Substances 0.000 description 9
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 7
- 150000002466 imines Chemical class 0.000 description 7
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 6
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 6
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical compound C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 description 6
- GBROPGWFBFCKAG-UHFFFAOYSA-N picene Chemical compound C1=CC2=C3C=CC=CC3=CC=C2C2=C1C1=CC=CC=C1C=C2 GBROPGWFBFCKAG-UHFFFAOYSA-N 0.000 description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 150000004756 silanes Chemical class 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 150000001345 alkine derivatives Chemical class 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000004404 heteroalkyl group Chemical group 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 5
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 5
- 125000005647 linker group Chemical group 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- GIEMHYCMBGELGY-UHFFFAOYSA-N 10-undecen-1-ol Chemical compound OCCCCCCCCCC=C GIEMHYCMBGELGY-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 229910004749 OS(O)2 Inorganic materials 0.000 description 4
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 4
- 239000013504 Triton X-100 Substances 0.000 description 4
- 229920004890 Triton X-100 Polymers 0.000 description 4
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 4
- 239000012346 acetyl chloride Substances 0.000 description 4
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 4
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 4
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- NQFOGDIWKQWFMN-UHFFFAOYSA-N phenalene Chemical compound C1=CC([CH]C=C2)=C3C2=CC=CC3=C1 NQFOGDIWKQWFMN-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- MZFGYVZYLMNXGL-UHFFFAOYSA-N undec-10-enoyl chloride Chemical compound ClC(=O)CCCCCCCCC=C MZFGYVZYLMNXGL-UHFFFAOYSA-N 0.000 description 4
- 239000003039 volatile agent Substances 0.000 description 4
- AIFRHYZBTHREPW-UHFFFAOYSA-N β-carboline Chemical compound N1=CC=C2C3=CC=CC=C3NC2=C1 AIFRHYZBTHREPW-UHFFFAOYSA-N 0.000 description 4
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 3
- OFHHDSQXFXLTKC-UHFFFAOYSA-N 10-undecenal Chemical compound C=CCCCCCCCCC=O OFHHDSQXFXLTKC-UHFFFAOYSA-N 0.000 description 3
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 3
- MFJCPDOGFAYSTF-UHFFFAOYSA-N 1H-isochromene Chemical compound C1=CC=C2COC=CC2=C1 MFJCPDOGFAYSTF-UHFFFAOYSA-N 0.000 description 3
- AAQTWLBJPNLKHT-UHFFFAOYSA-N 1H-perimidine Chemical compound N1C=NC2=CC=CC3=CC=CC1=C32 AAQTWLBJPNLKHT-UHFFFAOYSA-N 0.000 description 3
- ODMMNALOCMNQJZ-UHFFFAOYSA-N 1H-pyrrolizine Chemical compound C1=CC=C2CC=CN21 ODMMNALOCMNQJZ-UHFFFAOYSA-N 0.000 description 3
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 3
- UXGVMFHEKMGWMA-UHFFFAOYSA-N 2-benzofuran Chemical compound C1=CC=CC2=COC=C21 UXGVMFHEKMGWMA-UHFFFAOYSA-N 0.000 description 3
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 3
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 3
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 3
- JFKUBRAOUZEZSL-UHFFFAOYSA-N 4-butylbenzoic acid Chemical compound CCCCC1=CC=C(C(O)=O)C=C1 JFKUBRAOUZEZSL-UHFFFAOYSA-N 0.000 description 3
- GDRVFDDBLLKWRI-UHFFFAOYSA-N 4H-quinolizine Chemical compound C1=CC=CN2CC=CC=C21 GDRVFDDBLLKWRI-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- 229940127007 Compound 39 Drugs 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- JDPAVWAQGBGGHD-UHFFFAOYSA-N aceanthrylene Chemical group C1=CC=C2C(C=CC3=CC=C4)=C3C4=CC2=C1 JDPAVWAQGBGGHD-UHFFFAOYSA-N 0.000 description 3
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 3
- SQFPKRNUGBRTAR-UHFFFAOYSA-N acephenanthrylene Chemical group C1=CC(C=C2)=C3C2=CC2=CC=CC=C2C3=C1 SQFPKRNUGBRTAR-UHFFFAOYSA-N 0.000 description 3
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 3
- BVUSIQTYUVWOSX-UHFFFAOYSA-N arsindole Chemical compound C1=CC=C2[As]C=CC2=C1 BVUSIQTYUVWOSX-UHFFFAOYSA-N 0.000 description 3
- KNNXFYIMEYKHBZ-UHFFFAOYSA-N as-indacene Chemical compound C1=CC2=CC=CC2=C2C=CC=C21 KNNXFYIMEYKHBZ-UHFFFAOYSA-N 0.000 description 3
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000000105 evaporative light scattering detection Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
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- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000012434 mixed-mode chromatography Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PIDFDZJZLOTZTM-KHVQSSSXSA-N ombitasvir Chemical compound COC(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@H]1C(=O)NC1=CC=C([C@H]2N([C@@H](CC2)C=2C=CC(NC(=O)[C@H]3N(CCC3)C(=O)[C@@H](NC(=O)OC)C(C)C)=CC=2)C=2C=CC(=CC=2)C(C)(C)C)C=C1 PIDFDZJZLOTZTM-KHVQSSSXSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- HAIMOVORXAUUQK-UHFFFAOYSA-J zirconium(iv) hydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[Zr+4] HAIMOVORXAUUQK-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
- B01J20/3261—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic structures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
- B01J20/287—Non-polar phases; Reversed phases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
- B01J20/3259—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulfur with at least one silicon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
Definitions
- the present invention relates generally to novel silicon compounds, methods for making these novel silicon compounds, compositions comprising these novel silicon compounds attached to substrates, methods for attaching the novel silicon compounds to substrates and methods for using the compositions in a variety of chromatographic applications.
- Polar-embedded phases improve the peak shape of basic analytes and enable operation of reverse phase HPLC columns in highly aqueous environments (O'Gara et al., LC-GC 2001, 19 (6):632-641).
- Commonly used polar groups include, for example, amides, ureas, ethers and carbamates.
- polar-embedded phases provide superior peak shapes of basic analytes and are more compatible with highly aqueous environments when compared to general purpose reverse phases. Further, polar embedded phases often have selectivities which are substantially different from those exhibited by conventional C-18 packings.
- Surfactants are important components of a variety of consumer, industrial, agricultural and pharmaceutical products. Surfactant analysis is often complicated by the presence of mixtures which are difficult to resolve using conventional chromatography. Surfactants have been analyzed by liquid chromatography on reversed-phase columns (e.g., C18, C8, cyano, phenyl, etc.), normal phase columns, ion-exchange columns and size-exclusion columns (Schmitt, “Analysis of Surfactants,” 2 nd edition, Marcel Dekker, Inc, New York, 2001, 197-292). C18 columns provide reasonable separation, peak efficiency and asymmetry, especially for anionic surfactants.
- reversed-phase columns e.g., C18, C8, cyano, phenyl, etc.
- normal phase columns e.g., ion-exchange columns and size-exclusion columns
- silica-based reversed-phase columns often prevents satisfactory resolution of cationic surfactants.
- C18 reversed phase columns fail to separate individual oligomers of polyethylene glycol (PEG) based surfactants.
- PEG polyethylene glycol
- conventional high-density C18 columns are unsuitable for analysis of highly hydrophilic hydrotopes, (e.g. sodium naphthalene sulfonate and xylene sulfonate).
- novel silane compounds which have both hydrophobic and polar functionality, substrates functionalized with these new silane compounds and the use of these novel functionalized substrates to simultaneously separate cationic, nonionic and anionic surfactants.
- the present invention satisfies these and other needs by providing a new class of silane compounds, which have hydrophobic and polar functionality, substrates functionalized with these new silane compounds and the use of these novel functionalized substrates to simultaneously separate cationic, nonionic, and anionic surfactants.
- the compound of Formula (I) has at least one activated silyl group (e.g., Si(OMe) 3 , —SiMe(OMe) 2 , —SiMe 2 (OMe), —Si(OEt) 3 , —SiMe(OEt) 2 , —SiMe 2 (OEt), —SiMe 2 NMe 2 , —SiCl 3 , etc.), at least one polar group (e.g., amide, sulfonamide, carbamate, urea, ester, etc.) and a short head chain (e.g., (C 1 -C 6 ) alkyl) connected to the polar group.
- activated silyl group e.g., Si(OMe) 3 , —SiMe(OMe) 2 , —SiMe 2 (OMe), —Si(OEt) 3 , —SiMe(OEt) 2 ,
- R 1 , R 2 and R 3 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more R 12 groups, provided that at least one of R 1 , R 2 and R 3 are not alkyl, aryl or hydroxyl;
- L 1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl;
- Y is —C(O)N(R 4 )(R 5 ), —N(R 4 )C(O)R 7 , —N(R 4 )S(O 2 )R 7 , —S(O) 2 N(R 4 )(R 5 ), —OC(O)R 7 , —OC(O)N(R 4 )(R 5 ), —N(R 4 )C(O)OR 7 , —N(R 4 )C(O)N(R 5 )(R 6 ) or —N(R 4 )S(O 2 )N(R 5 )(R 6 ); and
- R 4 , R 5 and R 6 are independently hydrogen, (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups;
- R 7 is (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups;
- R 14 is (C 1 -C 6 )alkyl
- R 4 , R 5 or R 6 is not hydrogen.
- compositions including a compound of Formula (II) covalently bonded to a substrate are provided.
- the composition is in a flow-through bed suitable for use a reverse phase chromatographic medium.
- composition comprising the compound of structural Formula (II) covalently bonded to a substrate and a compound of structural Formula (IV) covalently bonded to the substrate is provided wherein:
- R 8 , R 9 , and R 10 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl optionally substituted with one or more of the same or different R 14 groups, provided that at least one of R 1 , R 2 and R 3 are not alkyl, aryl or hydroxyl;
- R 15 is (C 1 -C 6 )alkyl
- L 2 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl;
- W is an ionizable group.
- a chromatographic method is provided.
- An aqueous liquid is flowed through a bed of separation medium, which includes either a composition containing a compound of Formula (II) covalently bonded to a substrate or a composition comprising the compound of structural Formula (II) covalently bonded to a substrate and a compound of structural Formula (IV) covalently bonded to the substrate.
- a method for chromatographic separation of analytes in a liquid sample is provided.
- the liquid sample is flowed through medium, which includes a composition containing a compound of Formula (II) covalently bonded to a substrate or a composition comprising the compound of structural Formula (II) covalently bonded to a substrate and a compound of structural Formula (IV) covalently bonded to the substrate.
- a method for simultaneous analysis of inorganic analytes and organic analytes in a liquid sample is provided.
- the liquid sample is flowed through medium, which includes a composition containing a compound of Formula (II) covalently bonded to a substrate or a composition of a compound of structural Formula (II) and a compound of structural Formula (IV) covalently bonded to a substrate.
- FIG. 1 illustrates the synthesis of an amide of Formula (II);
- FIG. 2 illustrates the synthesis of amine derivatives of Formula (II);
- FIG. 3 illustrates the synthesis of alcohol derivatives of Formula (II);
- FIG. 4 illustrates synthesis of a compound of Formula (IV).
- FIG. 5 illustrates the separation of uracil, p-butyl benzoic acid and phenanthrene by a C8 column and a column packed with composition 27 ;
- FIG. 6 illustrates separation of a number of surfactants with and a column packed with composition 36 ;
- FIG. 7 illustrates the separation of Triton X-100 with a conventional C18 column and a column packed with composition 36 ;
- FIG. 8 illustrates the separation of a number of surfactants with a conventional C18 column and a column packed with composition 36 ;
- FIG. 9 illustrates the separation of lauryldimethylbenzyl ammonium chloride with a conventional C18 column and a column packed with composition 36 ;
- FIG. 10 illustrates the separation of sodium xylene sulfonate with a conventional C18 column and a column packed with composition 36 .
- Alkyl by itself or as part of another substituent, refers to a saturated or unsaturated, branched, straight-chain or cyclic monovalent hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent alkane, alkene or alkyne.
- Typical alkyl groups include, but are not limited to, methyl; ethyls such as ethanyl, ethenyl, ethynyl; propyls such as propan-1-yl, propan-2-yl, cyclopropan-1-yl, prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl(allyl), cycloprop-1-en-1-yl; cycloprop-2-en-1-yl, prop-1-yn-1-yl, prop-2-yn-1-yl, etc.; butyls such as butan-1-yl, butan-2-yl, 2-methyl-propan-1-yl, 2-methyl-propan-2-yl, cyclobutan-1-yl, but-1-en-1-yl, but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-2-yl, buta-1,
- alkyl is specifically intended to include groups having any degree or level of saturation, i.e., groups having exclusively single carbon-carbon bonds, groups having one or more double carbon-carbon bonds, groups having one or more triple carbon-carbon bonds and groups having mixtures of single, double and triple carbon-carbon bonds. Where a specific level of saturation is intended, the expressions “alkanyl,” “alkenyl,” and “alkynyl” are used. In some embodiments, an alkyl group comprises from 1 to 20 carbon atoms. In other embodiments, an alkyl group comprises from 1 to 10 carbon atoms.
- Alkanyl by itself or as part of another substituent, refers to a saturated branched, straight-chain or cyclic alkyl radical derived by the removal of one hydrogen atom from a single carbon atom of a parent alkane.
- Typical alkanyl groups include, but are not limited to, methanyl; ethanyl; propanyls such as propan-1-yl, propan-2-yl(isopropyl), cyclopropan-1-yl, etc.; butanyls such as butan-1-yl, butan-2-yl(sec-butyl), 2-methyl-propan-1-yl(isobutyl), 2-methyl-propan-2-yl (t-butyl), cyclobutan-1-yl, etc.; and the like.
- Alkenyl by itself or as part of another substituent, refers to an unsaturated branched, straight-chain or cyclic alkyl radical having at least one carbon-carbon double bond derived by the removal of one hydrogen atom from a single carbon atom of a parent alkene.
- the group may be in either the cis or trans conformation about the double bond(s).
- Typical alkenyl groups include, but are not limited to, ethenyl; propenyls such as prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl(allyl), prop-2-en-2-yl, cycloprop-1-en-1-yl, cycloprop-2-en-1-yl; butenyls such as but-1-en-1-yl, but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-1-yl, but-2-en-2-yl, buta-1,3-dien-1-yl, buta-1,3-dien-2-yl, cyclobut-1-en-1-yl, cyclobut-1-en-3-yl, cyclobuta-1,3-dien-1-yl, etc.; and the like.
- Alkynyl by itself or as part of another substituent, refers to an unsaturated branched, straight-chain or cyclic alkyl radical having at least one carbon-carbon triple bond derived by the removal of one hydrogen atom from a single carbon atom of a parent alkyne.
- Typical alkynyl groups include, but are not limited to, ethynyl; propynyls such as prop-1-yn-1-yl, prop-2-yn-1-yl, etc.; butynyls such as but-1-yn-1-yl, but-1-yn-3-yl, but-3-yn-1-yl, etc.; and the like.
- Alkyldiyl by itself or as part of another substituent, refers to a saturated or unsaturated, branched, straight-chain or cyclic divalent hydrocarbon group derived by the removal of one hydrogen atom from each of two different carbon atoms of a parent alkane, alkene or alkyne, or by the removal of two hydrogen atoms from a single carbon atom of a parent alkane, alkene or alkyne.
- the two monovalent radical centers or each valency of the divalent radical center can form bonds with the same or different atoms.
- Typical alkyldiyl groups include, but are not limited to methandiyl; ethyldiyls such as ethan-1,1-diyl, ethan-1,2-diyl, ethen-1,1-diyl, ethen-1,2-diyl; propyldiyls such as propan-1,1-diyl, propan-1,2-diyl, propan-2,2-diyl, propan-1,3-diyl, cyclopropan-1,1-diyl, cyclopropan-1,2-diyl, prop-1-en-1,1-diyl, prop-1-en-1,2-diyl, prop-2-en-1,2-diyl, prop-1-en-1,3-diyl, cycloprop-1-en-1,2-diyl, cycloprop-2-en-1,2-diyl, cycloprop-2-en-1,2-di
- alkanyldiyl alkenyldiyl and/or alkynyldiyl is used.
- the alkyldiyl group is (C 1 -C 20 )alkyldiyl. In other embodiments, the alkyldiyl group is (C 1 -C 10 )alkyldiyl.
- the alkyldiyl group is a saturated acyclic alkanyldiyl group in which the radical centers are at the terminal carbons, e.g., methandiyl(methano); ethan-1,2-diyl(ethano); propan-1,3-diyl (propano); butan-1,4-diyl(butano); and the like (also referred to as alkyleno, defined infra).
- Alkyleno by itself or as part of another substituent, refers to a straight-chain alkyldiyl group having two terminal monovalent radical centers derived by the removal of one hydrogen atom from each of the two terminal carbon atoms of straight-chain parent alkane, alkene or alkyne.
- Typical alkyleno groups include, but are not limited to, methano; ethylenos such as ethano, etheno, ethyno; propylenos such as propano, prop[1]eno, propa[1,2]dieno, prop[1]yno, etc.; butylenos such as butano, but[1]eno, but[2]eno, buta[1,3]dieno, but[1]yno, but[2]yno, but[1,3]diyno, etc.; and the like. Where specific levels of saturation are intended, the nomenclature alkano, alkeno and/or alkyno is used.
- the alkyleno group is (C 1 -C 20 )alkyleno. In other embodiments, the alkyleno group is (C 1 -C 10 ) alkyleno. In still other embodiments, the alkyleno group is a straight-chain saturated alkano groups, e.g., methano, ethano, propano, butano, and the like.
- Alkylsulfonyloxy by itself or as part of another substituent, refers to a radical —OS(O) 2 R 30 where R 30 represents an alkyl or cycloalkyl group as defined herein.
- Alkoxy by itself or as part of another substituent, refers to a radical —OR 31 where R 31 represents an alkyl or cycloalkyl group as defined herein Representative examples include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy and the like.
- Alkoxycarbonyl by itself or as part of another substituent, refers to a radical —C(O)OR 32 where R 32 represents an alkyl or cycloalkyl group as defined herein.
- Aryl by itself or as part of another substituent, refers to a monovalent aromatic hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent aromatic ring system.
- Typical aryl groups include, but are not limited to, groups derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexylene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, pic
- Aryldiyl by itself or as part of another substituent refers to a divalent hydrocarbon radical derived by the removal of one hydrogen atom from each of two different carbon atoms of a parent aromatic system or by removal of two hydrogen atoms from a single carbon atom of a parent aromatic ring system.
- the two monovalent radical centers or each valency of the divalent center can form bonds with the same or different atom(s).
- Typical aryldiyl groups include, but are not limited to, groups derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexylene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene and the like.
- Aryloxycarbonyl by itself or as part of another substituent, refers to a radical —C(O)OR 33 where R 33 represents an aryl group as defined herein.
- Arylsulfonyloxy by itself or as part of another substituent, refers to a radical —OS(O) 2 R 35 where R 35 represents an alkyl or cycloalkyl group as defined herein.
- Cycloalkyl by itself or as part of another substituent, refers to a saturated or unsaturated cyclic alkyl radical. Where a specific level of saturation is intended, the nomenclature “cycloalkanyl” or “cycloalkenyl” is used. Typical cycloalkyl groups include, but are not limited to, groups derived from cyclopropane, cyclobutane, cyclopentane, cyclohexane and the like. In some embodiments, the cycloalkyl group is (C 3 -C 10 ) cycloalkyl. In other embodiments, the cycloalkyl group is (C 3 -C 7 ) cycloalkyl.
- Heteroalkyl, Heteroalkanyl Heteroalkenyl, Heteroalkanyl, Heteroalkyldiyl and Heteroalkyleno by themselves or as part of another substituent, refer to alkyl, alkanyl, alkenyl, alkynyl, alkyldiyl and alkyleno groups, respectively, in which one or more of the carbon atoms (and any associated hydrogen atoms) are each independently replaced with the same or different heteroatomic groups.
- Typical heteroatomic groups which can be included in these groups include, but are not limited to, —O—, —S—, —O—O—, —S—S—, —O—S—, —NR 35 R 36 —, ⁇ N—N ⁇ , —N ⁇ N—, —N ⁇ N—NR 37 R 38 , —PR 39 —, —P(O) 2 —, —POR 40 —, —O—P(O) 2 —, —SO—, —SO 2 —, —SnR 41 R 42 — and the like, where R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 and R 42 are independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, substituted arylalkyl, cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substituted cycloheteroal
- Heteroaryl by itself or as part of another substituent, refers to a monovalent heteroaromatic radical derived by the removal of one hydrogen atom from a single atom of a parent heteroaromatic ring system.
- Typical heteroaryl groups include, but are not limited to, groups derived from acridine, arsindole, carbazole, ⁇ -carboline, chromane, chromene, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine
- the heteroaryl group is from 5-20 membered heteroaryl. In other embodiments, the heteroaryl group is from 5-10 membered heteroaryl. In still other embodiments, the heteroaryl groups are those derived from thiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine, quinoline, imidazole, oxazole and pyrazine.
- Heteroaryldiyl by itself or as part of another substituent refers to a divalent radical derived by the removal of one hydrogen atom from each of two different carbon atoms of a parent heteroaromatic system or by removal of two hydrogen atoms from a single carbon atom of a parent aromatic ring system.
- heteroaryldiyl groups include, but are not limited to, groups derived from acridine, arsindole, carbazole, ⁇ -carboline, chromane, chromene, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyr
- Parent aromatic ring system by itself or as part of another substituent, refers to an unsaturated cyclic or polycyclic ring system having a conjugated n electron system.
- parent aromatic ring system fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, fluorene, indane, indene, phenalene, etc.
- Typical parent aromatic ring systems include, but are not limited to, aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexylene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene and the like.
- Parent Heteroaromatic Ring System by itself or as part of another substituent, refers to a parent aromatic ring system in which one or more carbon atoms (and any associated hydrogen atoms) are independently replaced with the same or different heteroatom.
- Typical heteroatoms to replace the carbon atoms include, but are not limited to, N, P, O, S, Si, etc.
- fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, arsindole, benzodioxan, benzofuran, chromane, chromene, indole, indoline, xanthene, etc.
- Typical parent heteroaromatic ring systems include, but are not limited to, arsindole, carbazole, ⁇ -carboline, chromane, chromene, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline, quinolizine, quinoxaline, tetrazole, thi
- “Substituted” refers to a group in which one or more hydrogen atoms are independently replaced with the same or different substituent(s).
- Typical substituents include, but are not limited to, -M, —R 60 , —O—, ⁇ O, —OR 60 , —SR 60 , —S ⁇ , ⁇ S, —NR 60 R 61 , ⁇ NR 60 , —CF 3 , —CN, —OCN, —SCN, —NO, —NO 2 , ⁇ N 2 , —N 3 , —S(O) 2 O ⁇ , —S(O) 2 OH, —S(O) 2 R 60 , —OS(O 2 )O ⁇ , —OS(O) 2 R 61 , —P(O)(O ⁇ ) 2 , —P(O)(OR 60 )(O ⁇ ), —OP(O)(OR 60 )(OR 61
- substituents include -M, —R 60 , ⁇ O, —OR 60 , —SR 60 , —S ⁇ , ⁇ S, —NR 60 R 61 , ⁇ NR 60 , —CF 3 , —CN, —OCN, —SCN, —NO, —NO 2 , ⁇ N 2 , —N 3 , —S(O) 2 R 60 , —OS(O 2 )O ⁇ , —OS(O) 2 R 60 , —P(O)(O ⁇ ) 2 , —P(O)(OR 60 )(O ⁇ ), —OP(O)(OR 60 )(OR 61 ), —C(O)R 60 , —C(S)R 60 , —C(O)OR 60 , —C(O)NR 60 R 61 , —C(O)O ⁇ , —NR 62 C(O)NR 60 R 61 ),
- the present invention provides novel silane compounds which have both hydrophobic and ionic functionality.
- a silyl group which can be covalently attached to a substrate.
- a short head chain e.g., (C 1 -C 6 )alkyl.
- the silyl group and the short head chain are connected via a linker joined to a polar group.
- the linkers may be alkyl, aryl, heteroaryl or heteroalkyl groups while the polar group may be amide, carbamate, urea, sulfonamide, etc.
- Compounds of Formula (I) have at least one activated silyl group, a head chain joined by a linker connected to a polar group.
- an “activated silyl group” refers to silicon moieties, which are capable of reacting with the surface of a substrate to form a covalent bond with the surface.
- an activated silyl group can react with the surface of a silica substrate comprising surface Si—OH groups to create siloxane bonds between compounds of Formula (I) and the substrate.
- Exemplary activated silyl groups include, but are not limited to, —Si(OMe) 3 , —SiMe(OMe) 2 , —SiMe 2 (OMe), —Si(OEt) 3 , —SiMe(OEt) 2 , —SiMe 2 (OEt), —SiMe 2 NMe 2 and —SiCl 3 .
- a “linker” refers to an alkyl, heteroalkyl, aryl or heteroaryl group.
- a “polar group” refers to an amide, sulfonamide, carbamate, urea, ester, etc. The linker in compounds of Formula (I) serve as a spacer between the activated silyl group and the polar group.
- R 1 , R 2 and R 3 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more R 14 groups, provided that at least one of R 1 , R 2 and R 3 are not alkyl, aryl or hydroxyl;
- L 1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl;
- Y is —C(O)N(R 4 )(R 5 ), —N(R 4 )C(O)R 7 , —N(R 4 )S(O 2 )R 7 , —S(O) 2 N(R 4 )(R 5 ), —OC(O)R 7 —OC(O)N(R 4 )(R 5 ), —N(R 4 )C(O)OR 7 , —N(R 4 )C(O)N(R 5 )(R 6 ) or —N(R 4 )S(O 2 )N(R 5 )(R 6 ); and
- R 4 , R 5 and R 6 are independently hydrogen, (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups;
- R 7 is (C 1 -C 6 )alkyl optionally substituted with one or more hydroxy or cyano groups or (C 5 -C 7 )aryl optionally substituted with one or more hydroxy or cyano groups and
- R 14 is (C 1 -C 6 )alkyl
- R 4 , R 5 or R 6 is not hydrogen.
- R 1 , R 2 and R 3 are independently alkyl, alkoxy or halo. In other embodiments, R 1 , R 2 and R 3 are alkoxy. In still other embodiments, R 1 , R 2 and R 3 are alkyl or alkoxy. In still other embodiments, R 1 , R 2 and R 3 are ethoxy or methyl.
- L 1 is alkyldiyl. In other embodiments, L 1 is alkanyldiyl. In still other embodiments, L 1 is alkyleno. In still other embodiments, L 1 is (C 6 -C 20 )alkanyleno. In still other embodiments, L 1 is (C 8 -C 15 )alkanyleno. In still other embodiments, L 1 is (C 10 -C 11 ) alkanyleno.
- R 4 , R 5 and R 6 are independently hydrogen, alkyl, or aryl. In other embodiments, R 4 , R 5 and R 6 are independently alkyl, or aryl. In still other embodiments, R 4 , R 5 and R 6 are independently methyl or phenyl. In still other embodiments, R 4 , R 5 and R 6 are methyl.
- R 1 , R 2 and R 3 are independently alkyl, alkoxy or halo, L 1 is alkyldiyl and R 4 , R 5 and R 6 are independently hydrogen, alkyl, or aryl. In other embodiments, R 1 , R 2 and R 3 are alkyl or alkoxy, L 1 is (C 8 -C 15 )alkanyleno and R 4 , R 5 and R 6 are independently alkyl, or aryl. In still other embodiments R 1 , R 2 and R 3 are ethoxy or methyl, L 1 is (C 10 -C 11 ) alkanyleno and R 4 , R 5 and R 6 are independently methyl or phenyl.
- R 4 , R 5 and R 6 are methyl. In other embodiments, R 5 is phenyl.
- the compounds of Formula (II) have the structure:
- 10-undecenoyl chloride 10 is reacted with dimethylamine 11 to provide amide 12 .
- Amide 12 is then hydrosilylated with silane 13 in presence of a platinum catalyst to yield compound 1 .
- the imine of undecylenic aldehyde 14 is formed upon treatment with methylamine 15 .
- the imine 16 is reduced with sodium borohydride 17 to provide amine 18 which is hydrosilylated with silane 13 in the presence of a platinum catalyst to provide the mono-methylated amine 19 .
- Amine 19 may be reacted with acetyl chloride 20 , benzenesulfonyl chloride 21 , ethyl chloroformate 22 , N,N-dimethylcarbamyl chloride 23 or N,N-dimethylsulphamoyl chloride 24 to provide silicon compounds 3 , 4 , 5 , 6 and 7 , respectively.
- 10-undecen-1-ol 25 is hydrosilylated with silane 13 in the presence of a platinum catalyst to provide silyl alcohol 26 .
- Acylation of silyl alcohol 26 with acetyl chloride 20 or N,N-dimethylcarbamyl chloride 23 provides silicon compounds 8 and 9 , respectively.
- bromide 37 is displaced with dimethylamine 11 to provide the amine 38 which is then hydrosilated with silane in the presence of platinum catalyst to yield the silylamine 39 .
- Compound 39 may be used as the ionizable component of a mixed mode chromatography support.
- the compounds disclosed, supra may be reacted with substrates to form functionalized substrates, which can be used in a wide range of different applications.
- the compounds disclosed, supra incorporate both hydrophobic and polar sites in one molecular structure and have reproducible surface chemistries in reactions with substrate surfaces.
- a compound of structural Formula (II) is covalently bonded to a substrate.
- the compound of structural Formula (II) is covalently bonded to the substrate by reaction of one or more of R 1 , R 2 and R 3 groups with reactive groups on the substrate such, for example, silanol, alkoxysilane, halosilane or aminosilane.
- a compound of structural Formula (II) is covalently bonded through the SiR 1 (R 2 )(R 3 ) group, to another compound of structural Formula (II) by reaction with reactive groups selected from the group consisting of silanol, alkoxysilane or halosilane on the other compound.
- the two compounds are both covalently bonded to the substrate.
- compositions of structural Formula (III) are provided.
- R 1 , R 3 , L and Y are as defined, supra.
- compositions having the following structures are provided:
- compositions of at least one compound of structural Formula (II) and at least one compound of structural Formula (IV) covalently bonded to a substrate are provided where
- R 8 , R 9 , and R 10 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl optionally substituted with one or more of the same or different R 15 groups, provided that at least one of R 1 , R 2 and R 3 are not alkyl, aryl or hydroxyl;
- R 15 is (C 1 -C 6 )alkyl
- L 2 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl;
- W is an ionizable group.
- R 1 , R 3 , L 1 , L 2 , Y and W are as defined, supra
- R 8 , R 9 and R 10 are independently alkyl, alkoxy or halo. In other embodiments, R 8 , R 9 and R 10 are alkoxy. In still other embodiments, R 8 , R 9 and R 10 are alkyl or alkoxy. In still other embodiments, R 8 , R 9 and R 10 are ethoxy or methyl.
- L 2 is alkyldiyl. In other embodiments, L 2 is alkanyldiyl. In still other embodiments, L 2 is alkyleno. In still other embodiments, L 2 is (C 6 -C 20 )alkanyleno. In still other embodiments, L 2 is (C 8 -C 15 )alkanyleno. In still other embodiments, L 2 is (C 10 -C 11 ) alkanyleno.
- W is —CO 2 , —SO 3 , —P(O)(OR 11 )O—, —NR 11 R 12 , or —N + R 11 R 12 R 13 , where R 11 , R 12 , R 13 are independently hydrogen or (C 1 -C 6 )alkyl.
- W is —NR 11 R 12 , or —N + R 11 R 12 R 13 wherein R 11 , R 12 and R 13 are methyl.
- R 1 , R 2 , R 3 , R 8 , R 9 and R 10 are independently alkyl, alkoxy or halo
- L 1 and L 2 are alkyldiyl
- R 4 , R 5 and R 6 are independently hydrogen, alkyl, or aryl
- W is —NR 11 R 12 , or —N + R 11 R 12 R 13 where R 11 , R 12 and R 13 are independently (C 1 -C 6 )alkyl.
- R 1 , R 2 , R 3 , R 8 , R 9 and R 10 are alkyl or alkoxy
- L 1 and L 2 are (C 8 -C 15 )alkanyleno
- R 4 , R 5 and R 6 are independently alkyl, or aryl
- W is —NR 11 R 12 , or —N + R 11 R 12 R 13 where R 11 , R 12 and R 13 are independently (C 1 -C 6 )alkyl.
- R 1 , R 2 , R 3 , R 8 , R 9 and R 10 are ethoxy or methyl
- L 1 and L 2 are (C 10 -C 11 ) alkanyleno
- R 4 , R 5 and R 6 are independently methyl or phenyl and W is —NR 11 R 12 , or —NR + R 11 R 12 R 13 where R 11 , R 12 and R 13 are methyl.
- R 4 , R 5 and R 6 are methyl.
- R 5 is phenyl.
- a compound of Formula (II) and the compound of Formula (IV) are covalently bonded to the substrate by reaction of one or more of R 1 , R 2 and R 3 and one or more of R 8 , R 9 and R 10 with reactive groups on the substrate selected from the group consisting of silanol, alkoxysilane, halosilane or aminosilane.
- R 2 and R 9 are —OEt.
- a composition where the compound of Formula (II) is
- compounds of Formulae (I) and (II) are covalently attached to substrates as shown, supra.
- the polar group is disposed from the surface of the substrate, which may improve hydrolytic stability of the functionalized substrate.
- Compounds of Formulae (I) and (II) can be attached to substrates (e.g., silica) to provide a functionalized stationary phase for various chromatographic separations such as reversed phase separations of surfactants.
- compounds of Formulae (I) and (II) may be mixed with silyl ligands containing one or more ion exchange functionality (e.g., compounds of Formula (IV) prior to reaction with the substrate to provide mixed mode substrates of varying selectivity that also can be used for reversed phase separations of surfactants.
- silyl ligands containing one or more ion exchange functionality e.g., compounds of Formula (IV) prior to reaction with the substrate to provide mixed mode substrates of varying selectivity that also can be used for reversed phase separations of surfactants.
- Compounds of Formulae (I), (II) and (IV) may be covalently bound to a substrate by reaction of R 1 , R 2 or R 3 of the Si functionality with reactive groups on the substrate selected from the group consisting of silanol, alkoxysilane, halosilane and aminosilane moieties.
- compounds of Formulae (I), (II) and (IV) which are covalently bonded to a substrate may be cross linked to one or more compounds of Formulae (I), (II) or (IV) by reaction with reactive groups selected from the group consisting of silanol, alkoxysilane or halosilane on other compound of Formulae (I), (II) or (IV).
- Compounds of Formulae (I), (II) and (IV) can be covalently attached to a variety of substrates.
- Exemplary substrates include materials that have a functional group that can react with activated silyl groups in compounds of Formulae (I), (II) and (IV).
- compounds of Formulae (I), (II) and (IV) can be attached, for example, to silica based materials such as glass surfaces, or the surfaces of other silicon oxide, titanium oxide, germanium oxide, zirconium oxide and aluminum oxide based materials; and also to the surfaces of various carbonized materials, metals, crosslinked and non-crosslinked polymers, which contain suitable functional groups for reacting with activated silyl groups.
- Suitable functional groups include silanols, alkoxysilanes, titanium hydroxides, zirconium hydroxides, etc.
- Compounds of Formulae (I), (II) and (IV) can also be incorporated into polymeric or sol-gel networks by utilizing reactive silicon functionalities.
- Compounds of Formulae (I), (II) and (IV) containing polymerizable groups or groups that can be converted into radicals and/or ion-radicals and/or ions can be used for making polymeric materials and for surface grafting, by utilizing those groups and/or reactive silicon functionalities.
- the resulting materials can be applied for a development of adsorbents, membranes, filters, microfluidic devices, microchips, and functionalized surfaces for various types of separation, detection, and analysis.
- mono- and multi-layered surfaces are prepared by treating silica substrates with compounds of Formulae (I), (II) and/or (IV).
- Compounds of Formulae (I), (II) and/or (IV) can be covalently attached to a variety of substrates, such as silica gel, zirconia, hybrid sol-gel/polymers or glass plates.
- Suitable silica gels comprise non-porous, or porous silica particles of different pore sizes, preferably from 20 ⁇ to 3000 ⁇ and more preferably, from 60 ⁇ to 2000 ⁇ ; and of different particle sizes, preferably, from 0.2 um to 1000 um, and more preferably, from 2 um to 50 um.
- the attachment reaction can be carried out in a slurry of silica gel in an inert solvent, such as toluene, at elevated temperature.
- Water, acid or base catalyst can be applied to enhance the surface coverage, depending on the type of properties desired for the separation media.
- an aminosilane compound such as bis(trimethoxysilylpropyl)amine can be used for modifying underivatized silica gel by incorporating the reactive amino group onto a surface.
- a reagent such as acyl chloride, carbamyl chloride, sulfonyl chloride, or isocyanate, containing a proper functional group, can be reacted with the aminated silica gel to form the corresponding bonded phase.
- compositions described herein may be used as packing for chromatography columns.
- the packing may be particles, monoliths (i.e., material containing pores) or packed bed resins which are loaded into a housing suitable for a chromatography column.
- the substrates are silica substrates.
- compositions described herein may be used to resolve a variety of compounds. Generally, the compositions described herein may be used to separate surfactants. The compositions described herein may also be used, in some situations to resolve a mixture including cationic surfactants, anionic surfactants and neutral surfactants in a single chromatographic run.
- This invention provides simple and versatile approaches to produce a variety of novel solid supports with excellent hydrolytic stability.
- the method of synthesis allows for efficient incorporation of different functionalities onto the surfaces of the substrates and silica substrates, in particular.
- the resulting materials can be applied for development of adsorbents, membranes, filters, microfluidic devices, microchips, and functionalized surfaces for various types of separation, detection and analysis.
- Dimethylamine was mixed with an excess of triethylamine (2.0 eq.) in anhydrous CH 2 Cl 2 and kept at between about 0° C. and about 5° C. for 20 min. Then, a solution of 10-undecenoyl chloride (1.0 eq.) in CH 2 Cl 2 was added dropwise and the mixture was stirred at ambient temperature for 12 h. The reaction mixture was washed with water, dried over Na 2 SO 4 and the solvent was removed in vacuo to yield the dimethylamide of 10-undecenoic acid.
- compounds 4 , 5 , 6 and 7 can be prepared by reacting compound 19 with sulfonyl chloride, ethyl chloroformate, N,N-dimethylcarbamyl chloride and N,N-dimethylsulphamoyl chloride, respectively.
- compound 9 can be prepared by reacting compound 26 with N,N-dimethylcarbamyl chloride.
- FIG. 1 illustrates the high polarity of composition 27 , since the relative retention of the polar compound p-butyl benzoic acid to neutral compound phenanthrene is higher on composition 27 than that on C8 column despite that fact that the latter has lower carbon content. Enhancement of polarity may be due to the placement of polar group at the end of the ligand furthest disposed from the silica surface.
- test mixture injection volume of about 25 ⁇ L
- CH 3 CN A
- 0.1 M NH 4 OAc at about pH 5.8
- mobile phases using a gradient method (25% to 85% A in 30 min, then keep at 85% A for additional 10 min), at a flow rate of about 1 mL/min, at about 30° C. and was detected with evaporative light scattering detection (ELS).
- ELS evaporative light scattering detection
- a column packed with composition 36 was compared with a conventional C18 column of the same column dimension (5 ⁇ m, in 4.6 ⁇ 150 mm stainless steel tubes) in analysis of an ethoxylated nonionic surfactant Triton X-100.
- the sample injection volume of about 10 ⁇ L
- CH 3 CN and 0.1 M NH 4 OAc at about pH 5.4 (isocratic mobile phases) at a flow rate of about 1 mL/min, at about 30° C. and was detected by UV at 225 nm.
- test mixture injection volume of about 25 ⁇ L
- CH 3 CN A
- 0.1 M NH 4 OAc at about pH 5.8
- mobile phases using a gradient method (25% to 85% A in 30 min, then keep at 85% A for additional 10 min) at a flow rate of about 1 mL/min at about 30° C. and detected with an evaporative light scatting detector.
- the same test mixture was also chromatographed on a C18 column of the same column dimension.
- a column packed with composition 36 was compared with a conventional C18 column of the same column dimension (5 ⁇ m, in 4.6 ⁇ 150 mm stainless steel tubes) in analyzing the cationic surfactant lauryldimethylbenzyl ammonium chloride.
- the sample injection volume of about 5 ⁇ L
- the column packed with composition 36 exhibits superior peak shape over the C18 column.
- a column packed with composition 36 was compared with a conventional C18 column of the same column dimension (5 ⁇ m, in 4.6 ⁇ 150 mm stainless steel tubes) in analyzing the highly hydrophilic surfactant, sodium xylene sulfonate.
- the sample injection volume of about 5 ⁇ L
- the sample was eluted with, CH 3 CN/0.1 M NH 4 OAc, about pH 5.4 v/v 30/70 (isocratic mobile phases) at a flow rate of about 1 mL/min, at about 30° C. and detected by UV at about 225 nm.
- the column packed with composition 36 exhibits excellent resolution among the isomers with decent retention times.
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Abstract
The present invention provides novel silicon compounds, methods for making these novel silicon compounds, compositions comprising these novel silicon compounds attached to substrates, methods for attaching the novel silicon compounds to substrates and methods for using the compositions in a variety of chromatographic applications.
Description
- This application is a divisional application of pending U.S. application Ser. No. 11/059,179 filed on Feb. 15, 2005.
- The present invention relates generally to novel silicon compounds, methods for making these novel silicon compounds, compositions comprising these novel silicon compounds attached to substrates, methods for attaching the novel silicon compounds to substrates and methods for using the compositions in a variety of chromatographic applications.
- Conventional reversed phase silica columns (e.g., ODS) are widely used as general-purpose stationary phases for chromatographic separations (Neue, “HPLC Columns—Theory, Technology, and Practice,” WILEY-VCH, New York, 1997, 183-203). However, some drawbacks, including, for example, “phase collapse” (i.e., dewetting) in highly aqueous environments, weak retention of ionic compounds and residual silanol activity which leads to peak tailing of basic analytes prevent employment of conventional reverse phase silica columns in certain applications.
- Polar-embedded phases improve the peak shape of basic analytes and enable operation of reverse phase HPLC columns in highly aqueous environments (O'Gara et al., LC-GC 2001, 19 (6):632-641). Commonly used polar groups include, for example, amides, ureas, ethers and carbamates. In general, polar-embedded phases provide superior peak shapes of basic analytes and are more compatible with highly aqueous environments when compared to general purpose reverse phases. Further, polar embedded phases often have selectivities which are substantially different from those exhibited by conventional C-18 packings.
- Surfactants are important components of a variety of consumer, industrial, agricultural and pharmaceutical products. Surfactant analysis is often complicated by the presence of mixtures which are difficult to resolve using conventional chromatography. Surfactants have been analyzed by liquid chromatography on reversed-phase columns (e.g., C18, C8, cyano, phenyl, etc.), normal phase columns, ion-exchange columns and size-exclusion columns (Schmitt, “Analysis of Surfactants,” 2nd edition, Marcel Dekker, Inc, New York, 2001, 197-292). C18 columns provide reasonable separation, peak efficiency and asymmetry, especially for anionic surfactants. However, the presence of underivatized silanols on silica-based reversed-phase columns often prevents satisfactory resolution of cationic surfactants. For example, C18 reversed phase columns fail to separate individual oligomers of polyethylene glycol (PEG) based surfactants. In addition, because of “de-wetting” caused by necessary usage of high aqueous mobile phases, conventional high-density C18 columns are unsuitable for analysis of highly hydrophilic hydrotopes, (e.g. sodium naphthalene sulfonate and xylene sulfonate). Despite the availability of a variety of HPLC columns to analyze a wide range of surfactants using a plurality of different conditions, no single column can be used to separate cationic, nonionic, and anionic surfactants in a single run using simple and volatile, mass spectroscopy compatible, mobile phases.
- Accordingly, what is needed are novel silane compounds which have both hydrophobic and polar functionality, substrates functionalized with these new silane compounds and the use of these novel functionalized substrates to simultaneously separate cationic, nonionic and anionic surfactants.
- The present invention satisfies these and other needs by providing a new class of silane compounds, which have hydrophobic and polar functionality, substrates functionalized with these new silane compounds and the use of these novel functionalized substrates to simultaneously separate cationic, nonionic, and anionic surfactants.
- In one aspect, a compound described by Formula (I) is disclosed:
- or salts, solvates or hydrates thereof. The compound of Formula (I) has at least one activated silyl group (e.g., Si(OMe)3, —SiMe(OMe)2, —SiMe2(OMe), —Si(OEt)3, —SiMe(OEt)2, —SiMe2(OEt), —SiMe2NMe2, —SiCl3, etc.), at least one polar group (e.g., amide, sulfonamide, carbamate, urea, ester, etc.) and a short head chain (e.g., (C1-C6) alkyl) connected to the polar group.
- In another aspect, a compound of structural Formula (II) is provided:
- or salts, solvates or hydrates thereof
- wherein:
- R1, R2 and R3 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more R12 groups, provided that at least one of R1, R2 and R3 are not alkyl, aryl or hydroxyl;
- L1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl;
- Y is —C(O)N(R4)(R5), —N(R4)C(O)R7, —N(R4)S(O2)R7, —S(O)2N(R4)(R5), —OC(O)R7, —OC(O)N(R4)(R5), —N(R4)C(O)OR7, —N(R4)C(O)N(R5)(R6) or —N(R4)S(O2)N(R5)(R6); and
- R4, R5 and R6 are independently hydrogen, (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups;
- R7 is (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups; and
- R14 is (C1-C6)alkyl;
- provided that one of R4, R5 or R6 is not hydrogen.
- In another aspect, a composition including a compound of Formula (II) covalently bonded to a substrate is provided. In some embodiments, the composition is in a flow-through bed suitable for use a reverse phase chromatographic medium.
- In still another aspect, a composition comprising the compound of structural Formula (II) covalently bonded to a substrate and a compound of structural Formula (IV) covalently bonded to the substrate is provided wherein:
- R8, R9, and R10 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl optionally substituted with one or more of the same or different R14 groups, provided that at least one of R1, R2 and R3 are not alkyl, aryl or hydroxyl;
- R15 is (C1-C6)alkyl;
- L2 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and
- W is an ionizable group.
- In still another aspect, a chromatographic method is provided. An aqueous liquid is flowed through a bed of separation medium, which includes either a composition containing a compound of Formula (II) covalently bonded to a substrate or a composition comprising the compound of structural Formula (II) covalently bonded to a substrate and a compound of structural Formula (IV) covalently bonded to the substrate.
- In still another aspect, a method for chromatographic separation of analytes in a liquid sample is provided. The liquid sample is flowed through medium, which includes a composition containing a compound of Formula (II) covalently bonded to a substrate or a composition comprising the compound of structural Formula (II) covalently bonded to a substrate and a compound of structural Formula (IV) covalently bonded to the substrate.
- In still another aspect, a method for simultaneous analysis of inorganic analytes and organic analytes in a liquid sample is provided. The liquid sample is flowed through medium, which includes a composition containing a compound of Formula (II) covalently bonded to a substrate or a composition of a compound of structural Formula (II) and a compound of structural Formula (IV) covalently bonded to a substrate.
-
FIG. 1 illustrates the synthesis of an amide of Formula (II); -
FIG. 2 illustrates the synthesis of amine derivatives of Formula (II); -
FIG. 3 illustrates the synthesis of alcohol derivatives of Formula (II); -
FIG. 4 illustrates synthesis of a compound of Formula (IV); -
FIG. 5 illustrates the separation of uracil, p-butyl benzoic acid and phenanthrene by a C8 column and a column packed withcomposition 27; -
FIG. 6 illustrates separation of a number of surfactants with and a column packed withcomposition 36; -
FIG. 7 illustrates the separation of Triton X-100 with a conventional C18 column and a column packed withcomposition 36; -
FIG. 8 illustrates the separation of a number of surfactants with a conventional C18 column and a column packed withcomposition 36; -
FIG. 9 illustrates the separation of lauryldimethylbenzyl ammonium chloride with a conventional C18 column and a column packed withcomposition 36; and -
FIG. 10 illustrates the separation of sodium xylene sulfonate with a conventional C18 column and a column packed withcomposition 36. - “Alkyl” by itself or as part of another substituent, refers to a saturated or unsaturated, branched, straight-chain or cyclic monovalent hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent alkane, alkene or alkyne. Typical alkyl groups include, but are not limited to, methyl; ethyls such as ethanyl, ethenyl, ethynyl; propyls such as propan-1-yl, propan-2-yl, cyclopropan-1-yl, prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl(allyl), cycloprop-1-en-1-yl; cycloprop-2-en-1-yl, prop-1-yn-1-yl, prop-2-yn-1-yl, etc.; butyls such as butan-1-yl, butan-2-yl, 2-methyl-propan-1-yl, 2-methyl-propan-2-yl, cyclobutan-1-yl, but-1-en-1-yl, but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-2-yl, buta-1,3-dien-1-yl, buta-1,3-dien-2-yl, cyclobut-1-en-1-yl, cyclobut-1-en-3-yl, cyclobuta-1,3-dien-1-yl, but-1-yn-1-yl, but-1-yn-3-yl, but-3-yn-1-yl, etc.; and the like.
- The term “alkyl” is specifically intended to include groups having any degree or level of saturation, i.e., groups having exclusively single carbon-carbon bonds, groups having one or more double carbon-carbon bonds, groups having one or more triple carbon-carbon bonds and groups having mixtures of single, double and triple carbon-carbon bonds. Where a specific level of saturation is intended, the expressions “alkanyl,” “alkenyl,” and “alkynyl” are used. In some embodiments, an alkyl group comprises from 1 to 20 carbon atoms. In other embodiments, an alkyl group comprises from 1 to 10 carbon atoms.
- “Alkanyl” by itself or as part of another substituent, refers to a saturated branched, straight-chain or cyclic alkyl radical derived by the removal of one hydrogen atom from a single carbon atom of a parent alkane. Typical alkanyl groups include, but are not limited to, methanyl; ethanyl; propanyls such as propan-1-yl, propan-2-yl(isopropyl), cyclopropan-1-yl, etc.; butanyls such as butan-1-yl, butan-2-yl(sec-butyl), 2-methyl-propan-1-yl(isobutyl), 2-methyl-propan-2-yl (t-butyl), cyclobutan-1-yl, etc.; and the like.
- “Alkenyl” by itself or as part of another substituent, refers to an unsaturated branched, straight-chain or cyclic alkyl radical having at least one carbon-carbon double bond derived by the removal of one hydrogen atom from a single carbon atom of a parent alkene. The group may be in either the cis or trans conformation about the double bond(s). Typical alkenyl groups include, but are not limited to, ethenyl; propenyls such as prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl(allyl), prop-2-en-2-yl, cycloprop-1-en-1-yl, cycloprop-2-en-1-yl; butenyls such as but-1-en-1-yl, but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-1-yl, but-2-en-2-yl, buta-1,3-dien-1-yl, buta-1,3-dien-2-yl, cyclobut-1-en-1-yl, cyclobut-1-en-3-yl, cyclobuta-1,3-dien-1-yl, etc.; and the like.
- “Alkynyl” by itself or as part of another substituent, refers to an unsaturated branched, straight-chain or cyclic alkyl radical having at least one carbon-carbon triple bond derived by the removal of one hydrogen atom from a single carbon atom of a parent alkyne. Typical alkynyl groups include, but are not limited to, ethynyl; propynyls such as prop-1-yn-1-yl, prop-2-yn-1-yl, etc.; butynyls such as but-1-yn-1-yl, but-1-yn-3-yl, but-3-yn-1-yl, etc.; and the like.
- “Alkyldiyl” by itself or as part of another substituent, refers to a saturated or unsaturated, branched, straight-chain or cyclic divalent hydrocarbon group derived by the removal of one hydrogen atom from each of two different carbon atoms of a parent alkane, alkene or alkyne, or by the removal of two hydrogen atoms from a single carbon atom of a parent alkane, alkene or alkyne. The two monovalent radical centers or each valency of the divalent radical center can form bonds with the same or different atoms. Typical alkyldiyl groups include, but are not limited to methandiyl; ethyldiyls such as ethan-1,1-diyl, ethan-1,2-diyl, ethen-1,1-diyl, ethen-1,2-diyl; propyldiyls such as propan-1,1-diyl, propan-1,2-diyl, propan-2,2-diyl, propan-1,3-diyl, cyclopropan-1,1-diyl, cyclopropan-1,2-diyl, prop-1-en-1,1-diyl, prop-1-en-1,2-diyl, prop-2-en-1,2-diyl, prop-1-en-1,3-diyl, cycloprop-1-en-1,2-diyl, cycloprop-2-en-1,2-diyl, cycloprop-2-en-1,1-diyl, prop-1-yn-1,3-diyl, etc.; butyldiyls such as, butan-1,1-diyl, butan-1,2-diyl, butan-1,3-diyl, butan-1,4-diyl, butan-2,2-diyl, 2-methyl-propan-1,1-diyl, 2-methyl-propan-1,2-diyl, cyclobutan-1,1-diyl; cyclobutan-1,2-diyl, cyclobutan-1,3-diyl, but-1-en-1,1-diyl, but-1-en-1,2-diyl, but-1-en-1,3-diyl, but-1-en-1,4-diyl, 2-methyl-prop-1-en-1,1-diyl, 2-methanylidene-propan-1,1-diyl, buta-1,3-dien-1,1-diyl, buta-1,3-dien-1,2-diyl, buta-1,3-dien-1,3-diyl, buta-1,3-dien-1,4-diyl, cyclobut-1-en-1,2-diyl, cyclobut-1-en-1,3-diyl, cyclobut-2-en-1,2-diyl, cyclobuta-1,3-dien-1,2-diyl, cyclobuta-1,3-dien-1,3-diyl, but-1-yn-1,3-diyl, but-1-yn-1,4-diyl, buta-1,3-diyn-1,4-diyl, etc.; and the like. Where specific levels of saturation are intended, the nomenclature alkanyldiyl, alkenyldiyl and/or alkynyldiyl is used. In some embodiments, the alkyldiyl group is (C1-C20)alkyldiyl. In other embodiments, the alkyldiyl group is (C1-C10)alkyldiyl. In still other embodiments, the alkyldiyl group is a saturated acyclic alkanyldiyl group in which the radical centers are at the terminal carbons, e.g., methandiyl(methano); ethan-1,2-diyl(ethano); propan-1,3-diyl (propano); butan-1,4-diyl(butano); and the like (also referred to as alkyleno, defined infra).
- “Alkyleno” by itself or as part of another substituent, refers to a straight-chain alkyldiyl group having two terminal monovalent radical centers derived by the removal of one hydrogen atom from each of the two terminal carbon atoms of straight-chain parent alkane, alkene or alkyne. Typical alkyleno groups include, but are not limited to, methano; ethylenos such as ethano, etheno, ethyno; propylenos such as propano, prop[1]eno, propa[1,2]dieno, prop[1]yno, etc.; butylenos such as butano, but[1]eno, but[2]eno, buta[1,3]dieno, but[1]yno, but[2]yno, but[1,3]diyno, etc.; and the like. Where specific levels of saturation are intended, the nomenclature alkano, alkeno and/or alkyno is used. In some embodiments, the alkyleno group is (C1-C20)alkyleno. In other embodiments, the alkyleno group is (C1-C10) alkyleno. In still other embodiments, the alkyleno group is a straight-chain saturated alkano groups, e.g., methano, ethano, propano, butano, and the like.
- “Alkylsulfonyloxy” by itself or as part of another substituent, refers to a radical —OS(O)2R30 where R30 represents an alkyl or cycloalkyl group as defined herein.
- “Alkoxy” by itself or as part of another substituent, refers to a radical —OR31 where R31 represents an alkyl or cycloalkyl group as defined herein Representative examples include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy and the like.
- “Alkoxycarbonyl” by itself or as part of another substituent, refers to a radical —C(O)OR32 where R32 represents an alkyl or cycloalkyl group as defined herein.
- “Aryl” by itself or as part of another substituent, refers to a monovalent aromatic hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent aromatic ring system. Typical aryl groups include, but are not limited to, groups derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexylene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene and the like. In some embodiments, an aryl group comprises from 5 to 20 carbon atoms. In other embodiments, an aryl group comprises from 5 to 12 carbon atoms.
- “Aryldiyl” by itself or as part of another substituent refers to a divalent hydrocarbon radical derived by the removal of one hydrogen atom from each of two different carbon atoms of a parent aromatic system or by removal of two hydrogen atoms from a single carbon atom of a parent aromatic ring system. The two monovalent radical centers or each valency of the divalent center can form bonds with the same or different atom(s). Typical aryldiyl groups include, but are not limited to, groups derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexylene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene and the like. In some embodiments, an aryldiyl group comprises from 5 to 20 carbon atoms. In other embodiments, an aryldiyl group comprises from 5 to 12 carbon atoms.
- “Aryloxycarbonyl” by itself or as part of another substituent, refers to a radical —C(O)OR33 where R33 represents an aryl group as defined herein.
- “Arylsulfonyloxy” by itself or as part of another substituent, refers to a radical —OS(O)2R35 where R35 represents an alkyl or cycloalkyl group as defined herein.
- “Cycloalkyl” by itself or as part of another substituent, refers to a saturated or unsaturated cyclic alkyl radical. Where a specific level of saturation is intended, the nomenclature “cycloalkanyl” or “cycloalkenyl” is used. Typical cycloalkyl groups include, but are not limited to, groups derived from cyclopropane, cyclobutane, cyclopentane, cyclohexane and the like. In some embodiments, the cycloalkyl group is (C3-C10) cycloalkyl. In other embodiments, the cycloalkyl group is (C3-C7) cycloalkyl.
- “Heteroalkyl, Heteroalkanyl Heteroalkenyl, Heteroalkanyl, Heteroalkyldiyl and Heteroalkyleno” by themselves or as part of another substituent, refer to alkyl, alkanyl, alkenyl, alkynyl, alkyldiyl and alkyleno groups, respectively, in which one or more of the carbon atoms (and any associated hydrogen atoms) are each independently replaced with the same or different heteroatomic groups. Typical heteroatomic groups which can be included in these groups include, but are not limited to, —O—, —S—, —O—O—, —S—S—, —O—S—, —NR35R36—, ═N—N═, —N═N—, —N═N—NR37R38, —PR39—, —P(O)2—, —POR40—, —O—P(O)2—, —SO—, —SO2—, —SnR41R42— and the like, where R35, R36, R37, R38, R39, R40, R41 and R42 are independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, substituted arylalkyl, cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substituted cycloheteroalkyl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, heteroarylalkyl or substituted heteroarylalkyl.
- “Heteroaryl” by itself or as part of another substituent, refers to a monovalent heteroaromatic radical derived by the removal of one hydrogen atom from a single atom of a parent heteroaromatic ring system. Typical heteroaryl groups include, but are not limited to, groups derived from acridine, arsindole, carbazole, β-carboline, chromane, chromene, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline, quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and the like. In some embodiments, the heteroaryl group is from 5-20 membered heteroaryl. In other embodiments, the heteroaryl group is from 5-10 membered heteroaryl. In still other embodiments, the heteroaryl groups are those derived from thiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine, quinoline, imidazole, oxazole and pyrazine.
- “Heteroaryldiyl” by itself or as part of another substituent refers to a divalent radical derived by the removal of one hydrogen atom from each of two different carbon atoms of a parent heteroaromatic system or by removal of two hydrogen atoms from a single carbon atom of a parent aromatic ring system. The two monovalent radical centers or each valency of the divalent center can form bonds with the same or different atom(s) Typical heteroaryldiyl groups include, but are not limited to, groups derived from acridine, arsindole, carbazole, α-carboline, chromane, chromene, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline, quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and the like. In some embodiments, a heteroaryldiyl group comprises from 5 to 20 carbon atoms. In other embodiments, a heteroaryldiyl group comprises from 5 to 12 carbon atoms.
- “Parent Aromatic Ring System” by itself or as part of another substituent, refers to an unsaturated cyclic or polycyclic ring system having a conjugated n electron system. Specifically included within the definition of “parent aromatic ring system” are fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, fluorene, indane, indene, phenalene, etc. Typical parent aromatic ring systems include, but are not limited to, aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexylene, as-indacene, s-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene and the like.
- “Parent Heteroaromatic Ring System” by itself or as part of another substituent, refers to a parent aromatic ring system in which one or more carbon atoms (and any associated hydrogen atoms) are independently replaced with the same or different heteroatom. Typical heteroatoms to replace the carbon atoms include, but are not limited to, N, P, O, S, Si, etc. Specifically included within the definition of “parent heteroaromatic ring systems” are fused ring systems in which one or more of the rings are aromatic and one or more of the rings are saturated or unsaturated, such as, for example, arsindole, benzodioxan, benzofuran, chromane, chromene, indole, indoline, xanthene, etc. Typical parent heteroaromatic ring systems include, but are not limited to, arsindole, carbazole, β-carboline, chromane, chromene, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline, quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and the like.
- “Substituted” refers to a group in which one or more hydrogen atoms are independently replaced with the same or different substituent(s). Typical substituents include, but are not limited to, -M, —R60, —O—, ═O, —OR60, —SR60, —S−, ═S, —NR60R61, ═NR60, —CF3, —CN, —OCN, —SCN, —NO, —NO2, ═N2, —N3, —S(O)2O−, —S(O)2OH, —S(O)2R60, —OS(O2)O−, —OS(O)2R61, —P(O)(O−)2, —P(O)(OR60)(O−), —OP(O)(OR60)(OR61), —C(O)R60, —C(S)R60, —C(O)OR60, —C(O)NR60R61, —C(O)O−, —C(S)OR60, —NR62C(O)NR60R61, —NR62C(S)NR60R61, —NR62C(NR63)NR60R61 and —C(NR62)NR60R61 where M is independently a halogen; R60, R61, R62 and R63 are independently hydrogen, alkyl, substituted alkyl, alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substituted cycloheteroalkyl, aryl, substituted aryl, heteroaryl or substituted heteroaryl, or optionally R60 and R61 together with the nitrogen atom to which they are bonded form a cycloheteroalkyl or substituted cycloheteroalkyl ring; and R64 and R65 are independently hydrogen, alkyl, substituted alkyl, aryl, cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substituted cycloheteroalkyl, aryl, substituted aryl, heteroaryl or substituted heteroaryl, or optionally R64 and R65 together with the nitrogen atom to which they are bonded form a cycloheteroalkyl or substituted cycloheteroalkyl ring. Preferably, substituents include -M, —R60, ═O, —OR60, —SR60, —S−, ═S, —NR60R61, ═NR60, —CF3, —CN, —OCN, —SCN, —NO, —NO2, ═N2, —N3, —S(O)2R60, —OS(O2)O−, —OS(O)2R60, —P(O)(O−)2, —P(O)(OR60)(O−), —OP(O)(OR60)(OR61), —C(O)R60, —C(S)R60, —C(O)OR60, —C(O)NR60R61, —C(O)O−, —NR62C(O)NR60R61, more preferably, -M, —R60, ═O, —OR60, —SR60, —NR60R61, —CF3, —CN, —NO2, —S(O)2R60, —P(O)(OR60)(O−), —OP(O)(OR60)(OR61), —C(O)R60, —C(O)OR60, —C(O)NR60R61, —C(O)O−, most preferably, -M, —R60, ═O, —OR60, —SR60, —NR60R61, —CF3, —CN, —NO2, —S(O)2R60, —OP(O)(OR60)(OR61), —C(O)R60, —C(O)OR60, —C(O)O−, where R60, R61 and R62 are as defined above.
- The present invention provides novel silane compounds which have both hydrophobic and ionic functionality. At one terminus of the novel silane compound is a silyl group, which can be covalently attached to a substrate. At the other end of the novel silane compound is a short head chain (e.g., (C1-C6)alkyl). The silyl group and the short head chain are connected via a linker joined to a polar group. The linkers may be alkyl, aryl, heteroaryl or heteroalkyl groups while the polar group may be amide, carbamate, urea, sulfonamide, etc.
- In one aspect, a compound described by Formula (I) is provided
- or salts, solvates or hydrates thereof. Compounds of Formula (I) have at least one activated silyl group, a head chain joined by a linker connected to a polar group.
- An “activated silyl group” refers to silicon moieties, which are capable of reacting with the surface of a substrate to form a covalent bond with the surface. For example, an activated silyl group can react with the surface of a silica substrate comprising surface Si—OH groups to create siloxane bonds between compounds of Formula (I) and the substrate. Exemplary activated silyl groups include, but are not limited to, —Si(OMe)3, —SiMe(OMe)2, —SiMe2(OMe), —Si(OEt)3, —SiMe(OEt)2, —SiMe2(OEt), —SiMe2NMe2 and —SiCl3. A “linker” refers to an alkyl, heteroalkyl, aryl or heteroaryl group. A “polar group” refers to an amide, sulfonamide, carbamate, urea, ester, etc. The linker in compounds of Formula (I) serve as a spacer between the activated silyl group and the polar group.
- In some embodiments, a compound of structural Formula (II) is provided:
- or salts, solvates or hydrates thereof
- wherein:
- R1, R2 and R3 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more R14 groups, provided that at least one of R1, R2 and R3 are not alkyl, aryl or hydroxyl;
- L1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl;
- Y is —C(O)N(R4)(R5), —N(R4)C(O)R7, —N(R4)S(O2)R7, —S(O)2N(R4)(R5), —OC(O)R7—OC(O)N(R4)(R5), —N(R4)C(O)OR7, —N(R4)C(O)N(R5)(R6) or —N(R4)S(O2)N(R5)(R6); and
- R4, R5 and R6 are independently hydrogen, (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups;
- R7 is (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups and
- R14 is (C1-C6)alkyl;
- provided that one of R4, R5 or R6 is not hydrogen.
- In some embodiments, R1, R2 and R3 are independently alkyl, alkoxy or halo. In other embodiments, R1, R2 and R3 are alkoxy. In still other embodiments, R1, R2 and R3 are alkyl or alkoxy. In still other embodiments, R1, R2 and R3 are ethoxy or methyl.
- In some embodiments, L1 is alkyldiyl. In other embodiments, L1 is alkanyldiyl. In still other embodiments, L1 is alkyleno. In still other embodiments, L1 is (C6-C20)alkanyleno. In still other embodiments, L1 is (C8-C15)alkanyleno. In still other embodiments, L1 is (C10-C11) alkanyleno.
- In some embodiments, R4, R5 and R6 are independently hydrogen, alkyl, or aryl. In other embodiments, R4, R5 and R6 are independently alkyl, or aryl. In still other embodiments, R4, R5 and R6 are independently methyl or phenyl. In still other embodiments, R4, R5 and R6 are methyl.
- In some embodiments, R1, R2 and R3 are independently alkyl, alkoxy or halo, L1 is alkyldiyl and R4, R5 and R6 are independently hydrogen, alkyl, or aryl. In other embodiments, R1, R2 and R3 are alkyl or alkoxy, L1 is (C8-C15)alkanyleno and R4, R5 and R6 are independently alkyl, or aryl. In still other embodiments R1, R2 and R3 are ethoxy or methyl, L1 is (C10-C11) alkanyleno and R4, R5 and R6 are independently methyl or phenyl.
- In some embodiments, R4, R5 and R6 are methyl. In other embodiments, R5 is phenyl.
- In some embodiments, the compounds of Formula (II) have the structure:
- Exemplary methods of synthesizing compounds described herein are presented in Schemes 1-4, infra. Starting materials useful for preparing compounds described herein are commercially available or can be prepared by well-known synthetic methods. Other methods for synthesis of the compounds described herein will be readily apparent to the skilled artisan. Accordingly, the methods presented in Schemes 1-4 herein are illustrative rather than comprehensive.
- Referring now to
FIG. 1 , 10-undecenoyl chloride 10 is reacted withdimethylamine 11 to provideamide 12.Amide 12 is then hydrosilylated withsilane 13 in presence of a platinum catalyst to yieldcompound 1. - Referring now to
FIG. 2 , the imine ofundecylenic aldehyde 14 is formed upon treatment withmethylamine 15. Theimine 16 is reduced withsodium borohydride 17 to provideamine 18 which is hydrosilylated withsilane 13 in the presence of a platinum catalyst to provide the mono-methylatedamine 19.Amine 19 may be reacted withacetyl chloride 20,benzenesulfonyl chloride 21,ethyl chloroformate 22, N,N-dimethylcarbamyl chloride 23 or N,N-dimethylsulphamoyl chloride 24 to providesilicon compounds - Referring now to
FIG. 3 , 10-undecen-1-ol 25 is hydrosilylated withsilane 13 in the presence of a platinum catalyst to providesilyl alcohol 26. Acylation ofsilyl alcohol 26 withacetyl chloride 20 or N,N-dimethylcarbamyl chloride 23, providessilicon compounds - Referring now to
FIG. 4 ,bromide 37 is displaced withdimethylamine 11 to provide theamine 38 which is then hydrosilated with silane in the presence of platinum catalyst to yield thesilylamine 39.Compound 39 may be used as the ionizable component of a mixed mode chromatography support. - Those of skill in the art will appreciate that the synthetic strategies disclosed, supra, may be readily adapted to make silanes with aryl, heteroaryl and heteroalkyl linkers by varying the starting amine or acyl chloride or alkyl halide. Further, diverse methods are known to those of skill in the art to accomplish the transformations above (or equivalents thereof) and may be found in any compendia of organic synthesis (see e.g., Harrison et al., “Compendium of Synthetic Organic Methods”, Vols. 1-8 (John Wiley and Sons, 1971-1996); “Beilstein Handbook of Organic Chemistry,” Beilstein Institute of Organic Chemistry, Frankfurt, Germany; Feiser et al., “Reagents for Organic Synthesis,” Volumes 1-17, Wiley Interscience; Trost et al., “Comprehensive Organic Synthesis,” Pergamon Press, 1991; “Theilheimer's Synthetic Methods of Organic Chemistry,” Volumes 1-45, Karger, 1991; March, “Advanced Organic Chemistry,” Wiley Interscience, 1991; Larock “Comprehensive Organic Transformations,” VCH Publishers, 1989; and Paquette, “Encyclopedia of Reagents for Organic Synthesis,” John Wiley & Sons, 1995).
- The compounds disclosed, supra, may be reacted with substrates to form functionalized substrates, which can be used in a wide range of different applications. The compounds disclosed, supra, incorporate both hydrophobic and polar sites in one molecular structure and have reproducible surface chemistries in reactions with substrate surfaces.
- In some embodiments, a compound of structural Formula (II) is covalently bonded to a substrate. In other embodiments, the compound of structural Formula (II) is covalently bonded to the substrate by reaction of one or more of R1, R2 and R3 groups with reactive groups on the substrate such, for example, silanol, alkoxysilane, halosilane or aminosilane.
- In some embodiments, a compound of structural Formula (II) is covalently bonded through the SiR1(R2)(R3) group, to another compound of structural Formula (II) by reaction with reactive groups selected from the group consisting of silanol, alkoxysilane or halosilane on the other compound. In this embodiment, the two compounds are both covalently bonded to the substrate.
- In some embodiments, compositions of structural Formula (III) are provided
- where R1, R3, L and Y are as defined, supra.
- In other embodiments, compositions having the following structures are provided:
- In still other embodiments, compositions of at least one compound of structural Formula (II) and at least one compound of structural Formula (IV) covalently bonded to a substrate are provided where
- R8, R9, and R10 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl optionally substituted with one or more of the same or different R15 groups, provided that at least one of R1, R2 and R3 are not alkyl, aryl or hydroxyl;
- R15 is (C1-C6)alkyl;
- L2 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and
- W is an ionizable group.
- In other embodiments, a composition of structural Formula (V) is provided
- where R1, R3, L1, L2, Y and W are as defined, supra
- In some embodiments, R8, R9 and R10 are independently alkyl, alkoxy or halo. In other embodiments, R8, R9 and R10 are alkoxy. In still other embodiments, R8, R9 and R10 are alkyl or alkoxy. In still other embodiments, R8, R9 and R10 are ethoxy or methyl.
- In some embodiments, L2 is alkyldiyl. In other embodiments, L2 is alkanyldiyl. In still other embodiments, L2 is alkyleno. In still other embodiments, L2 is (C6-C20)alkanyleno. In still other embodiments, L2 is (C8-C15)alkanyleno. In still other embodiments, L2 is (C10-C11) alkanyleno.
- In some embodiments, W is —CO2, —SO3, —P(O)(OR11)O—, —NR11R12, or —N+R11R12R13, where R11, R12, R13 are independently hydrogen or (C1-C6)alkyl. In other embodiments, W is —NR11R12, or —N+R11R12R13 wherein R11, R12 and R13 are methyl.
- In some embodiments, R1, R2, R3, R8, R9 and R10 are independently alkyl, alkoxy or halo, L1 and L2 are alkyldiyl, R4, R5 and R6 are independently hydrogen, alkyl, or aryl and W is —NR11R12, or —N+R11R12R13 where R11, R12 and R13 are independently (C1-C6)alkyl.
- In some embodiments, R1, R2, R3, R8, R9 and R10 are alkyl or alkoxy, L1 and L2 are (C8-C15)alkanyleno, R4, R5 and R6 are independently alkyl, or aryl and W is —NR11R12, or —N+R11R12R13 where R11, R12 and R13 are independently (C1-C6)alkyl. In other embodiments, R1, R2, R3, R8, R9 and R10 are ethoxy or methyl, L1 and L2 are (C10-C11) alkanyleno, R4, R5 and R6 are independently methyl or phenyl and W is —NR11R12, or —NR+R11R12R13 where R11, R12 and R13 are methyl. In a more specific embodiment, R4, R5 and R6 are methyl. In another more specific embodiment, R5 is phenyl.
- In some embodiments, a compound of Formula (II) and the compound of Formula (IV) are covalently bonded to the substrate by reaction of one or more of R1, R2 and R3 and one or more of R8, R9 and R10 with reactive groups on the substrate selected from the group consisting of silanol, alkoxysilane, halosilane or aminosilane. In other embodiments, R2 and R9 are —OEt. In still other embodiments, a composition where the compound of Formula (II) is
- and the compound of Formula (IV) is
- is provided.
-
- In still other embodiments a composition of the following structure is provided:
- In some embodiments, compounds of Formulae (I) and (II) are covalently attached to substrates as shown, supra. In these embodiments, the polar group is disposed from the surface of the substrate, which may improve hydrolytic stability of the functionalized substrate. Compounds of Formulae (I) and (II) can be attached to substrates (e.g., silica) to provide a functionalized stationary phase for various chromatographic separations such as reversed phase separations of surfactants. Further, compounds of Formulae (I) and (II) may be mixed with silyl ligands containing one or more ion exchange functionality (e.g., compounds of Formula (IV) prior to reaction with the substrate to provide mixed mode substrates of varying selectivity that also can be used for reversed phase separations of surfactants.
- Compounds of Formulae (I), (II) and (IV) may be covalently bound to a substrate by reaction of R1, R2 or R3 of the Si functionality with reactive groups on the substrate selected from the group consisting of silanol, alkoxysilane, halosilane and aminosilane moieties. In some embodiments, compounds of Formulae (I), (II) and (IV) which are covalently bonded to a substrate may be cross linked to one or more compounds of Formulae (I), (II) or (IV) by reaction with reactive groups selected from the group consisting of silanol, alkoxysilane or halosilane on other compound of Formulae (I), (II) or (IV).
- Compounds of Formulae (I), (II) and (IV) can be covalently attached to a variety of substrates. Exemplary substrates include materials that have a functional group that can react with activated silyl groups in compounds of Formulae (I), (II) and (IV). Thus, compounds of Formulae (I), (II) and (IV) can be attached, for example, to silica based materials such as glass surfaces, or the surfaces of other silicon oxide, titanium oxide, germanium oxide, zirconium oxide and aluminum oxide based materials; and also to the surfaces of various carbonized materials, metals, crosslinked and non-crosslinked polymers, which contain suitable functional groups for reacting with activated silyl groups. Examples of suitable functional groups include silanols, alkoxysilanes, titanium hydroxides, zirconium hydroxides, etc. Compounds of Formulae (I), (II) and (IV) can also be incorporated into polymeric or sol-gel networks by utilizing reactive silicon functionalities. Compounds of Formulae (I), (II) and (IV) containing polymerizable groups or groups that can be converted into radicals and/or ion-radicals and/or ions, can be used for making polymeric materials and for surface grafting, by utilizing those groups and/or reactive silicon functionalities. The resulting materials can be applied for a development of adsorbents, membranes, filters, microfluidic devices, microchips, and functionalized surfaces for various types of separation, detection, and analysis.
- In some embodiments, mono- and multi-layered surfaces are prepared by treating silica substrates with compounds of Formulae (I), (II) and/or (IV). Compounds of Formulae (I), (II) and/or (IV) can be covalently attached to a variety of substrates, such as silica gel, zirconia, hybrid sol-gel/polymers or glass plates. Suitable silica gels comprise non-porous, or porous silica particles of different pore sizes, preferably from 20 Å to 3000 Å and more preferably, from 60 Å to 2000 Å; and of different particle sizes, preferably, from 0.2 um to 1000 um, and more preferably, from 2 um to 50 um. The attachment reaction can be carried out in a slurry of silica gel in an inert solvent, such as toluene, at elevated temperature. Water, acid or base catalyst can be applied to enhance the surface coverage, depending on the type of properties desired for the separation media.
- Alternatively, an aminosilane compound, such as bis(trimethoxysilylpropyl)amine can be used for modifying underivatized silica gel by incorporating the reactive amino group onto a surface. Then, a reagent, such as acyl chloride, carbamyl chloride, sulfonyl chloride, or isocyanate, containing a proper functional group, can be reacted with the aminated silica gel to form the corresponding bonded phase.
- The compositions described herein may be used as packing for chromatography columns. The packing may be particles, monoliths (i.e., material containing pores) or packed bed resins which are loaded into a housing suitable for a chromatography column.
- Also provided is a packing of a compound of structural Formula (I) covalently bonded to a substrate and a compound of structural Formula (IV) bonded to another substrate. In some embodiments, the substrates are silica substrates.
- The compositions described herein may be used to resolve a variety of compounds. Generally, the compositions described herein may be used to separate surfactants. The compositions described herein may also be used, in some situations to resolve a mixture including cationic surfactants, anionic surfactants and neutral surfactants in a single chromatographic run.
- This invention provides simple and versatile approaches to produce a variety of novel solid supports with excellent hydrolytic stability. The method of synthesis allows for efficient incorporation of different functionalities onto the surfaces of the substrates and silica substrates, in particular. The resulting materials can be applied for development of adsorbents, membranes, filters, microfluidic devices, microchips, and functionalized surfaces for various types of separation, detection and analysis.
- The following examples are provided by way of illustration only and not by way of limitation. Those of skill in the art will readily recognize a variety of noncritical parameters that could be changed or modified to yield essentially similar results.
- Dimethylamine was mixed with an excess of triethylamine (2.0 eq.) in anhydrous CH2Cl2 and kept at between about 0° C. and about 5° C. for 20 min. Then, a solution of 10-undecenoyl chloride (1.0 eq.) in CH2Cl2 was added dropwise and the mixture was stirred at ambient temperature for 12 h. The reaction mixture was washed with water, dried over Na2SO4 and the solvent was removed in vacuo to yield the dimethylamide of 10-undecenoic acid. Excess dimethylethoxysilane (10 eq.) was added to the amide followed by addition of a solution of catalyst (0.1 mol %), (e.g., hexachloroplatinic acid in a minimum amount of ethanol). After stirring at 50° C. for 24 h, the silane and solvent were removed in vacuo to provide
compound 1. - To a solution of 10-undecylenic aldehyde (1 eq.) in anhydrous methanol was added excess methylamine in anhydrous methanol (3 eq.). After 6 h at ambient temperature, the reaction mixture was filtered followed by concentration in vacuo to give
imine 16. - Then
imine 16 was reduced with sodium borohydride (6 eq.) in methanol at ambient temperature for 24 h. After removal of all volatiles in vacuo,amine 18 was obtained by partitioning the residue between Et2O and H2O, drying over Na2SO4 and concentrating in vacuo. - Then excess dimethylethoxysilane (10 eq.) was added to compound 18 followed by addition of a solution of catalyst (0.1 mol %), (e.g., hexachloroplatinic acid in a minimum amount of ethanol). After stirring at 50° C. for 24 h, the silane and solvent were removed in vacuo to provide
silyl compound 19. -
Compound 19 was mixed with excess triethylamine (2.0 eq.) in anhydrous CH2Cl2 and kept at between about 0° C. and about 5° C. for 20 min. A solution of acetyl chloride (1.2 equiv) in anhydrous CH2Cl2 was then added dropwise and the mixture was stirred at ambient temperature for 12 h. All volatiles were removed in vacuo and hexanes were added to precipitate triethylammonium chloride salt.Compound 3 was obtained after filtration and removal of solvent in vacuo. - Similarly, compounds 4, 5, 6 and 7 can be prepared by reacting
compound 19 with sulfonyl chloride, ethyl chloroformate, N,N-dimethylcarbamyl chloride and N,N-dimethylsulphamoyl chloride, respectively. - Excess dimethylethoxysilane (10 equiv) was added to 10-undecen-1-ol (25) followed by addition of a solution of catalyst (0.1 mol %), (e.g., hexachloroplatinic acid in a minimum amount of ethanol). After stirring at 50° C. for 24 h, the silane and solvent were removed in vacuo to provide
silyl compound 26. -
Compound 26 was then mixed with excess triethylamine (2.0 eq.) in anhydrous CH2Cl2 and kept at between about 0° C. and about 5° C. for 20 min. Then, a solution of acetyl chloride (1.2 eq.) in anhydrous CH2Cl2 was added dropwise and the mixture stirred at ambient temperature for 12 h. All volatiles were removed in vacuo and hexanes were added to precipitate triethylammonium chloride salt.Compound 8 was obtained after filtration and concentration in vacuo. - Similarly
compound 9 can be prepared by reactingcompound 26 with N,N-dimethylcarbamyl chloride. - A 5° C. solution of 11-bromo-1-undecene in THF was added dropwise to a solution of dimethylamine (10 eq.) in THF and stirred at ambient temperature for 12 h. The volatiles were removed in vacuo and the residue was partitioned between CH2Cl2 and H2O, dried over Na2SO4 followed by removal of solvent in vacuo to provide 38.
- Excess dimethylethoxysilane (10 eq.) was added to compound 38 followed by addition of a solution of catalyst (0.1 mol %), (e.g., hexachloroplatinic acid in a minimum amount of ethanol). After stirring at 50° C. for 24 h, the silane and solvent were removed in vacuo to provide
silyl compound 39. -
Compounds -
Compounds composition 36. A proper end-capping reagent, such as a trialkylsilyl chloride, may also be required to produce a packing material for the reversed-phase chromatographic separation. - HPLC chromatography of a test mixture containing uracil, p-butyl benzoic acid and phenanthrene on
composition 27 packed into 4.6×150 mm stainless steel tubes using traditional high pressure slurry techniques yielded the results illustrated inFIG. 1 . The mixture (injection volume of about 5 μL) was eluted with CH3CN/25 mM phosphate buffer at about pH 3.2 at a flow rate of about 1 mL/min at about 30° C. and was detected at 210 nm. For comparison, a C8 column of the same column dimension and prepared using the same silica substrate was also used in chromatography of the test mixture. -
FIG. 1 illustrates the high polarity ofcomposition 27, since the relative retention of the polar compound p-butyl benzoic acid to neutral compound phenanthrene is higher oncomposition 27 than that on C8 column despite that fact that the latter has lower carbon content. Enhancement of polarity may be due to the placement of polar group at the end of the ligand furthest disposed from the silica surface. - HPLC chromatography of a test mixture containing 7 common surfactants including two cationic surfactants (lauryldimethylbenzyl ammonium chloride and octylphenoxyethoxyethyl dimethylbenzyl ammonium chloride), four anionic surfactants (sodium salts of xylene sulfonate, dodecylbenzene sulfonate, decyl sulfate, and dodecyl sulfate) and one nonionic surfactant (Triton X-100), on
composition 36 packed into 4.6×150 mm stainless steel tubes using traditional high pressure slurry techniques yielded the results illustrated inFIG. 6 . The test mixture (injection volume of about 25 μL) was eluted with, CH3CN (A) and 0.1 M NH4OAc at about pH 5.8 (B) mobile phases using a gradient method (25% to 85% A in 30 min, then keep at 85% A for additional 10 min), at a flow rate of about 1 mL/min, at about 30° C. and was detected with evaporative light scattering detection (ELS). - As shown in
FIG. 7 , a column packed withcomposition 36 was compared with a conventional C18 column of the same column dimension (5 μm, in 4.6×150 mm stainless steel tubes) in analysis of an ethoxylated nonionic surfactant Triton X-100. The sample (injection volume of about 10 μL) was eluted with CH3CN and 0.1 M NH4OAc at about pH 5.4 (isocratic mobile phases) at a flow rate of about 1 mL/min, at about 30° C. and was detected by UV at 225 nm. - HPLC chromatography of a test mixture containing 5 common surfactants including four anionic surfactants (sodium salts of xylene sulfonate, dodecylbenzene sulfonate, decyl sulfate and dodecyl sulfate) and one nonionic surfactant (Triton X-100), on
composition 36 packed into 4.6×150 mm stainless steel tubes using traditional high pressure slurry techniques yielded the results illustrated inFIG. 8 . The test mixture (injection volume of about 25 μL) was eluted with CH3CN (A) and 0.1 M NH4OAc at about pH 5.8 (B) mobile phases using a gradient method (25% to 85% A in 30 min, then keep at 85% A for additional 10 min) at a flow rate of about 1 mL/min at about 30° C. and detected with an evaporative light scatting detector. For comparison, the same test mixture was also chromatographed on a C18 column of the same column dimension. - As shown in
FIG. 9 , a column packed withcomposition 36 was compared with a conventional C18 column of the same column dimension (5 μm, in 4.6×150 mm stainless steel tubes) in analyzing the cationic surfactant lauryldimethylbenzyl ammonium chloride. The sample (injection volume of about 5 μL) was eluted with CH3CN and 0.1 M NH4OAc at pH 5.4 (isocratic mobile phases) at a flow rate of about 1 mL/min at about 30° C. and was detected by ELS. The column packed withcomposition 36 exhibits superior peak shape over the C18 column. - As shown in
FIG. 10 , a column packed withcomposition 36 was compared with a conventional C18 column of the same column dimension (5 μm, in 4.6×150 mm stainless steel tubes) in analyzing the highly hydrophilic surfactant, sodium xylene sulfonate. The sample (injection volume of about 5 μL) was eluted with, CH3CN/0.1 M NH4OAc, about pH 5.4 v/v 30/70 (isocratic mobile phases) at a flow rate of about 1 mL/min, at about 30° C. and detected by UV at about 225 nm. The column packed withcomposition 36 exhibits excellent resolution among the isomers with decent retention times. - Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it will be readily apparent to one of ordinary skill in the art in light of the teachings of this invention that certain changes and modifications may be made thereto without departing from the spirit or scope of the appended claims.
- All publications and patent documents cited in this specification are herein incorporated by reference in their entirety.
Claims (14)
1. A composition comprising a compound of structural Formula (II):
or salts, solvates or hydrates thereof
wherein:
R1, R2 and R3 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more R14 groups, provided that at least one of R1, R2 and R3 are not alkyl, aryl or hydroxyl;
L1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl;
Y is —C(O)N(R4)(R5), —N(R4)C(O)R7, —N(R4)S(O2)R7, —S(O)2N(R4)(R5), —OC(O)R7, —OC(O)N(R4)(R5), —N(R4)C(O)OR7, —N(R4)C(O)N(R5)(R6) or —N(R4)S(O2)N(R5)(R6); and
R4, R5 and R6 are independently hydrogen, (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups;
R7 is (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups and
R14 is (C1-C6)alkyl; provided that one of R4, R5 or R6 is not hydrogen;
wherein said compound is covalently bonded to a substrate.
3. The composition of claim 1 in which the compound is covalently bonded to the substrate by reaction of one or more of R1, R2 and R3 with reactive groups on the substrate selected from the group consisting of silanol, alkoxysilane, halosilane or aminosilane.
4. The composition of claim 1 in which —SiR1(R2)(R3) is covalently bonded to another compound of claim 1 by reaction with reactive groups selected from the group consisting of silanol, alkoxysilane or halosilane on the other compound.
7. A chromatographic method comprising flowing an aqueous liquid through a bed of separation medium comprising a compound of structural Formula (II):
or salts, solvates or hydrates thereof
wherein:
R1, R2 and R3 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more R14 groups, provided that at least one of R1, R2 and R3 are not alkyl, aryl or hydroxyl;
L1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl;
Y is —C(O)N(R4)(R5), —N(R4)C(O)R7, —N(R4)S(O2)R7, —S(O)2N(R4)(R5), —OC(O)R7, —OC(O)N(R4)(R5), —N(R4)C(O)OR7, —N(R4)C(O)N(R5)(R6) or —N(R4)S(O2)N(R5)(R6); and
R4, R5 and R6 are independently hydrogen, (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups;
R7 is (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups and
R14 is (C1-C6)alkyl; provided that one of R4, R5 or R6 is not hydrogen;
wherein said compound is covalently bonded to a substrate.
8. A chromatographic method comprising flowing an aqueous liquid through a bed of separation medium comprising a compound of structural Formula (II):
or salts, solvates or hydrates thereof,
wherein
R1, R2 and R3 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more (C1-C6)alkyl groups, provided that at least one of R1, R2 and R3 is not alkyl, aryl or hydroxyl;
L1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and
Y is —C(O)N(R4)(R5), —N(R4)C(O)R7, —N(R4)S(O2)R7, —S(O)2N(R4)(R5), —OC(O)R7, —OC(O)N(R4)(R5), —N(R4)C(O)OR7, —N(R4)C(O)N(R5)(R6) or —N(R4)S(O2)N(R5)(R6),
wherein
R4, R5 and R6 are independently hydrogen, (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups, provided that at least one of R4, R5 and R6 is not hydrogen; and
R7 is (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups;
wherein said compound is covalently bonded to a substrate,
said composition further comprising a compound of structural Formula (IV) covalently bonded to said substrate:
wherein
R8, R9, and R10 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl optionally substituted with one or more independently selected (C1-C6)alkyl groups, provided that at least one of R1, R2 and R3 is not alkyl, aryl or hydroxyl;
L2 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and
W is an ionizable group and different than Y.
9. A method for the chromatographic separation of analytes in a liquid sample comprising flowing the liquid sample through medium comprising a compound of structural Formula (II):
or salts, solvates or hydrates thereof
wherein:
R1, R2 and R3 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more R14 groups, provided that at least one of R1, R2 and R3 are not alkyl, aryl or hydroxyl;
L1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl;
Y is —C(O)N(R4)(R5), —N(R4)C(O)R7, —N(R4)S(O2)R7, —S(O)2N(R4)(R5), —OC(O)R7, —OC(O)N(R4)(R5), —N(R4)C(O)OR7, —N(R4)C(O)N(R5)(R6) or —N(R4)S(O2)N(R5)(R6); and
R4, R5 and R6 are independently hydrogen, (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups;
R7 is (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups and
R14 is (C1-C6)alkyl; provided that one of R4, R5 or R6 is not hydrogen;
wherein said compound is covalently bonded to a substrate.
10. A method for the chromatographic separation of analytes in a liquid sample comprising flowing the liquid sample through medium comprising a compound of structural Formula (II):
or salts, solvates or hydrates thereof,
wherein
R1, R2 and R3 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more (C1-C6)alkyl groups, provided that at least one of R1, R2 and R3 is not alkyl, aryl or hydroxyl;
L1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and
Y is —C(O)N(R4)(R5), —N(R4)C(O)R7, —N(R4)S(O2)R7, —S(O)2N(R4)(R5), —OC(O)R7, —OC(O)N(R4)(R5), —N(R4)C(O)OR7, —N(R4)C(O)N(R5)(R6) or —N(R4)S(O2)N(R5)(R6),
wherein
R4, R5 and R6 are independently hydrogen, (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups, provided that at least one of R4, R5 and R6 is not hydrogen; and
R7 is (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups;
wherein said compound is covalently bonded to a substrate,
said composition further comprising a compound of structural Formula (IV) covalently bonded to said substrate:
wherein
R8, R9, and R10 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl optionally substituted with one or more independently selected (C1-C6)alkyl groups, provided that at least one of R1, R2 and R3 is not alkyl, aryl or hydroxyl;
L2 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and
W is an ionizable group and different than Y.
11. A method for simultaneous analysis of cationic, neutral and anionic surfactants in a liquid sample comprising flowing the liquid sample through medium comprising the composition of a compound of structural Formula (II):
or salts, solvates or hydrates thereof,
wherein
R1, R2 and R3 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more (C1-C6)alkyl groups, provided that at least one of R1, R2 and R3 is not alkyl, aryl or hydroxyl;
L1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and
Y is —C(O)N(R4)(R5), —N(R4)C(O)R7, —N(R4)S(O2)R7, —S(O)2N(R4)(R5), —OC(O)R7, —OC(O)N(R4)(R5), —N(R4)C(O)OR7, —N(R4)C(O)N(R5)(R6) or —N(R4)S(O2)N(R5)(R6),
wherein
R4, R5 and R6 are independently hydrogen, (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups, provided that at least one of R4, R5 and R6 is not hydrogen; and
R7 is (C1-C6)alkyl optionally substituted with one or more hydroxy or cyano groups or (C5-C7)aryl optionally substituted with one or more hydroxy or cyano groups;
wherein said compound is covalently bonded to a substrate,
said composition further comprising a compound of structural Formula (IV) covalently bonded to said substrate:
wherein
R8, R9, and R10 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl optionally substituted with one or more independently selected (C1-C6)alkyl groups, provided that at least one of R1, R2 and R3 is not alkyl, aryl or hydroxyl;
L2 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and
W is an ionizable group and different than Y.
12. A chromatography column comprising the composition of claim 1 packed in a suitable housing.
13. A packing comprising the compound of claim 1 covalently bonded to a first substrate and a compound of structural Formula (IV) bonded to a second substrate wherein Formula (IV) is:
R8, R9, and R10 are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl, optionally substituted with one or more of the same or different R13 groups, provided that at least one of R1, R2 and R3 are not alkyl, aryl or hydroxyl;
R13 is (C1-C6)alkyl;
L2 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and
W is an ionizable group.
14. The compound of claim 13 , in which the first substrate and the second substrate are a silica substrate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US12/275,117 US20090130767A1 (en) | 2005-02-15 | 2008-11-20 | Organosilanes and substrates covalently bonded with same and methods for synthesis and use |
Applications Claiming Priority (2)
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US11/059,179 US7468130B2 (en) | 2005-02-15 | 2005-02-15 | Organosilanes and substrates covalently bonded with same and methods for synthesis and use same |
US12/275,117 US20090130767A1 (en) | 2005-02-15 | 2008-11-20 | Organosilanes and substrates covalently bonded with same and methods for synthesis and use |
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US11/059,179 Division US7468130B2 (en) | 2005-02-15 | 2005-02-15 | Organosilanes and substrates covalently bonded with same and methods for synthesis and use same |
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US20090130767A1 true US20090130767A1 (en) | 2009-05-21 |
Family
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US11/059,179 Active 2026-01-19 US7468130B2 (en) | 2005-02-15 | 2005-02-15 | Organosilanes and substrates covalently bonded with same and methods for synthesis and use same |
US12/275,117 Abandoned US20090130767A1 (en) | 2005-02-15 | 2008-11-20 | Organosilanes and substrates covalently bonded with same and methods for synthesis and use |
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US11/059,179 Active 2026-01-19 US7468130B2 (en) | 2005-02-15 | 2005-02-15 | Organosilanes and substrates covalently bonded with same and methods for synthesis and use same |
Country Status (8)
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US (2) | US7468130B2 (en) |
EP (1) | EP1848726B1 (en) |
JP (2) | JP5667335B2 (en) |
KR (1) | KR20070104377A (en) |
CN (1) | CN101120007A (en) |
AU (1) | AU2006214491A1 (en) |
CA (1) | CA2597899A1 (en) |
WO (1) | WO2006088760A1 (en) |
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CN107106931A (en) * | 2014-10-29 | 2017-08-29 | 戴安公司 | Chromatographic material and its preparation method |
US11504707B2 (en) | 2017-11-06 | 2022-11-22 | Dionex Corporation | Ion exchange stationary phases for analyzing polyvalent ions |
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US10766026B2 (en) | 2018-08-10 | 2020-09-08 | Dionex Corporation | Anion exchange stationary phases based on crosslinked hydroxyalkylamine layer and glycidol |
US11198117B2 (en) | 2019-11-04 | 2021-12-14 | Dionex Corporation | Longitudinal gradient chromatography columns |
Also Published As
Publication number | Publication date |
---|---|
JP2008530209A (en) | 2008-08-07 |
EP1848726B1 (en) | 2014-08-13 |
JP5667335B2 (en) | 2015-02-12 |
KR20070104377A (en) | 2007-10-25 |
EP1848726A1 (en) | 2007-10-31 |
US20060180549A1 (en) | 2006-08-17 |
JP2015034163A (en) | 2015-02-19 |
AU2006214491A1 (en) | 2006-08-24 |
CN101120007A (en) | 2008-02-06 |
US7468130B2 (en) | 2008-12-23 |
WO2006088760A1 (en) | 2006-08-24 |
JP6181014B2 (en) | 2017-08-16 |
CA2597899A1 (en) | 2006-08-24 |
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