US20210061824A1 - Silanol compound and method for producing silanol compound - Google Patents
Silanol compound and method for producing silanol compound Download PDFInfo
- Publication number
- US20210061824A1 US20210061824A1 US16/606,487 US201816606487A US2021061824A1 US 20210061824 A1 US20210061824 A1 US 20210061824A1 US 201816606487 A US201816606487 A US 201816606487A US 2021061824 A1 US2021061824 A1 US 2021061824A1
- Authority
- US
- United States
- Prior art keywords
- silanol compound
- compound according
- producing
- mmol
- liquid
- 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
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- -1 Silanol compound Chemical class 0.000 title claims description 137
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 150000001768 cations Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 117
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 68
- 150000003863 ammonium salts Chemical class 0.000 claims description 37
- 150000007513 acids Chemical class 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 150000002430 hydrocarbons Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000008247 solid mixture Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000007859 condensation product Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000010494 dissociation reaction Methods 0.000 claims description 8
- 230000005593 dissociations Effects 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 114
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 66
- 239000007787 solid Substances 0.000 description 66
- 239000000243 solution Substances 0.000 description 59
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 57
- 239000000725 suspension Substances 0.000 description 45
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 41
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 36
- 238000005259 measurement Methods 0.000 description 36
- 239000006185 dispersion Substances 0.000 description 30
- 239000000706 filtrate Substances 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 19
- ZMXDDKWLCZADIW-YYWVXINBSA-N N,N-dimethylformamide-d7 Chemical compound [2H]C(=O)N(C([2H])([2H])[2H])C([2H])([2H])[2H] ZMXDDKWLCZADIW-YYWVXINBSA-N 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- GXHFUVWIGNLZSC-UHFFFAOYSA-N meldrum's acid Chemical group CC1(C)OC(=O)CC(=O)O1 GXHFUVWIGNLZSC-UHFFFAOYSA-N 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 0 C*(*)N(C)CC* Chemical compound C*(*)N(C)CC* 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 238000004455 differential thermal analysis Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 238000004949 mass spectrometry Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 7
- 239000012429 reaction media Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004896 high resolution mass spectrometry Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- DWSIQAGIPZVGNM-UHFFFAOYSA-N CC(C)[Si](C)(C(C)C)C(C)C.CC(C)[Si](O)(C(C)C)C(C)C Chemical compound CC(C)[Si](C)(C(C)C)C(C)C.CC(C)[Si](O)(C(C)C)C(C)C DWSIQAGIPZVGNM-UHFFFAOYSA-N 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 4
- 150000004819 silanols Chemical class 0.000 description 4
- HSNUIYJWTSJUMS-UHFFFAOYSA-N sodium;trimethyl(oxido)silane Chemical compound [Na+].C[Si](C)(C)[O-] HSNUIYJWTSJUMS-UHFFFAOYSA-N 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 4
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 4
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N Azide Chemical compound [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- GWBJIMWNRHZBAL-UHFFFAOYSA-N O[Si]12O[Si]3(O)O[Si](O)(O1)O[Si]1(O)O[Si](O)(O[Si](O)(O1)O3)O2 Chemical compound O[Si]12O[Si]3(O)O[Si](O)(O1)O[Si]1(O)O[Si](O)(O[Si](O)(O1)O3)O2 GWBJIMWNRHZBAL-UHFFFAOYSA-N 0.000 description 2
- LNADLFZROPUKAJ-UHFFFAOYSA-N O[Si]12O[Si]3(O)O[Si]4(O)O[Si](O)(O1)O[Si]1(O)O[Si](O)(O2)O[Si](O)(O3)O[Si](O)(O4)O1 Chemical compound O[Si]12O[Si]3(O)O[Si]4(O)O[Si](O)(O1)O[Si]1(O)O[Si](O)(O2)O[Si](O)(O3)O[Si](O)(O4)O1 LNADLFZROPUKAJ-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GJSGYPDDPQRWPK-UHFFFAOYSA-N tetrapentylammonium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CCCCC GJSGYPDDPQRWPK-UHFFFAOYSA-N 0.000 description 2
- SXAWRMKQZKPHNJ-UHFFFAOYSA-M tetrapentylazanium;chloride Chemical compound [Cl-].CCCCC[N+](CCCCC)(CCCCC)CCCCC SXAWRMKQZKPHNJ-UHFFFAOYSA-M 0.000 description 2
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XGBWXISUZXYULS-UHFFFAOYSA-N 2,3-ditert-butylpyridine Chemical compound CC(C)(C)C1=CC=CN=C1C(C)(C)C XGBWXISUZXYULS-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GKDFDQYLOFQXOH-UHFFFAOYSA-N CC(=O)CC(C)=O.CC1(C)CC(=O)CC(=O)C1.CC1(C)OC(=O)CC(=O)O1 Chemical compound CC(=O)CC(C)=O.CC1(C)CC(=O)CC(=O)C1.CC1(C)OC(=O)CC(=O)O1 GKDFDQYLOFQXOH-UHFFFAOYSA-N 0.000 description 1
- VDQRNQHWPXWFJU-UHFFFAOYSA-N CC(=O)N(C)C.CN(C)C(=O)N(C)C Chemical compound CC(=O)N(C)C.CN(C)C(=O)N(C)C VDQRNQHWPXWFJU-UHFFFAOYSA-N 0.000 description 1
- QBHKSTVLPMOQTB-UHFFFAOYSA-N CC(C)[Si](C)(C(C)C)C(C)C.CC(C)[Si](O)(C(C)C)C(C)C.CC(C)[Si](O[Si](C(C)C)(C(C)C)C(C)C)(C(C)C)C(C)C.O Chemical compound CC(C)[Si](C)(C(C)C)C(C)C.CC(C)[Si](O)(C(C)C)C(C)C.CC(C)[Si](O[Si](C(C)C)(C(C)C)C(C)C)(C(C)C)C(C)C.O QBHKSTVLPMOQTB-UHFFFAOYSA-N 0.000 description 1
- TVAXFTGBKQBHSO-UHFFFAOYSA-N CC1(C)OC(=O)CC(=O)O1.COC(=O)CC(=O)OC Chemical compound CC1(C)OC(=O)CC(=O)O1.COC(=O)CC(=O)OC TVAXFTGBKQBHSO-UHFFFAOYSA-N 0.000 description 1
- HZWDAUVVQXNQBD-UHFFFAOYSA-N CC1(C)OC(=O)CC(=O)O1.C[Si](C)(C)O.C[Si](C)(C)O[Na] Chemical compound CC1(C)OC(=O)CC(=O)O1.C[Si](C)(C)O.C[Si](C)(C)O[Na] HZWDAUVVQXNQBD-UHFFFAOYSA-N 0.000 description 1
- XDBUMHMROLHNKP-UHFFFAOYSA-L CC1(C)OC(=O)CC(=O)O1.C[Si]1(O)O[Si](C)(O)O[Si](C)(O)O[Si](C)(O)O1.C[Si]1(O[K])O[Si](C)(O[K])O[Si](C)([K]O)O[Si](C)([K]O)O1 Chemical compound CC1(C)OC(=O)CC(=O)O1.C[Si]1(O)O[Si](C)(O)O[Si](C)(O)O[Si](C)(O)O1.C[Si]1(O[K])O[Si](C)(O[K])O[Si](C)([K]O)O[Si](C)([K]O)O1 XDBUMHMROLHNKP-UHFFFAOYSA-L 0.000 description 1
- MLLOTQBUYBVDJM-UHFFFAOYSA-M CC1(C)OC(=O)CC(=O)O1.O[Na][Si](O[Na])(O[Na])O[Na].O[Si](O)(O)O Chemical compound CC1(C)OC(=O)CC(=O)O1.O[Na][Si](O[Na])(O[Na])O[Na].O[Si](O)(O)O MLLOTQBUYBVDJM-UHFFFAOYSA-M 0.000 description 1
- RBRPKECWYUNQCM-UHFFFAOYSA-N CCC(C)C1=CC=C(CCC2(C)OC(=O)CC(=O)O2)C=C1 Chemical compound CCC(C)C1=CC=C(CCC2(C)OC(=O)CC(=O)O2)C=C1 RBRPKECWYUNQCM-UHFFFAOYSA-N 0.000 description 1
- HHBBQEYKNUCXDJ-UHFFFAOYSA-N CCN(CC)(CC)(CC)O[Si]12O[Si]3(C)O[Si](C)(O[Si]4(C)O[Si](C)(O3)O[Si](ON(CC)(CC)(CC)CC)(O4)O1)O2.O=[N+]([O-])O.O[Si]12O[Si]3(O)O[Si](O)(O1)O[Si]1(O)O[Si](O)(O[Si](O)(O1)O3)O2 Chemical compound CCN(CC)(CC)(CC)O[Si]12O[Si]3(C)O[Si](C)(O[Si]4(C)O[Si](C)(O3)O[Si](ON(CC)(CC)(CC)CC)(O4)O1)O2.O=[N+]([O-])O.O[Si]12O[Si]3(O)O[Si](O)(O1)O[Si]1(O)O[Si](O)(O[Si](O)(O1)O3)O2 HHBBQEYKNUCXDJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- JUWJWPHXJOSWFP-UHFFFAOYSA-N O[Si]12O[SiH]3O[Si]4(O[Si]56O[Si]7(O)O[Si]8(O)O[Si]9(O)O[Si](O)(O7)O[Si](O)(O[Si](O)(O9)O[Si](O)(O8)O5)O6)O[Si](O)(O1)O[Si]1(O)O[Si](O)(O2)O[Si](O[Si]25O[Si]6(O)O[Si]7(O)O[Si]8(O)O[Si](O)(O6)O[Si](O)(O[Si](O)(O8)O[Si](O)(O7)O2)O5)(O3)O[Si](O)(O1)O4.O[Si]12O[Si]3(O)O[Si]4(O)O[Si](O)(O1)O[Si]1(O)O[Si](O)(O2)O[Si](O)(O3)O[Si](O[Si]23O[Si]5(O)O[Si]6(O)O[Si]7(O)O[Si](O)(O5)O[Si](O)(O[Si](O)(O7)O[Si](O)(O6)O2)O3)(O4)O1 Chemical compound O[Si]12O[SiH]3O[Si]4(O[Si]56O[Si]7(O)O[Si]8(O)O[Si]9(O)O[Si](O)(O7)O[Si](O)(O[Si](O)(O9)O[Si](O)(O8)O5)O6)O[Si](O)(O1)O[Si]1(O)O[Si](O)(O2)O[Si](O[Si]25O[Si]6(O)O[Si]7(O)O[Si]8(O)O[Si](O)(O6)O[Si](O)(O[Si](O)(O8)O[Si](O)(O7)O2)O5)(O3)O[Si](O)(O1)O4.O[Si]12O[Si]3(O)O[Si]4(O)O[Si](O)(O1)O[Si]1(O)O[Si](O)(O2)O[Si](O)(O3)O[Si](O[Si]23O[Si]5(O)O[Si]6(O)O[Si]7(O)O[Si](O)(O5)O[Si](O)(O[Si](O)(O7)O[Si](O)(O6)O2)O3)(O4)O1 JUWJWPHXJOSWFP-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- ZJBHFQKJEBGFNL-UHFFFAOYSA-N methylsilanetriol Chemical compound C[Si](O)(O)O ZJBHFQKJEBGFNL-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000003566 sealing material Substances 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
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- KCIKCCHXZMLVDE-UHFFFAOYSA-N silanediol Chemical compound O[SiH2]O KCIKCCHXZMLVDE-UHFFFAOYSA-N 0.000 description 1
- 229940089952 silanetriol Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0836—Compounds with one or more Si-OH or Si-O-metal 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
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
Definitions
- the present invention relates to a silanol compound and a method for producing a silanol compound, and more specifically, to a method for producing a silanol compound, wherein the silanol compound is formed from a silicate.
- Siloxane is a very important compound that, because of its specific nature, is used in a wide range of fields, such as automobiles, construction, electronics, and medicine. In recent years, siloxane is essential even in the field of environment and energy, such as in sealing materials for LEDs and silane coupling agents for eco-friendly tires. It is no exaggeration to say that there are no fields that do not use siloxane compounds.
- the market size of siloxane compounds in 2009 was 11.5 billion dollars, with an annual production of 1.23 million tons.
- siloxanes are synthesized via silanol by hydrolysis, such as in a sol-gel method using an alkoxysilane, a halogenated silane or the like as a raw material.
- This silanol which includes silanediol, silanetriol and silanetetraol, except for some silanediols and silanetriols having bulky substituents such as phenyl groups, condenses simultaneously with the hydrolysis in the presence of water, and hence it is difficult to synthesize with a good yield. It is also known that silanol is unstable in the presence of water and condenses rapidly (see Non Patent Literature 1 and Non Patent Literature 2).
- An object of the present invention is to provide a method for producing a silanol compound capable of efficiently producing a silanol compound.
- a silanol compound can be efficiently produced by proton exchange of a silicate with an acid compound having an acid dissociation constant pK a in a specific range, thereby completing the present invention.
- the method for producing a silanol compound of the present invention comprises a proton exchange step of forming a silanol compound having a structure represented by following formula (c) by reacting a silicate having a structure represented by following formula (a) with an acidic compound having an acid dissociation constant pK a of ⁇ 1 to 20 in dimethyl sulfoxide (DMSO).
- DMSO dimethyl sulfoxide
- Q i+ represents an i-valent cation and i represents an integer of 1 to 4.
- the silanol compound of the present invention is represented by following formula (D).
- the solid composition of the present invention comprises a silanol compound represented by the above formula (D).
- the composition of the present invention comprises 30% by mass or more of a silanol compound represented by the above formula (D).
- Another composition of the present invention comprises a crystal structure formed with a silanol compound represented by the above formula (D) and an amide compound.
- the dehydrated condensation product of the present invention is obtained by dehydration condensation of a silanol compound represented by the above formula (D).
- a silanol compound can be produced efficiently. Further, the silanol compound of the present invention, a solid composition and a composition including the silanol compound, and a dehydrated condensation product of the silanol compound are useful as a raw material and the like of a siloxane compound to be used in a wide range of fields.
- FIG. 1 shows the 29 Si-NMR measurement results of a solution obtained in Example 1.
- FIG. 2( a ) shows the 29 Si-NMR measurement results of a solution obtained in Example 5
- FIG. 2( b ) shows the high-resolution mass spectrometry (TOF-MS) measurement results of the solution obtained in Example 5.
- FIG. 3 shows a schematic view illustrating a proton exchange step of forming a silanol compound by passing a silicate having a structure represented by formula (a) through a column packed with a resin having a Meldrum's acid structure.
- FIG. 4 shows the measurement results of thermogravimetric differential thermal analysis of a solid obtained in Example 16.
- FIG. 5 shows the 29 Si-NMR measurement results of a solution obtained in Example 31.
- FIG. 6 shows the measurement results of thermogravimetric differential thermal analysis of a solid obtained in Example 31.
- FIG. 7( a ) shows the 1 H-NMR measurement results of a solution of a solid obtained in Example 41
- FIG. 7( b ) shows the 29 Si-NMR measurement results of a solution of the solid obtained in Example 41.
- FIG. 8 shows the measurement results of thermogravimetric differential thermal analysis of a solid obtained in Example 41.
- FIG. 9( a ) shows the 1 H-NMR measurement results of a solution of a solid obtained in Example 42
- FIG. 9( b ) shows the 29 Si-NMR measurement results of a solution of the solid obtained in Example 42.
- FIG. 10 shows the measurement results of thermogravimetric differential thermal analysis of a solid obtained in Example 42.
- FIG. 11( a ) shows the 1 H-NMR measurement results of a solution of a solid obtained in Example 47
- FIG. 11( b ) shows the 29 Si-NMR measurement results of a solution of the solid obtained in Example 47.
- FIG. 12 shows the measurement results of thermogravimetric differential thermal analysis of a solid obtained in Example 47.
- FIG. 13 shows the high-resolution mass spectrometry (TOF-MS) measurement results of a solid obtained in Example 48.
- FIG. 14 shows the 29 Si-NMR measurement results of a solution obtained in Example 49.
- FIG. 15 shows the high-resolution mass spectrometry (TOF-MS) measurement results of the solution obtained in Example 49.
- FIG. 16( a ) shows the 1 H-NMR measurement results of a solution of the liquid obtained in Example 50
- FIG. 16( b ) shows the 29 Si-NMR measurement results of the solution of the liquid obtained in Example 50.
- the method for producing a silanol compound as one embodiment of the present invention comprises a proton exchange step of forming a silanol compound having a structure represented by following formula (c) (hereinafter sometimes abbreviated as “proton exchange step”) by reacting a silicate having a structure represented by following formula (a) (hereinafter sometimes abbreviated as “silicate”) with an acidic compound having an acid dissociation constant pK a of ⁇ 1 to 20 (hereinafter sometimes abbreviated as “acidic compound”) in dimethyl sulfoxide (DMSO) (hereinafter sometimes abbreviated as “pK a (DMSO)”).
- DMSO dimethyl sulfoxide
- Q i+ represents an i-valent cation and i represents an integer of 1 to 4.
- silanol compound Even if an alkoxysilane, a halogenated silane, or the like is simply reacted with water, the formed silanol condenses to form a siloxane (see the following formula), and hence it is difficult to synthesize the silanol itself with a good yield.
- a silanol compound can be efficiently produced by proton exchange of a silicate having a structure represented by formula (a) with an acidic compound having a pK a (DMSO) of ⁇ 1 to 20.
- a silicate having a structure represented by formula (a) with an acidic compound having a pK a (DMSO) of ⁇ 1 to 20.
- the pK a (DMSO) is ⁇ 1 to 20
- the exchange of the silicate cations (Q i+ ) and the acidic compound protons (H + ) progresses efficiently, and a side reaction and the condensation of the formed silanol compound can be suppressed.
- the silanol compound itself can be synthesized with a good yield.
- the production method of the present invention is a production method that is industrially very suitable because the reaction proceeds rapidly under mild conditions. The smaller the pK a (DMSO) is, the faster the proton exchange step proceeds.
- the “silanol compound” may be any compound in which at least one hydroxyl group (—OH) is bonded to a silicon atom (Si), and the number of hydroxyl groups and other structures are not particularly limited.
- the silanol compound may also include a functional group or the like not involved in the reaction.
- the pK a (DMSO) means a known value calculated from the concentration of each component in acid dissociation equilibrium at 25° C. of the acidic compound in DMSO. Specifically, the pK a (DMSO) is a numerical value obtained by common logarithmizing the value K a calculated by the following expression.
- silicate having a structure represented by formula (a) and the acidic compound having a pK a (DMSO) of ⁇ 1 to 20 in the proton exchange step, as well as the other reaction conditions and the like will be described in detail.
- the specific kind of a silicate, the specific kind of an acidic compound, the amount of the acidic compound used, the kind of a reaction medium, which is a solvent or a dispersion medium, the reaction conditions, and the like used in the proton exchange step shown in the following chemical reaction formula are not particularly limited, and can be selected appropriately according to the purpose.
- Q i+ represents an i-valent cation and i represents an integer of 1 to 4.
- Q i+ examples include alkali metal ions such as a lithium ion (Li + ), a sodium ion (Na + ), and a potassium ion (K + ), alkaline earth metal ions such as a magnesium ion (Mg 2+ ) and a calcium ion (Ca 2+ ), transition metal ions such as an iron(III) ion (Fe 3+ ), a copper(II) ion (Cu 2+ ), and a zinc ion (Zn 2+ ), ammonium ions such as an ammonium ion (NH 4 + ), a tetramethylammonium ion (NMe 4 + ), an ethyltrimethylammonium ion (NEtMe 3 + ), a diethyldimethylammonium ion (NEt 2 Me 2 + ), a triethylmethylammonium ion (NEt 3 Me + ),
- a sodium ion (Nat), a potassium ion (K + ), a tetramethylammonium ion (NMe 4 + ), a tetraethylammonium ion (NEt 4 + ), and an ethyltrimethylammonium ion (NEtMe 3 + ) are particularly preferable.
- Q + represents a monovalent cation
- each R independently represents a hydrocarbon group having 1 to 20 carbon atoms which may include at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom
- n represents an integer of 1 to 4.
- “may include at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom” not only means a functional group including a nitrogen atom, an oxygen atom, a halogen atom, or the like may be included, this expression also means that a linking group including a nitrogen atom, an oxygen atom, and the like may be included inside or at the end of the carbon skeleton.
- the “hydrocarbon group” may have a branched structure, a cyclic structure, and a carbon-carbon unsaturated bond (carbon-carbon double bond or carbon-carbon triple bond), respectively, and may be any of a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, and the like.
- Examples of the functional group or the linking group included in the hydrocarbon group of R include an amido group (—NHCO—), an ether group (oxa group, —O—), a fluorine atom (fluoro group, —F), a chlorine atom (chloro group, —Cl), a bromine atom (bromo group, —Br), and an iodine atom (iodo group, —I).
- the hydrocarbon group of R preferably has 1 or more carbon atoms, preferably 14 or fewer carbon atoms, more preferably 10 or fewer carbon atoms, and still more preferably 6 or fewer carbon atoms. When R is an aromatic hydrocarbon group, the number of carbon atoms is usually 6 or more. A silanol compound can be efficiently produced when the number of carbon atoms is in the above range.
- R examples include a methyl group (-Me), an ethyl group (-Et), a n-propyl group (- n Pr), an i-propyl group (- i Pr), a n-butyl group (- n Bu), a sec-butyl group (- s Bu), a t-butyl group (- t Bu), a phenyl group (-Ph), an aryl group (-Ar), a vinyl group (-Vi), and an allyl group (—CH 2 CH ⁇ CH 2 ).
- the acidic compound is a compound having a pK a (DMSO) of ⁇ 1 to 20, and preferably, the pK a (DMSO) is 0 or more, more preferably 1 or more, and still more preferably 3 or more, and is preferably 16 or less, more preferably 14 or less, and still more preferably 8 or less.
- a silanol compound can be efficiently produced when the pK a (DMSO) is in the above range.
- the specific structure and the like of the acidic compound are not particularly limited as long as the pK a (DMSO) is ⁇ 1 to 20.
- the acidic compound examples include inorganic acids such as nitric acid (pK a (DMSO) of 1.4), sulfuric acid (pK a 1 (DMSO) of 1.4 and pK a 2 (DMSO) of 14.7), hydrochloric acid (pK a (DMSO) of 2.1), phosphoric acid (pK a 1 (DMSO) of 1.83, pK a 2 (DMSO) of 6.43, pK a 3 (DMSO) of 11.46), or at least one organic acid selected from the group consisting of acetic acid or compounds having a structure represented by any of the following formulas (b-1) to (b-5).
- inorganic acids such as nitric acid (pK a (DMSO) of 1.4), sulfuric acid (pK a 1 (DMSO) of 1.4 and pK a 2 (DMSO) of 14.7), hydrochloric acid (pK a (DMSO) of 2.1), phosphoric acid (pK a 1 (DMSO)
- the acidic compound is preferably an inorganic acid.
- nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid are preferable, and nitric acid or sulfuric acid is particularly preferable.
- nitric acid or sulfuric acid is particularly preferable.
- the reason for this is because nitrate ions, hydrogen sulfate ions, and sulfate ions have weak interactions (hydrogen bonds etc.) with the silanol compound, and the ammonium salt produced as a by-product does not easily form a complex insoluble in the reaction medium with the silanol compound.
- chloride ions, dihydrogen phosphate ions, hydrogen phosphate ions, and phosphate ions have strong interactions (hydrogen bonds etc.) with the silanol compound, and as a result, in proton exchange using hydrochloric acid or phosphoric acid, the silanol compound and the ammonium salt sometimes form a complex that is insoluble in the reaction medium, which may cause the yield of the desired silanol compound to be slightly reduced.
- each X independently represents an oxygen atom, a sulfur atom, or an amino group (—NR 3 —)
- R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms
- each R 2 independently represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms.
- the acidic compound may include a functional group or the like not involved in the reaction. Therefore, for example, the acidic compound having the structure represented by formula (b-4) may be a compound including a hydrocarbon group such as a methyl group attached to the oxygen atom corresponding to X, like the dimethyl malonate having the following formula. Further, for example, the acidic compound having the structure represented by formula (b-4) may be a compound in which the hydrocarbon groups attached to the oxygen atoms corresponding to X are bonded to form a cyclic structure, like the Meldrum's acid having the following formula.
- the structures represented by formulas (b-1) to (b-5) are so-called ⁇ -dicarbonyl structures, but the hydrogen of a methylene group sandwiched between the two carbonyl groups, i.e., the ⁇ -hydrogen, is known to act as an acid site.
- the acid compound exhibits an appropriate acid dissociation constant, and the electrons of the anion formed by the dissociation of protons are delocalized in the structure.
- the protons dissociate in the manner represented by the following formula.
- the acidic compounds having a structure represented by any of formulas (b-1) to (b-5) can suppress the basicity and nucleophilicity of the anion, and a side reaction and condensation of the silanol compound can be effectively suppressed.
- Examples of the amino group (—NR 3 —) as X include secondary amino groups (—NH—). It is particularly preferred that X be an oxygen atom.
- R 1 is a hydrocarbon group, the number of carbon atoms is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less.
- Examples of R 1 include a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), a n-propyl group (- n Pr), an i-propyl group (- i Pr), a n-butyl group (- n Bu), and a phenyl group (-Ph), and a hydrogen atom is preferable.
- R 2 is a hydrocarbon group
- the number of carbon atoms is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less.
- R 2 include a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), a n-propyl group (- n Pr), an i-propyl group (- i Pr), and a n-butyl group (- n Bu), and a hydrogen atom is preferable.
- Examples of the acidic compound represented by formula (b-4) include acidic compounds represented by following formula (b-4-1).
- Examples of the acidic compound represented by formula (b-5) include acidic compounds represented by following formula (b-5-1).
- R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms
- R 4 represents a divalent hydrocarbon group having 1 to 14 carbon atoms.
- R 4 examples include a methylene group (—CH 2 —), an ethylene group (—CH 2 CH 2 —), a n-propylene group (—CH 2 CH 2 CH 2 —), a dimethylmethylene group (—C(CH 3 ) 2 —), and an i-propylene group (—CH(CH 3 )CH 2 —).
- Examples of the acidic compound include acetic acid (pK a (DMSO) of 12.6), benzoic acid (pK a (DMSO) of 11.1), Meldrum's acid (pK a (DMSO) of 7.3), a Meldrum's acid derivative, dimedone (pK a (DMSO) of 11.2), a dimedone derivative, acetylacetone (pK a (DMSO) of 13.3), and an acetylacetone derivative (see the following formulas)
- the acidic compound there may be used a solid obtained by introducing a compound represented by any of formulas (b-2) to (b-5) into a low molecular weight compound, such as Meldrum's acid, or an organic solid material, such as a resin, or an inorganic solid material, such as silica or carbon. If the acidic compound is such a solid, the acidic compound can be packed in a column as shown in FIG. 3 and used as an ion exchange resin. This enables the silanol compound to be produced very efficiently.
- a compound represented by any of formulas (b-2) to (b-5) into a low molecular weight compound, such as Meldrum's acid, or an organic solid material, such as a resin, or an inorganic solid material, such as silica or carbon.
- the acidic compound is preferably a resin having at least one structure selected from the group consisting of formulas (b-2) to (b-5). It is preferred that the acid compound be capable of being regenerated by exposing to an aqueous acidic solution, such as hydrochloric acid, after the proton exchange step.
- an aqueous acidic solution such as hydrochloric acid
- the amount of the acidic compound used in the proton exchange step is, in terms of the amount of substance with respect to the silicate, usually 1 times or more, preferably 1.05 times or more, and more preferably 1.1 times or more, and usually 50 times or less, preferably 20 times or less, and more preferably 5 times or less.
- the amount used is in the above range, a silanol compound can be efficiently produced.
- the liquid include ether liquids such as THF, tetrahydropyran, dioxane, diethyl ether (Et 2 O), dimethyl ether, diisopropyl ether, diphenyl ether, methyl ethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, alcohol liquids such as methanol, ethanol, n-propanol, and i-propanol, amide liquids such as formamide, N,N-dimethylformamide (DMF), acetamide, N-methylacetamide, DMAc, urea, and tetramethylurea, ester liquids such as ethyl acetate, n-amyl acetate, and ethyl lactate, halogen liquids such as methylene chloride, chloroform, carbon tetrachloride, tetrach
- the amount of liquid used in the proton exchange step is preferably such that the content of the silicate is 0.005 to 0.04 mol/L. This is because a silanol compound can be produced efficiently with such a silicate content.
- the reaction temperature in the proton exchange step is usually ⁇ 80° C. or more, preferably 0° C. or more, and more preferably 20° C. or more, and is usually 200° C. or less, preferably 70° C. or less, and more preferably 40° C. or less.
- the reaction time in the proton exchange step is usually 48 hours or less, preferably 24 hours or less, more preferably 8 hours or less, and particularly preferably 1 hour or less.
- a silanol compound can be efficiently produced when these factors are in the respective ranges above.
- the production method of the present invention may include steps other than the proton exchange step.
- steps other than the proton exchange step include an ammonium salt addition step of adding an ammonium salt to the product obtained in the proton exchange step (hereinafter sometimes abbreviated as “ammonium salt addition step”), a freeze-drying step of freezing the product obtained in the proton exchange step or the product obtained in the ammonium salt addition step and exposing the product to reduced pressure (hereinafter sometimes abbreviated as “freeze-drying step”), and a crystallization step of precipitating crystals from the product obtained in the proton exchange step or the product obtained in the ammonium salt addition step by a poor solvent method or an evaporation method (hereinafter sometimes abbreviated as “crystallization step”).
- the “ammonium salt addition step”, the “freeze-drying step”, the “crystallization step” and the like are now described below in detail.
- ammonium salt means a compound formed with an ammonium ion and a counter anion, and the structures of the ammonium ion and the counter anion are not particularly limited. It is considered that the addition of the ammonium salt suppresses condensation of the silanol compound.
- ammonium ion examples include a tetrahydroammonium ion (NH 4 + ), a tetramethylammonium ion (NMe 4 + ), a tetrapropylammonium ion (NPr 4 + ), a tetrabutylammonium ion (NBu 4 + ), a benzyltributylammonium ion (NBnBu 3 + ), a tributyl(methyl)ammonium (NBu 3 Me + ) ion, a tetrapentylammonium ion (NPen 4 + ), a tetrahexylammonium ion (NHex 4 + ), a tetraheptylammonium ion (NHep 4 + ), an 1-butyl-1 methylpyrrolidinium ion (BuMePyr + ), a methyltrioctylammonium ion (NH
- Examples of the counter anion include a fluoride ion (F ⁇ ), a chloride ion (Cl ⁇ ), a bromide ion (Br ⁇ ), an iodide ion (I ⁇ ), an acetoxy ion (AcO ⁇ ), a nitrate ion (NO 3 ⁇ ), an azide ion (N 3 ⁇ ), a tetrafluoroborate ion (BF 4 ⁇ ), a perchlorate ion (ClO 4 ⁇ ), and a hydrogen sulfate ion (HSO 4 ⁇ ).
- the ammonium salt is particularly preferably tetrabutylammonium chloride (NBu 4 Cl), tetrabutylammonium bromide (NBu 4 Br), tetrapentylammonium chloride (NPen 4 Cl), a Meldrum's acid-tetramethylammonium salt, or dimethyldioctadecylammonium chloride.
- the ammonium salt included in the composition is not limited to one kind, and may include two or more kinds.
- the amount of the ammonium salt used is preferably 1 to 4 times in terms of the amount of substance with respect to the silanol compound.
- the freezing temperature, the drying temperature, the drying pressure, the drying time, and the like in the freeze-drying step are not particularly limited, and can be appropriately selected according to the purpose.
- the freezing temperature is not particularly limited as long as the product obtained in the proton exchange step or the product obtained in the ammonium salt addition step freezes, but it is usually 10° C. or less, preferably 0° C. or less, and more preferably ⁇ 20° C. or less, and is usually ⁇ 196° C. or more, preferably ⁇ 150° C. or more, and more preferably ⁇ 100° C. or more.
- the drying temperature is usually 10° C. or less, preferably 0° C. or less, and more preferably ⁇ 20° C. or less, and is usually ⁇ 196° C. or more, preferably ⁇ 150° C. or more, and more preferably ⁇ 100° C. or more.
- the drying pressure is usually 100 Pa or less, preferably 20 Pa or less, and more preferably 3 Pa or less, and is usually 10 ⁇ 5 Pa or more, preferably 0.01 Pa or more, more preferably 1 Pa or more.
- the drying time is usually 200 hours or less, preferably 100 hours or less, and more preferably 50 hours or less, and is usually 1 hour or more, preferably 5 hours or more, and more preferably 10 hours or more.
- the solvent used in the crystallization step, the crystallization time (standing time), and the like are not particularly limited, and can be appropriately selected according to the purpose.
- the boiling point of the solvent to be used is usually 0° C. or more, preferably 10° C. or more, and more preferably 30° C. or more, and is usually 300° C. or less, preferably 200° C. or less, and more preferably 100° C. or less.
- Examples of the solvent to be used include Et 2 O, THF, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, DMAc, N,N-dimethylformamide, N-methylacetamide, DMSO, and tetramethylurea.
- the crystallization time (standing time) is usually 720 hours or less, preferably 360 hours or less, and more preferably 168 hours or less, and is usually 1 hour or more, preferably 5 hours or more, and more preferably 10 hours or more.
- a silanol compound represented by following formula (D) (hereinafter sometimes abbreviated as “the silanol compound of the present invention”), a solid composition including a silanol compound represented by following formula (D) (hereinafter sometimes abbreviated as “the solid composition of the present invention”), a composition including a silanol compound represented by following formula (D) (hereinafter sometimes abbreviated as “the composition of the present invention”) and a dehydrated condensation product of a silanol compound represented by following formula (D) (hereinafter sometimes abbreviated as “the dehydrated condensation product of the present invention”), which can be produced by the production method of the present invention and are useful as a raw material and the like of a siloxane compound, are also embodiments of the present invention.
- the kind and the like of a compound other than a silanol compound represented by formula (D) that is included in the solid composition or the composition of the present invention are not particularly limited, and can be appropriately selected according to the purpose. It is also noted that since the silanol compound represented by formula (D) is obtained in a high concentration by the production method of the present invention, the content of the silanol compound represented by formula (D) in the solid composition or the composition of the present invention can be adjusted appropriately. For example, the content of the silanol compound represented by formula (D) in the solid composition or the composition can be 95% by mass or more by evaporating the solvent at about 100° C., at which dehydration condensation does not easily proceed. In addition, even if the solid composition of the present invention is heated at about 100° C., it is known from the results of Raman analysis that the basket-shaped skeletal structure of the silanol compound represented by formula (D) is maintained.
- Examples of the compound other than the silanol compound represented by formula (D) include water, an ether compound, an amine compound, an amide compound, and an ammonium salt.
- the amine compound, the amide compound, and the ammonium salt have an effect of suppressing the condensation of the silanol compound.
- water tends to be included in those compositions as a result of mixing from the atmosphere or generation by dehydration condensation of the silanol compound.
- the water content in the composition of the present invention is preferably as small as possible, for the reason that water promotes condensation of the silanol compound and causes a decrease in the stability of the solid composition or the composition of the present invention.
- the specific kind of the amine compound is not particularly limited, as long as the amine compound has an amino group (which may be any of a primary amine, a secondary amine, or a tertiary amine).
- compounds having both an amino group and an amide group are classified herein as being an “amide compound”.
- the amine compound include aniline (NH 2 Ph), diphenylamine (NHPh 2 ), dimethylpyridine (Me 2 Pyr), di-tert-butylpyridine ( t Bu 2 Pyr), pyrazine (Pyraz), triphenylamine (NPh 3 ), triethylamine (Et 3 N), and di-isopropylethylamine ( i Pr 2 EtN).
- aniline (NH 2 Ph) is particularly preferred.
- the amine compound included in the composition is not limited to one kind, and two or more kinds may be included.
- the content (the total content when including two or more kinds) of the amine compound in the solid composition or the composition of the present invention is preferably more than 0.1% by mass, more preferably 1% by mass or more, and even more preferably 10% by mass or more, and is usually less than 95% by mass, preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
- the specific kind of the amide compound is not particularly limited as long as the amine compound has an amide bond.
- Examples of the amide compound include compounds represented by following formula (i) or (ii).
- each R′ and R′′ independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- Example of R′ and R′′ include a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), a n-propyl group (- n Pr), an i-propyl group (- i Pr), and a phenyl group (-Ph).
- Examples of the compound represented by formula (i) include formamide, DMF, acetamide, N-methylacetamide, and DMAc.
- Examples of the compound represented by formula (ii) include urea, and tetramethylurea (Me 4 Urea).
- the content (the total content when including two or more kinds) of the amide compound in the solid composition or the composition of the present invention may be 0% by mass (not contained) or more and 90% by mass or less.
- ammonium salt is not particularly limited, as long as the ammonium salt is a compound formed with an ammonium ion and a counter anion.
- ammonium ion examples include a tetrahydroammonium ion (NH 4 + ), a tetramethyl ammonium ion (NMe 4 + ), a tetraethylammonium ion (NEt 4 + ), a tetrapropylammonium ion (NPr 4 + ), a tetrabutylammonium ion (NBu 4 + ), a benzyltributylammonium ion (NBnBu 3 + ), a tributyl(methyl)ammonium (NBu 3 Me + ) ion, a tetrapentylammonium ion (NPen 4 + ), a tetrahexylammonium ion (NHex 4 + ), a
- examples of the counter anion include a fluoride ion (F ⁇ ), a chloride ion (Cl ⁇ ), a bromide ion (Br ⁇ ), an iodide ion (I ⁇ ), an acetoxy ion (AcO ⁇ ), a nitrate ion (NO 3 ⁇ ), an azide ion (N 3 ⁇ ), a tetrafluoroborate ion (BF 4 ⁇ ), a perchlorate ion (ClO 4 ⁇ ), and a hydrogen sulfate ion (HSO 4 ⁇ ).
- the ammonium salt is particularly preferably tetrabutylammonium chloride (NBu 4 Cl), tetrabutylammonium bromide (NBu 4 Br), tetrapentylammonium chloride (NPen 4 Cl), dimethyldioctadecyl ammonium chloride, or a Meldrum's acid-tetramethylammonium salt.
- the ammonium salt included in the composition is not limited to one kind, and may include two or more kinds.
- the content (the total content when including two or more kinds) of the ammonium salt in the solid composition or the composition of the present invention is preferably more than 0.1% by mass, and more preferably 50% by mass or more, and is usually less than 95% by mass, and preferably 80% by mass or less.
- the ratio of the ammonium salt to the silanol compound in the solid composition or the composition of the present invention is preferably greater than 0, and more preferably 1 or more, and is usually 8 or less, preferably 6 or less, and more preferably 4 or less.
- the dehydrated condensation product of the present invention is a compound formed by dehydration condensation of the hydroxyl group of the silanol compound represented by formula (D), like a dimer or trimer represented by the following formula.
- the dehydrated condensation product of the present invention is usually a product in which two or more silanol compounds represented by formula (D) are condensed, and is usually a product in which 20 or less, preferably 10 or less, and more preferably 5 or less silanol compounds are condensed. In the above range, the dehydrated condensation product becomes easier to utilize as a raw material and the like of a siloxane compound.
- a solution of 34 mg (0.30 mmol) of sodium trimethylsilanolate (Me 3 SiONa) in 1 mL of THF solution was poured in the resin represented by the chemical formula (E) swollen with THF. The solution which flowed out was distilled off and trimethylsilanol was isolated by various NMR and mass spectrometry (yield: 99% or more).
- silica gel was then separated by filtration using a filter (washed with 10 mL of THF), 2.0 g of silica gel (Silica Gel 60, pH 6 (Kanto Chemical)) was added to the filtrate, and the mixture was stirred for 5 minutes.
- the silica gel was separated by filtration using a filter (washed with 5 mL of THF). The filtrate was concentrated by distilling under reduced pressure, and recrystallized at ⁇ 5° C.
- a colorless solid which was a composition including 37% by mass of Q 8 H 8 , was isolated in a yield of 72% (429 mg) (Q 8 H 8 ) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 19, except that the amount of nitric acid used was changed from 0.212 mL (3.35 mmol) to 0.250 mL (3.95 mmol).
- a colorless solid which was a composition including 36% by mass of Q 8 H 8 , was isolated in a yield of 62% (3.851 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 21, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 2.53 mL (40.0 mmol).
- a colorless solid which was a composition including 40% by mass of Q 8 H 8 , was isolated in a yield of 43% (2.427 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 24, except that the amount of THF used was changed from 200 mL to 150 mL.
- a colorless solid which was a composition including 37% by mass of Q 8 H 8 , was isolated in a yield of 50% (2.988 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 24, except that the amount of THF used was changed from 200 mL to 100 mL.
- a colorless solid which was a composition including 37% by mass of Q 8 H 8 , was isolated in a yield of 43% (2.552 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 24, except that the stirring time was changed from 5 minutes to 30 minutes.
- a colorless solid which was a composition including 43% by mass of Q 8 H 8 , was isolated in a yield of 63% (3.237 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 25, except that the stirring time was changed from 5 minutes to 30 minutes.
- a colorless solid which was a composition including 36% by mass of Q 8 H 8 , was isolated in a yield of 47% (2.872 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 27, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 2.53 mL (40.0 mmol).
- a colorless solid which was a composition including 41% by mass of Q 8 H 8 , was isolated in a yield of 86% (4.717 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 27, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 3.04 mL (48.0 mmol).
- a colorless solid which was a composition including 37% by mass of Q 8 H 8 , was isolated in a yield of 99% (5.889 g) in the same manner as in Example 27, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 3.55 mL (56.0 mmol).
- the 29 Si-NMR measurement results of this solid are shown in FIG. 5 ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm). Further, the measurement results of thermogravimetric differential thermal analysis of this solid are shown in FIG. 6 .
- a colorless solid which was a composition including 37% by mass of Q 8 H 8 , was isolated in a yield of 85% (5.135 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 28, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 3.04 mL (48.0 mmol).
- a colorless solid which was a composition including 37% by mass of Q 8 H 8 , was isolated in a yield of 84% (4.926 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.1 ppm) in the same manner as in Example 26, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 3.04 mL (48.0 mmol).
- a colorless solid which was a composition including 37% by mass of Q 8 H 8 , was isolated in a yield of 70% (4.168 g) ( 1 H-NMR (Acetone-d 6 ): 6.67 ppm, 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 35, except that the amount of sulfuric acid used was changed from 3.066 g (30.3 mmol) to 3.274 g (32.4 mmol).
- a colorless solid which was a composition including 39% by mass of Q 8 H 8 , was isolated in a yield of 91% (5.099 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 35, except that the amount of sulfuric acid used was changed from 3.066 g (30.3 mmol) to 3.492 g (34.5 mmol).
- a colorless solid which was a composition including 38% by mass of Q 8 H 8 , was isolated in a yield of 87% (5.104 g) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 35, except that the amount of sulfuric acid used was changed from 3.066 g (30.3 mmol) to 3.642 g (36.0 mmol).
- the 1 H-NMR measurement results of this solid are shown in FIG. 9( a ) ( 1 H-NMR (DMF-d 7 ): 7.73 ppm). Further, the 29 Si-NMR measurement results of this solid are shown in FIG. 9( b ) ( 29 Si-NMR (DMF-d 7 ): ⁇ 100.1 ppm). In addition, the measurement results of thermogravimetric differential thermal analysis of this solid are shown in FIG. 10 .
- a paste-like solid which was a composition including 31% by mass of Q 8 H 8 , was isolated in a yield of 87% (615 mg) ( 29 Si-NMR (Acetone-d 6 ): ⁇ 100.2 ppm) in the same manner as in Example 43, except that the 3 mL of diethylene glycol dimethyl ether was changed to 2 mL of triethylene glycol dimethyl ether.
- the 1 H-NMR measurement results of this solid are shown in FIG. 11( a ) ( 1 H-NMR (DMF-d 7 ): 7.73 ppm). Further, the 29 Si-NMR measurement results of this solid are shown in FIG. 11( b ) ( 29 Si-NMR (DMF-d 7 ): ⁇ 99.8 ppm). In addition, the measurement results of thermogravimetric differential thermal analysis of this solid are shown in FIG. 12 .
- nitric acid 0.0117 mL (0.18 mmol) of nitric acid was added to a dispersion of 48.5 mg (0.02 mmol) of hexakis(tetraethylammonium)tetracyclo[5.5.1.1 3,11 .1 5,9 ]hexa siloxane-1,3,5,7,9,11-hexakis(yloxide)hydrate (CAS No. 73697-41-3: hereinafter sometimes abbreviated as “Q 6 (TEA) 6 .nH 2 O”) suspended in 0.8 mL of DMAc. The mixture was stirred for 10 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 2 mL of DMAc).
- the 29 Si-NMR measurement results of this filtrate are shown in FIG. 14 ( 29 Si-NMR (Acetone-d 6 ): ⁇ 90.9 ppm). Further, the measurement results of high-resolution mass spectrometry (TOF-MS) are shown in FIG. 15 (theoretical value: H 6 NO 18 Si 6 [M+NO 3 ] ⁇ 475.8206, actual value: 475.8207). It was confirmed by various NMR and mass spectrometry that a proton-exchanged basket-shaped hexaol (composition formula Si 6 O 15 H 6 (hereinafter sometimes abbreviated as “Q 6 H 6 ”)) was formed in the solution.
- Q 6 H 6 composition formula Si 6 O 15 H 6
- a colorless liquid which was a composition including 0.6% by mass of Q 6 H 6 , was obtained in a yield of 81% ( 29 Si-NMR (Acetone-d 6 ): ⁇ 91.0 ppm) in the same manner as in Example 52, except that the amount of THF used was changed from 12 mL to 8 mL.
- a colorless liquid which was a composition including 0.5% by mass of Q 6 H 6 , was obtained in a yield of 88% ( 29 Si-NMR (Acetone-d 6 ): ⁇ 91.0 ppm) in the same manner as in Example 52, except that the amount of THF used was changed from 12 mL to 4 mL.
- silanol compounds represented by following formula (F) can be obtained.
- n an integer of 1 to 3.
- the silanol compound produced by the production method of the present invention is useful as a raw material and the like of a siloxane compound to be used in a wide range of fields, such as automobiles, construction, electronics, and medicine.
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Abstract
Description
- The present invention relates to a silanol compound and a method for producing a silanol compound, and more specifically, to a method for producing a silanol compound, wherein the silanol compound is formed from a silicate.
- Siloxane is a very important compound that, because of its specific nature, is used in a wide range of fields, such as automobiles, construction, electronics, and medicine. In recent years, siloxane is essential even in the field of environment and energy, such as in sealing materials for LEDs and silane coupling agents for eco-friendly tires. It is no exaggeration to say that there are no fields that do not use siloxane compounds. The market size of siloxane compounds in 2009 was 11.5 billion dollars, with an annual production of 1.23 million tons.
- In general, most siloxanes are synthesized via silanol by hydrolysis, such as in a sol-gel method using an alkoxysilane, a halogenated silane or the like as a raw material. This silanol, which includes silanediol, silanetriol and silanetetraol, except for some silanediols and silanetriols having bulky substituents such as phenyl groups, condenses simultaneously with the hydrolysis in the presence of water, and hence it is difficult to synthesize with a good yield. It is also known that silanol is unstable in the presence of water and condenses rapidly (see
Non Patent Literature 1 and Non Patent Literature 2). -
- Non Patent Literature 1: Fyfe, C. A.; Aroca, P. P. J. Phys. Chem. B 1997, 101, 9504.
- Non Patent Literature 2: Kim, Y.; Jung, E. Chem. Lett. 2002, 992.
- An object of the present invention is to provide a method for producing a silanol compound capable of efficiently producing a silanol compound.
- As a result of intensive studies to solve the above problem, the present inventors discovered that a silanol compound can be efficiently produced by proton exchange of a silicate with an acid compound having an acid dissociation constant pKa in a specific range, thereby completing the present invention.
- The method for producing a silanol compound of the present invention comprises a proton exchange step of forming a silanol compound having a structure represented by following formula (c) by reacting a silicate having a structure represented by following formula (a) with an acidic compound having an acid dissociation constant pKa of −1 to 20 in dimethyl sulfoxide (DMSO).
- In formula (a), Qi+ represents an i-valent cation and i represents an integer of 1 to 4.
- The silanol compound of the present invention is represented by following formula (D).
- The solid composition of the present invention comprises a silanol compound represented by the above formula (D). The composition of the present invention comprises 30% by mass or more of a silanol compound represented by the above formula (D). Another composition of the present invention comprises a crystal structure formed with a silanol compound represented by the above formula (D) and an amide compound. The dehydrated condensation product of the present invention is obtained by dehydration condensation of a silanol compound represented by the above formula (D).
- According to the production method of the present invention, a silanol compound can be produced efficiently. Further, the silanol compound of the present invention, a solid composition and a composition including the silanol compound, and a dehydrated condensation product of the silanol compound are useful as a raw material and the like of a siloxane compound to be used in a wide range of fields.
-
FIG. 1 shows the 29Si-NMR measurement results of a solution obtained in Example 1. -
FIG. 2(a) shows the 29Si-NMR measurement results of a solution obtained in Example 5, andFIG. 2(b) shows the high-resolution mass spectrometry (TOF-MS) measurement results of the solution obtained in Example 5. -
FIG. 3 shows a schematic view illustrating a proton exchange step of forming a silanol compound by passing a silicate having a structure represented by formula (a) through a column packed with a resin having a Meldrum's acid structure. -
FIG. 4 shows the measurement results of thermogravimetric differential thermal analysis of a solid obtained in Example 16. -
FIG. 5 shows the 29Si-NMR measurement results of a solution obtained in Example 31. -
FIG. 6 shows the measurement results of thermogravimetric differential thermal analysis of a solid obtained in Example 31. -
FIG. 7(a) shows the 1H-NMR measurement results of a solution of a solid obtained in Example 41, andFIG. 7(b) shows the 29Si-NMR measurement results of a solution of the solid obtained in Example 41. -
FIG. 8 shows the measurement results of thermogravimetric differential thermal analysis of a solid obtained in Example 41. -
FIG. 9(a) shows the 1H-NMR measurement results of a solution of a solid obtained in Example 42, andFIG. 9(b) shows the 29Si-NMR measurement results of a solution of the solid obtained in Example 42. -
FIG. 10 shows the measurement results of thermogravimetric differential thermal analysis of a solid obtained in Example 42. -
FIG. 11(a) shows the 1H-NMR measurement results of a solution of a solid obtained in Example 47, andFIG. 11(b) shows the 29Si-NMR measurement results of a solution of the solid obtained in Example 47. -
FIG. 12 shows the measurement results of thermogravimetric differential thermal analysis of a solid obtained in Example 47. -
FIG. 13 shows the high-resolution mass spectrometry (TOF-MS) measurement results of a solid obtained in Example 48. -
FIG. 14 shows the 29Si-NMR measurement results of a solution obtained in Example 49. -
FIG. 15 shows the high-resolution mass spectrometry (TOF-MS) measurement results of the solution obtained in Example 49. -
FIG. 16(a) shows the 1H-NMR measurement results of a solution of the liquid obtained in Example 50, andFIG. 16(b) shows the 29Si-NMR measurement results of the solution of the liquid obtained in Example 50. - The present invention is now described in detail by way of specific examples, but the present invention is not limited to the following subject matter and may be appropriately modified and implemented within the gist thereof. It is noted that when a numerical range between two values is represented using the word “to”, these two numerical values are also included in the range.
- <Method for Producing Silanol Compound>
- The method for producing a silanol compound as one embodiment of the present invention (hereinafter sometimes abbreviated as “production method of the present invention”) comprises a proton exchange step of forming a silanol compound having a structure represented by following formula (c) (hereinafter sometimes abbreviated as “proton exchange step”) by reacting a silicate having a structure represented by following formula (a) (hereinafter sometimes abbreviated as “silicate”) with an acidic compound having an acid dissociation constant pKa of −1 to 20 (hereinafter sometimes abbreviated as “acidic compound”) in dimethyl sulfoxide (DMSO) (hereinafter sometimes abbreviated as “pKa (DMSO)”).
- In formula (a), Qi+ represents an i-valent cation and i represents an integer of 1 to 4.
- To synthesize a silanol compound, even if an alkoxysilane, a halogenated silane, or the like is simply reacted with water, the formed silanol condenses to form a siloxane (see the following formula), and hence it is difficult to synthesize the silanol itself with a good yield.
- The present inventors discovered that a silanol compound can be efficiently produced by proton exchange of a silicate having a structure represented by formula (a) with an acidic compound having a pKa (DMSO) of −1 to 20. When the pKa (DMSO) is −1 to 20, the exchange of the silicate cations (Qi+) and the acidic compound protons (H+) progresses efficiently, and a side reaction and the condensation of the formed silanol compound can be suppressed. For this reason, the silanol compound itself can be synthesized with a good yield. In addition, the production method of the present invention is a production method that is industrially very suitable because the reaction proceeds rapidly under mild conditions. The smaller the pKa (DMSO) is, the faster the proton exchange step proceeds.
- The wavy lines in formula (a) and formula (c) mean that the tip has an arbitrary structure. Therefore, the “silanol compound” may be any compound in which at least one hydroxyl group (—OH) is bonded to a silicon atom (Si), and the number of hydroxyl groups and other structures are not particularly limited. The silanol compound may also include a functional group or the like not involved in the reaction. Further, the pKa (DMSO) means a known value calculated from the concentration of each component in acid dissociation equilibrium at 25° C. of the acidic compound in DMSO. Specifically, the pKa (DMSO) is a numerical value obtained by common logarithmizing the value Ka calculated by the following expression.
-
- Hereinafter, the silicate having a structure represented by formula (a) and the acidic compound having a pKa (DMSO) of −1 to 20 in the proton exchange step, as well as the other reaction conditions and the like will be described in detail.
- (Proton Exchange Step)
- The specific kind of a silicate, the specific kind of an acidic compound, the amount of the acidic compound used, the kind of a reaction medium, which is a solvent or a dispersion medium, the reaction conditions, and the like used in the proton exchange step shown in the following chemical reaction formula are not particularly limited, and can be selected appropriately according to the purpose.
- In formula (a), Qi+ represents an i-valent cation and i represents an integer of 1 to 4.
- It is particularly preferred that i be 1. Examples of Qi+ include alkali metal ions such as a lithium ion (Li+), a sodium ion (Na+), and a potassium ion (K+), alkaline earth metal ions such as a magnesium ion (Mg2+) and a calcium ion (Ca2+), transition metal ions such as an iron(III) ion (Fe3+), a copper(II) ion (Cu2+), and a zinc ion (Zn2+), ammonium ions such as an ammonium ion (NH4 +), a tetramethylammonium ion (NMe4 +), an ethyltrimethylammonium ion (NEtMe3 +), a diethyldimethylammonium ion (NEt2Me2 +), a triethylmethylammonium ion (NEt3Me+), a tetraethylammonium ion (NEt4 +), a tetrapropylammonium ion (NPr4 +), and a tetrabutylammonium ion (NBu4 +). Among these, a sodium ion (Nat), a potassium ion (K+), a tetramethylammonium ion (NMe4 +), a tetraethylammonium ion (NEt4 +), and an ethyltrimethylammonium ion (NEtMe3 +) are particularly preferable.
- Examples of the silicate include silicates represented by following formulas (A-1) to (A-33).
- In formulas (A-1) to (A-33), Q+ represents a monovalent cation, each R independently represents a hydrocarbon group having 1 to 20 carbon atoms which may include at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom, and n represents an integer of 1 to 4.
- Here, “may include at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a halogen atom” not only means a functional group including a nitrogen atom, an oxygen atom, a halogen atom, or the like may be included, this expression also means that a linking group including a nitrogen atom, an oxygen atom, and the like may be included inside or at the end of the carbon skeleton. The “hydrocarbon group” may have a branched structure, a cyclic structure, and a carbon-carbon unsaturated bond (carbon-carbon double bond or carbon-carbon triple bond), respectively, and may be any of a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, and the like.
- Examples of the functional group or the linking group included in the hydrocarbon group of R include an amido group (—NHCO—), an ether group (oxa group, —O—), a fluorine atom (fluoro group, —F), a chlorine atom (chloro group, —Cl), a bromine atom (bromo group, —Br), and an iodine atom (iodo group, —I). The hydrocarbon group of R preferably has 1 or more carbon atoms, preferably 14 or fewer carbon atoms, more preferably 10 or fewer carbon atoms, and still more preferably 6 or fewer carbon atoms. When R is an aromatic hydrocarbon group, the number of carbon atoms is usually 6 or more. A silanol compound can be efficiently produced when the number of carbon atoms is in the above range.
- Examples of R include a methyl group (-Me), an ethyl group (-Et), a n-propyl group (-nPr), an i-propyl group (-iPr), a n-butyl group (-nBu), a sec-butyl group (-sBu), a t-butyl group (-tBu), a phenyl group (-Ph), an aryl group (-Ar), a vinyl group (-Vi), and an allyl group (—CH2CH═CH2).
- The acidic compound is a compound having a pKa (DMSO) of −1 to 20, and preferably, the pKa (DMSO) is 0 or more, more preferably 1 or more, and still more preferably 3 or more, and is preferably 16 or less, more preferably 14 or less, and still more preferably 8 or less. A silanol compound can be efficiently produced when the pKa (DMSO) is in the above range. The specific structure and the like of the acidic compound are not particularly limited as long as the pKa (DMSO) is −1 to 20.
- Examples of the acidic compound include inorganic acids such as nitric acid (pKa (DMSO) of 1.4), sulfuric acid (pKa1 (DMSO) of 1.4 and pKa2 (DMSO) of 14.7), hydrochloric acid (pKa (DMSO) of 2.1), phosphoric acid (pKa1 (DMSO) of 1.83, pKa2 (DMSO) of 6.43, pKa3 (DMSO) of 11.46), or at least one organic acid selected from the group consisting of acetic acid or compounds having a structure represented by any of the following formulas (b-1) to (b-5).
- When a proton exchange reaction using an organic acid is performed in N,N-dimethylacetamide (DMAc), methanol (MeOH) or the like as a reaction medium, the formed ammonium salt is dissolved in the reaction medium. For this reason, it is necessary to separate the ammonium salt, which is a by-product, by column purification or the like. On the other hand, when a proton exchange reaction using an inorganic acid is performed in tetrahydrofuran (THF) or the like as a reaction medium, the formed ammonium salt is not dissolved in the reaction medium. Therefore, the ammonium salt can be separated by simple separation means such as filtration using a filter, and a silanol compound solution as the filtrate can be obtained. Accordingly, the acidic compound is preferably an inorganic acid.
- Among inorganic acids, nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid are preferable, and nitric acid or sulfuric acid is particularly preferable. The reason for this is because nitrate ions, hydrogen sulfate ions, and sulfate ions have weak interactions (hydrogen bonds etc.) with the silanol compound, and the ammonium salt produced as a by-product does not easily form a complex insoluble in the reaction medium with the silanol compound. On the other hand, chloride ions, dihydrogen phosphate ions, hydrogen phosphate ions, and phosphate ions have strong interactions (hydrogen bonds etc.) with the silanol compound, and as a result, in proton exchange using hydrochloric acid or phosphoric acid, the silanol compound and the ammonium salt sometimes form a complex that is insoluble in the reaction medium, which may cause the yield of the desired silanol compound to be slightly reduced.
- In formulas (b-1) to (b-5), each X independently represents an oxygen atom, a sulfur atom, or an amino group (—NR3—), R1 represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms, and each R2 independently represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms.
- The wavy lines in formulas (b-2) to (b-5) mean that the tip has an arbitrary structure. For example, the acidic compound may include a functional group or the like not involved in the reaction. Therefore, for example, the acidic compound having the structure represented by formula (b-4) may be a compound including a hydrocarbon group such as a methyl group attached to the oxygen atom corresponding to X, like the dimethyl malonate having the following formula. Further, for example, the acidic compound having the structure represented by formula (b-4) may be a compound in which the hydrocarbon groups attached to the oxygen atoms corresponding to X are bonded to form a cyclic structure, like the Meldrum's acid having the following formula.
- The structures represented by formulas (b-1) to (b-5) are so-called β-dicarbonyl structures, but the hydrogen of a methylene group sandwiched between the two carbonyl groups, i.e., the α-hydrogen, is known to act as an acid site. By having a structure represented by formulas (b-1) to (b-5), the acid compound exhibits an appropriate acid dissociation constant, and the electrons of the anion formed by the dissociation of protons are delocalized in the structure. For example, for the acidic compound having a structure represented by formula (b-2), the protons dissociate in the manner represented by the following formula. For this reason, it is considered that the acidic compounds having a structure represented by any of formulas (b-1) to (b-5) can suppress the basicity and nucleophilicity of the anion, and a side reaction and condensation of the silanol compound can be effectively suppressed.
- Examples of the amino group (—NR3—) as X include secondary amino groups (—NH—). It is particularly preferred that X be an oxygen atom. When R1 is a hydrocarbon group, the number of carbon atoms is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. Examples of R1 include a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), a n-propyl group (-nPr), an i-propyl group (-iPr), a n-butyl group (-nBu), and a phenyl group (-Ph), and a hydrogen atom is preferable.
- When R2 is a hydrocarbon group, the number of carbon atoms is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. Examples of R2 include a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), a n-propyl group (-nPr), an i-propyl group (-iPr), and a n-butyl group (-nBu), and a hydrogen atom is preferable.
- Examples of the acidic compound represented by formula (b-4) include acidic compounds represented by following formula (b-4-1). Examples of the acidic compound represented by formula (b-5) include acidic compounds represented by following formula (b-5-1).
- In formulas (b-4-1) and (b-5-1), R1 represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms, and R4 represents a divalent hydrocarbon group having 1 to 14 carbon atoms.
- Examples of R4 include a methylene group (—CH2—), an ethylene group (—CH2CH2—), a n-propylene group (—CH2CH2CH2—), a dimethylmethylene group (—C(CH3)2—), and an i-propylene group (—CH(CH3)CH2—).
- Examples of the acidic compound include acetic acid (pKa (DMSO) of 12.6), benzoic acid (pKa (DMSO) of 11.1), Meldrum's acid (pKa (DMSO) of 7.3), a Meldrum's acid derivative, dimedone (pKa (DMSO) of 11.2), a dimedone derivative, acetylacetone (pKa (DMSO) of 13.3), and an acetylacetone derivative (see the following formulas)
- As the acidic compound, there may be used a solid obtained by introducing a compound represented by any of formulas (b-2) to (b-5) into a low molecular weight compound, such as Meldrum's acid, or an organic solid material, such as a resin, or an inorganic solid material, such as silica or carbon. If the acidic compound is such a solid, the acidic compound can be packed in a column as shown in
FIG. 3 and used as an ion exchange resin. This enables the silanol compound to be produced very efficiently. - In particular, the acidic compound is preferably a resin having at least one structure selected from the group consisting of formulas (b-2) to (b-5). It is preferred that the acid compound be capable of being regenerated by exposing to an aqueous acidic solution, such as hydrochloric acid, after the proton exchange step.
- The amount of the acidic compound used in the proton exchange step is, in terms of the amount of substance with respect to the silicate, usually 1 times or more, preferably 1.05 times or more, and more preferably 1.1 times or more, and usually 50 times or less, preferably 20 times or less, and more preferably 5 times or less. When the amount used is in the above range, a silanol compound can be efficiently produced.
- It is preferable to perform the reaction in the proton exchange step in a liquid. Examples of the liquid include ether liquids such as THF, tetrahydropyran, dioxane, diethyl ether (Et2O), dimethyl ether, diisopropyl ether, diphenyl ether, methyl ethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, alcohol liquids such as methanol, ethanol, n-propanol, and i-propanol, amide liquids such as formamide, N,N-dimethylformamide (DMF), acetamide, N-methylacetamide, DMAc, urea, and tetramethylurea, ester liquids such as ethyl acetate, n-amyl acetate, and ethyl lactate, halogen liquids such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, and hexachloroethane, acetone, methyl ethyl ketone, phenyl methyl ketone, DMSO, and water. The liquid is not limited to one kind, and two or more kinds may be combined.
- The amount of liquid used in the proton exchange step is preferably such that the content of the silicate is 0.005 to 0.04 mol/L. This is because a silanol compound can be produced efficiently with such a silicate content. The reaction temperature in the proton exchange step is usually −80° C. or more, preferably 0° C. or more, and more preferably 20° C. or more, and is usually 200° C. or less, preferably 70° C. or less, and more preferably 40° C. or less. The reaction time in the proton exchange step is usually 48 hours or less, preferably 24 hours or less, more preferably 8 hours or less, and particularly preferably 1 hour or less. A silanol compound can be efficiently produced when these factors are in the respective ranges above.
- The production method of the present invention may include steps other than the proton exchange step. Examples of specific steps other than the proton exchange step include an ammonium salt addition step of adding an ammonium salt to the product obtained in the proton exchange step (hereinafter sometimes abbreviated as “ammonium salt addition step”), a freeze-drying step of freezing the product obtained in the proton exchange step or the product obtained in the ammonium salt addition step and exposing the product to reduced pressure (hereinafter sometimes abbreviated as “freeze-drying step”), and a crystallization step of precipitating crystals from the product obtained in the proton exchange step or the product obtained in the ammonium salt addition step by a poor solvent method or an evaporation method (hereinafter sometimes abbreviated as “crystallization step”). The “ammonium salt addition step”, the “freeze-drying step”, the “crystallization step” and the like are now described below in detail.
- (Ammonium Salt Addition Step)
- The kind and amount of the ammonium salt used, and the like are not particularly limited, and can be appropriately selected according to the purpose. In addition, “ammonium salt” means a compound formed with an ammonium ion and a counter anion, and the structures of the ammonium ion and the counter anion are not particularly limited. It is considered that the addition of the ammonium salt suppresses condensation of the silanol compound. Examples of the ammonium ion include a tetrahydroammonium ion (NH4 +), a tetramethylammonium ion (NMe4 +), a tetrapropylammonium ion (NPr4 +), a tetrabutylammonium ion (NBu4 +), a benzyltributylammonium ion (NBnBu3 +), a tributyl(methyl)ammonium (NBu3Me+) ion, a tetrapentylammonium ion (NPen4 +), a tetrahexylammonium ion (NHex4 +), a tetraheptylammonium ion (NHep4 +), an 1-butyl-1 methylpyrrolidinium ion (BuMePyr+), a methyltrioctylammonium ion (NMeOct3 +), a dimethyldioctadecylammonium ion, and a Meldrum's acid-tetramethylammonium salt.
- Examples of the counter anion include a fluoride ion (F−), a chloride ion (Cl−), a bromide ion (Br−), an iodide ion (I−), an acetoxy ion (AcO−), a nitrate ion (NO3 −), an azide ion (N3 −), a tetrafluoroborate ion (BF4 −), a perchlorate ion (ClO4 −), and a hydrogen sulfate ion (HSO4 −).
- The ammonium salt is particularly preferably tetrabutylammonium chloride (NBu4Cl), tetrabutylammonium bromide (NBu4Br), tetrapentylammonium chloride (NPen4Cl), a Meldrum's acid-tetramethylammonium salt, or dimethyldioctadecylammonium chloride. The ammonium salt included in the composition is not limited to one kind, and may include two or more kinds. The amount of the ammonium salt used is preferably 1 to 4 times in terms of the amount of substance with respect to the silanol compound.
- (Freeze-Drying Step)
- The freezing temperature, the drying temperature, the drying pressure, the drying time, and the like in the freeze-drying step are not particularly limited, and can be appropriately selected according to the purpose. The freezing temperature is not particularly limited as long as the product obtained in the proton exchange step or the product obtained in the ammonium salt addition step freezes, but it is usually 10° C. or less, preferably 0° C. or less, and more preferably −20° C. or less, and is usually −196° C. or more, preferably −150° C. or more, and more preferably −100° C. or more.
- The drying temperature is usually 10° C. or less, preferably 0° C. or less, and more preferably −20° C. or less, and is usually −196° C. or more, preferably −150° C. or more, and more preferably −100° C. or more. The drying pressure is usually 100 Pa or less, preferably 20 Pa or less, and more preferably 3 Pa or less, and is usually 10−5 Pa or more, preferably 0.01 Pa or more, more preferably 1 Pa or more. The drying time is usually 200 hours or less, preferably 100 hours or less, and more preferably 50 hours or less, and is usually 1 hour or more, preferably 5 hours or more, and more preferably 10 hours or more.
- (Crystallization Step)
- The solvent used in the crystallization step, the crystallization time (standing time), and the like are not particularly limited, and can be appropriately selected according to the purpose. The boiling point of the solvent to be used is usually 0° C. or more, preferably 10° C. or more, and more preferably 30° C. or more, and is usually 300° C. or less, preferably 200° C. or less, and more preferably 100° C. or less. Examples of the solvent to be used include Et2O, THF, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, DMAc, N,N-dimethylformamide, N-methylacetamide, DMSO, and tetramethylurea. The crystallization time (standing time) is usually 720 hours or less, preferably 360 hours or less, and more preferably 168 hours or less, and is usually 1 hour or more, preferably 5 hours or more, and more preferably 10 hours or more.
- <Silanol Compound/Solid Composition/Composition/Dehydrated Condensation Product of Silanol Compound>
- A silanol compound represented by following formula (D) (hereinafter sometimes abbreviated as “the silanol compound of the present invention”), a solid composition including a silanol compound represented by following formula (D) (hereinafter sometimes abbreviated as “the solid composition of the present invention”), a composition including a silanol compound represented by following formula (D) (hereinafter sometimes abbreviated as “the composition of the present invention”) and a dehydrated condensation product of a silanol compound represented by following formula (D) (hereinafter sometimes abbreviated as “the dehydrated condensation product of the present invention”), which can be produced by the production method of the present invention and are useful as a raw material and the like of a siloxane compound, are also embodiments of the present invention.
- The kind and the like of a compound other than a silanol compound represented by formula (D) that is included in the solid composition or the composition of the present invention are not particularly limited, and can be appropriately selected according to the purpose. It is also noted that since the silanol compound represented by formula (D) is obtained in a high concentration by the production method of the present invention, the content of the silanol compound represented by formula (D) in the solid composition or the composition of the present invention can be adjusted appropriately. For example, the content of the silanol compound represented by formula (D) in the solid composition or the composition can be 95% by mass or more by evaporating the solvent at about 100° C., at which dehydration condensation does not easily proceed. In addition, even if the solid composition of the present invention is heated at about 100° C., it is known from the results of Raman analysis that the basket-shaped skeletal structure of the silanol compound represented by formula (D) is maintained.
- Examples of the compound other than the silanol compound represented by formula (D) include water, an ether compound, an amine compound, an amide compound, and an ammonium salt. The amine compound, the amide compound, and the ammonium salt have an effect of suppressing the condensation of the silanol compound. Moreover, in compositions obtained by a production method utilizing hydrolysis of a halogenated silane, an alkoxysilane, or the like, water tends to be included in those compositions as a result of mixing from the atmosphere or generation by dehydration condensation of the silanol compound. The water content in the composition of the present invention is preferably as small as possible, for the reason that water promotes condensation of the silanol compound and causes a decrease in the stability of the solid composition or the composition of the present invention.
- The specific kind of the amine compound is not particularly limited, as long as the amine compound has an amino group (which may be any of a primary amine, a secondary amine, or a tertiary amine). In addition, compounds having both an amino group and an amide group are classified herein as being an “amide compound”. Examples of the amine compound include aniline (NH2Ph), diphenylamine (NHPh2), dimethylpyridine (Me2Pyr), di-tert-butylpyridine (tBu2Pyr), pyrazine (Pyraz), triphenylamine (NPh3), triethylamine (Et3N), and di-isopropylethylamine (iPr2EtN). Among amine compounds, aniline (NH2Ph) is particularly preferred. The amine compound included in the composition is not limited to one kind, and two or more kinds may be included.
- The content (the total content when including two or more kinds) of the amine compound in the solid composition or the composition of the present invention is preferably more than 0.1% by mass, more preferably 1% by mass or more, and even more preferably 10% by mass or more, and is usually less than 95% by mass, preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
- The specific kind of the amide compound is not particularly limited as long as the amine compound has an amide bond. Examples of the amide compound include compounds represented by following formula (i) or (ii).
- In formulas (i) and (ii), each R′ and R″ independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- Example of R′ and R″ include a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), a n-propyl group (-nPr), an i-propyl group (-iPr), and a phenyl group (-Ph). Examples of the compound represented by formula (i) include formamide, DMF, acetamide, N-methylacetamide, and DMAc. Examples of the compound represented by formula (ii) include urea, and tetramethylurea (Me4Urea). The content (the total content when including two or more kinds) of the amide compound in the solid composition or the composition of the present invention may be 0% by mass (not contained) or more and 90% by mass or less.
- The specific kind of the ammonium salt is not particularly limited, as long as the ammonium salt is a compound formed with an ammonium ion and a counter anion. Examples of the ammonium ion include a tetrahydroammonium ion (NH4 +), a tetramethyl ammonium ion (NMe4 +), a tetraethylammonium ion (NEt4 +), a tetrapropylammonium ion (NPr4 +), a tetrabutylammonium ion (NBu4 +), a benzyltributylammonium ion (NBnBu3 +), a tributyl(methyl)ammonium (NBu3Me+) ion, a tetrapentylammonium ion (NPen4 +), a tetrahexylammonium ion (NHex4 +), a tetraheptylammonium ion (NHep4 +), an 1-butyl-1 methylpyrrolidinium ion (BuMePyr+), a methyltrioctylammonium ion (NMeOct3 +), a dimethyldioctadecylammonium ion, a hydropyridinium ion (C5H5N+H), a hydroanilinium ion (PhNH2 +H), and a Meldrum's acid ion. Further, examples of the counter anion include a fluoride ion (F−), a chloride ion (Cl−), a bromide ion (Br−), an iodide ion (I−), an acetoxy ion (AcO−), a nitrate ion (NO3 −), an azide ion (N3 −), a tetrafluoroborate ion (BF4 −), a perchlorate ion (ClO4 −), and a hydrogen sulfate ion (HSO4 −).
- The ammonium salt is particularly preferably tetrabutylammonium chloride (NBu4Cl), tetrabutylammonium bromide (NBu4Br), tetrapentylammonium chloride (NPen4Cl), dimethyldioctadecyl ammonium chloride, or a Meldrum's acid-tetramethylammonium salt. The ammonium salt included in the composition is not limited to one kind, and may include two or more kinds.
- The content (the total content when including two or more kinds) of the ammonium salt in the solid composition or the composition of the present invention is preferably more than 0.1% by mass, and more preferably 50% by mass or more, and is usually less than 95% by mass, and preferably 80% by mass or less. Further, the ratio of the ammonium salt to the silanol compound in the solid composition or the composition of the present invention (the total amount of substance of ammonium salt/the total amount of substance of silanol compound) is preferably greater than 0, and more preferably 1 or more, and is usually 8 or less, preferably 6 or less, and more preferably 4 or less.
- The dehydrated condensation product of the present invention is a compound formed by dehydration condensation of the hydroxyl group of the silanol compound represented by formula (D), like a dimer or trimer represented by the following formula. The dehydrated condensation product of the present invention is usually a product in which two or more silanol compounds represented by formula (D) are condensed, and is usually a product in which 20 or less, preferably 10 or less, and more preferably 5 or less silanol compounds are condensed. In the above range, the dehydrated condensation product becomes easier to utilize as a raw material and the like of a siloxane compound.
- The present invention will now be more specifically described with respect to the following examples but it can be modified appropriately without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the specific examples shown below.
- As shown in the following chemical reaction formula, 56.2 mg (0.50 mmol) of sodium trimethylsilanolate (Me3SiONa) and 72.1 mg (0.50 mmol) of Meldrum's acid were placed in a flask, 2 mL of heavy tetrahydrofuran (THF-d8) was charged thereto, and the mixture was stirred for 3 minutes. The 29Si-NMR (condition: inverse gate decoupling method) of this reaction solution was measured. The results are shown in
FIG. 1 . It was confirmed by various NMR and mass spectrometry that trimethylsilanol was formed (yield: 99% or more). - 24 mg (0.24 mmol) of acetylacetone was placed in a flask, and 0.8 mL of heavy toluene (Tol-d8) was charged thereto. Then, 22 mg (0.20 mmol) of sodium trimethylsilanolate (Me3SiONa) was added, and the mixture was stirred for 30 minutes. Bistrimethylsilylbenzene was added as an internal standard, and it was confirmed by various NMR and mass spectrometry that trimethylsilanol was formed (yield: 76%).
- A resin represented by chemical formula (E), which was self-made with reference to a previously reported synthesis method (Xian Huang, Zhanxiang Liu, J. Org. Chem. 2002, 67, 6731), was synthesized, and 435 mg of the synthesized resin was packed in a column. A solution of 34 mg (0.30 mmol) of sodium trimethylsilanolate (Me3SiONa) in 1 mL of THF solution was poured in the resin represented by the chemical formula (E) swollen with THF. The solution which flowed out was distilled off and trimethylsilanol was isolated by various NMR and mass spectrometry (yield: 99% or more).
- 915 mg (equivalent to 5.00 mmol in carboxylic acid units) of acrylic-type DIAION WK4OL manufactured by Mitsubishi Chemical and 112 mg (1.00 mmol) of sodium trimethylsilanolate (Me3SiONa) were placed in a flask, and 3 mL of toluene was charged thereto. The mixture was stirred for 30 minutes, after which it was confirmed by various NMR and mass spectrometry of the reaction solution that trimethylsilanol was formed. The yield was calculated by using bistrimethylsilylbenzene as an internal standard (yield: 99% or more).
- As shown in the following chemical reaction formula, 411 mg (2.85 mmol) of Meldrum's acid was added to a dispersion of 633 mg (0.30 mmol) of octakis(tetramethylammonium)pentacyclo[9.5.1.13,9.15,15.17,13.]octasiloxane-1,3,5,7,9,11,13,15-octakis(yloxide)hydrate (CAS No. 69667-29-4 (hereinafter sometimes abbreviated as “Q8(TMA)8.nH2O”) suspended in 8 mL of DMAc. The mixture stirred for 10 minutes, and a clear, colorless solution was obtained.
- The 29Si-NMR and the high-resolution mass spectrometry (TOF-MS) of this solution were measured. The results are shown in
FIG. 2(a) andFIG. 2(b) , respectively. It was confirmed by various NMR, mass spectrometry, and X-ray crystal structure analysis that a proton-exchanged basket-shaped octaol (composition formula Si8O20H8 (hereinafter sometimes abbreviated as “Q8H8”)) was formed in the solution. The reaction solution was concentrated and the peak portion corresponding to Q8H8 was collected by GPC. - After concentrating the solution including the Q8H8 and recrystallizing at 2° C. by a poor solvent method, Q8H8 was successfully isolated as a colorless solid (plate-like crystals) in a yield of 84% (375 mg). In other words, a composition including 37.5% by mass of Q8H8 was obtained. Further, it was revealed by concentrating the reaction solution and recrystallizing at 2° C. by a poor solvent method that the composition has a crystal structure formed with one molecule of Q8H8 and 10 molecules of DMAc (1H-NMR (Acetone-d6): 6.44 ppm, 29Si-NMR (Acetone-d6): −100.2 ppm). In this, a composition having a crystal structure formed with Q8H8 and an amide compound was obtained.
- A solution of 171 mg (0.15 mmol) of Q8(TMA)8.54H2O dissolved in 0.5 mL of MeOH was added dropwise over 1.5 hours to a solution of 72 mg (1.20 mmol) of acetic acid dissolved in 10 mL of DMAc. It was confirmed by various NMR and mass spectrometry that Q8H8 was formed.
- As shown in the following chemical reaction formula, a solution of 28 mg (0.15 mmol) of sodium orthosilicate dissolved in 2 mL of heavy water was added to a solution of 86 mg (0.60 mmol) of Meldrum's acid dissolved in 1 mL of DMAc. This solution was stirred at room temperature for 1.5 hours, and the 29Si-NMR was measured. It was confirmed by various NMR and mass spectrometry that silanetetraol was formed in a yield of 81%.
- As shown in the following chemical reaction formula, a solution of 43 mg (0.30 mmol) of Meldrum's acid dissolved in 0.3 mL of heavy acetone was added to a dispersion of 21 mg (0.10 mmol) of potassium-all-cis-tetramethylcyclotetrasiloxane tetrasilanolate, which was self-made with reference to a previously reported synthesis method (O. I Shchegolikina, Yu. A. Pozdnyakova, A. A. Chetverikov, A. S. Peregudov, M. I. Buzin, E. V. Matukhina, Rus. Chem. Bull., Int. Ed., 2007, 56, 83-90), suspended in 0.3 mL of dimethylacetamide, and the mixture was stirred at room temperature for 10 minutes. It was confirmed by various NMR and mass spectrometry that all-cis-tetramethylcyclotetrasiloxanetetraol was formed. The yield was calculated by using bistrimethylsilylbenzene as an internal standard (yield 87%).
- 121 mg (0.84 mmol) of Meldrum's acid was added to a dispersion of 211 mg (0.10 mmol) of Q8(TMA)8.54H2O suspended in 5 mL of DMAc. The mixture was stirred for 5 minutes, a clear, colorless solution including Q8H8 was obtained. The 29Si-NMR of this solution was measured. The yield of Q8H8 was calculated by using bistrimethylsilylbenzene as an internal standard (yield: 94%, 29Si-NMR (Acetone-d6): −100.6 ppm).
- 77 mg (0.84 mmol) of nitric acid was added to a dispersion of 211 mg (0.10 mmol) of Q8(TMA)8.54H2O suspended in 5 mL of DMAc. The mixture was stirred for 15 minutes, and a suspension including Q8H8 was obtained. This suspension was filtered using a filter, and then the 29Si-NMR was measured. The yield of Q8H8 was calculated by using bistrimethylsilylbenzene as an internal standard (yield: 95%, 29Si-NMR (Acetone-d6): −100.4 ppm).
- 70 μL (0.84 mmol) of hydrochloric acid was added to a dispersion of 211 mg (0.10 mmol) of Q8(TMA)8.54H2O suspended in 5 mL of DMAc. The mixture was stirred for 10 minutes, and a suspension including Q8H8 was obtained. This suspension was filtered using a filter, and then the 29Si-NMR was measured (yield: 89%, 29Si-NMR (Acetone-d6): −100.4 ppm).
- 135 mg (0.96 mmol) of dimedone was added to a dispersion of 211 mg (0.10 mmol) of Q8(TMA)8.54H2O suspended in 2 mL of DMAc. The mixture was stirred for 5 minutes, and a clear, colorless solution including Q8H8 was obtained. The 29Si-NMR of this solution was measured, and the yield of Q8H8 was calculated (yield: 32%, 29Si-NMR (Acetone-d6): −101.2 ppm).
- 363 mg (2.52 mmol) of Meldrum's acid was added to a dispersion of 640 mg (0.30 mmol) of Q8(TMA)8.55.4H2O (manufactured by Aldrich, product number 522260-5G) suspended in 8 mL of DMAc. The mixture was stirred for 10 minutes, and a clear, colorless solution including Q8H8 was obtained. The peak portion corresponding to Q8H8 was collected from the reaction solution by GPC. After concentrating the solution including the Q8H8 and recrystallizing at 2° C. by a poor solvent method, Q8H8 was isolated as a colorless solid (white powder), which was a composition including 36.3% by mass of Q8H8, in a yield of 85% (390 mg) (1H-NMR (THF-d8): 6.30 ppm, 29Si-NMR (THF-d8): −100.0 ppm).
- 605 mg (4.20 mmol) of Meldrum's acid was added to a dispersion of 1055 mg (0.50 mmol) of Q8(TMA)8.54H2O suspended in 20 mL of DMAc. The mixture was stirred for 7 minutes, and a clear, colorless solution was obtained. After adding 200 mL of a mixed solvent of ethanol/acetonitrile (1/1 volume ratio) to this solution, 20 g of anhydrous magnesium sulfate was added thereto, the mixture was stirred for 10 minutes, and then filtered using a filter to obtain a solution. A silica gel column (ethanol/acetonitrile (1/1 volume ratio) mixed solvent as a developing solvent) of this solution was used to collect the peak portion corresponding to Q8H8. After concentrating the solution including the collected Q8H8 and recrystallizing at 2° C. by a poor solvent method, a colorless solid, which was a composition including 47% by mass of Q8H8, was isolated in a yield of 61% (349 mg) (29Si-NMR (THF-d8): −100.0 ppm).
- 20 mg of the Q8H8 composition obtained in Example 5 was dissolved in 1 mL of THF, and trace amounts of insoluble were separated by filtration using a filter. After recrystallizing of this solution at −30° C., a colorless solid (square columnar crystals), which was a composition including 68.4% by mass of Q8H8, was isolated. Further, it was revealed by single crystal X-ray crystal structure analysis that the obtained crystals had a crystal structure formed with one molecule of Q8H8, one molecule of DMAc, and two molecules of THF.
- 141 mg (0.98 mmol) of Meldrum's acid was added to a dispersion of 212 mg (0.10 mmol) of Q8(TMA)8.54H2O suspended in 4 mL of DMAc. The mixture was stirred for 10 minutes, and a clear, colorless solution was obtained. 2 mL of THF was gradually added to this solution. The mixture was then left to stand at room temperature, whereby a colorless solid (plate-like crystals), which was a composition including 35.3% by mass of Q8H8, was isolated in a yield of 94% (147 mg). Further, it was revealed by single crystal X-ray crystal structure analysis that the obtained crystals had a crystal structure formed with one molecule of Q8H8, four molecules of a Meldrum's acid-tetramethyl ammonium salt, and two molecules of THF. The measurement results of thermogravimetric differential thermal analysis of this solid are shown in
FIG. 4 . The solid line (-) represents “TG %”, the broken line (--) represents “DTA μV”, and the dotted line (..) represents “Temp Cel” (the same applies hereinafter). - 277 mg (1.92 mmol) of Meldrum's acid was added to a dispersion of 423 mg (0.20 mmol) of Q8(TMA)8.54H2O suspended in 8 mL of DMAc. The mixture was stirring for 10 minutes, and a clear, colorless solution was obtained. 10 mL of THF and 4.0 g of silica gel (
Silica Gel 60, pH 6 (Kanto Chemical)) were added to this solution, and the mixture was stirred for 5 minutes. The silica gel was then separated by filtration using a filter (washed with 10 mL of THF), 2.0 g of silica gel (Silica Gel 60, pH 6 (Kanto Chemical)) was added to the filtrate, and the mixture was stirred for 5 minutes. The silica gel was separated by filtration using a filter (washed with 5 mL of THF). The filtrate was concentrated by distilling under reduced pressure, and recrystallized at −5° C. by a poor solvent method to isolate a colorless solid, which was a composition including 65% by mass of Q8H8, in a yield of 40% (68 mg) (1H-NMR (THF-d8): 6.29 ppm, 29Si-NMR (THF-d8): −100.0 ppm). - 0.141 mL (1.67 mmol) of hydrochloric acid was added to a dispersion of 423 mg (0.20 mmol) of Q8(TMA)8.54H2O suspended in 8 mL of DMAc and 2.5 mL of THF. The mixture was stirring for 10 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 1 mL of THF), 1.0 g of silica gel (
Silica Gel 60, pH 6 (Kanto Chemical)) and 5 mL of THF were then added to the filtrate, and the mixture was stirred for 5 minutes. The silica gel was then separated by filtration using a filter (washed with 7.5 mL of THF). The filtrate was concentrated by distilling under reduced pressure, and recrystallized at −5° C. by a poor solvent method to isolate a colorless solid, which was a composition including 47% by mass of Q8H8, in a yield of 86% (202 mg) (1H-NMR (Acetone-d6): 6.37 ppm, 29Si-NMR (Acetone-d6): −100.0 ppm). - 0.212 mL (3.35 mmol) of nitric acid was added to a dispersion of 845 mg (0.40 mmol) of Q8(TMA)8.54H2O suspended in 15 mL of THF and 8 mL of DMAc. The mixture was stirred for 10 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 2 mL of THF), 2.0 g of silica gel (
Silica Gel 60, pH 6 (Kanto Chemical)) was then added to the filtrate, and the mixture was stirred for 5 minutes. The silica gel was then separated by filtration using a filter (washed with 6 mL of THF). The filtrate was concentrated by distilling under reduced pressure, and recrystallized at −5° C. by a poor solvent method to isolate a colorless solid, which was a composition including 44% by mass of Q8H8, in a yield of 68% (341 mg) (29Si-NMR (Acetone-d6): −100.2 ppm). - A colorless solid, which was a composition including 37% by mass of Q8H8, was isolated in a yield of 72% (429 mg) (Q8H8) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 19, except that the amount of nitric acid used was changed from 0.212 mL (3.35 mmol) to 0.250 mL (3.95 mmol).
- 2.12 mL (33.5 mmol) of nitric acid was added to a dispersion of 8.062 g (4.00 mmol) of Q8(TMA)8.48.7H2O suspended in 150 mL of THF and 80 mL of DMAc. The mixture was stirred for 10 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 20 mL of THF), 20.0 g of silica gel (
Silica Gel 60, pH 6 (Kanto Chemical)) was then added to the filtrate and the mixture was stirred for 5 minutes. The silica gel was then separated by filtration using a filter (washed with 60 mL of THF). The filtrate was concentrated by distilling under reduced pressure, and recrystallized at −5° C. by a poor solvent method to isolate a colorless solid, which was a composition including 39% by mass of Q8H8, in a yield of 63% (3.56 g) (29Si-NMR (Acetone-d6): −100.2 ppm). - A colorless solid, which was a composition including 36% by mass of Q8H8, was isolated in a yield of 62% (3.851 g) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 21, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 2.53 mL (40.0 mmol).
- 0.212 mL (3.35 mmol) of nitric acid was added to a dispersion of 846 mg (0.40 mmol) of Q8(TMA)8.54H2O suspended in 20 mL of THF. The mixture was stirred for 5 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 5 mL of THF). After adding 8 mL of DMAc to the filtrate, the mixture was concentrated by distilling under reduced pressure, and recrystallized at −5° C. by a poor solvent method to isolate a colorless solid, which was a composition including 43% by mass of Q8H8, in a yield of 73% (376 mg) (29Si-NMR (Acetone-d6): −100.2 ppm).
- 2.12 mL (33.5 mmol) of nitric acid was added to a dispersion of 8.062 g (4.00 mmol) of Q8(TMA)8.48.7H2O suspended in 200 mL of THF. The mixture was stirred for 5 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 50 mL of THF). After adding 80 mL of DMAc to the filtrate, the mixture was concentrated by distilling under reduced pressure, and recrystallized at −5° C. by a poor solvent method to isolate a colorless solid, which was a composition including 37% by mass of Q8H8, in a yield of 33% (2.022 g) (29Si-NMR (Acetone-d6): −100.2 ppm).
- A colorless solid, which was a composition including 40% by mass of Q8H8, was isolated in a yield of 43% (2.427 g) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 24, except that the amount of THF used was changed from 200 mL to 150 mL.
- A colorless solid, which was a composition including 37% by mass of Q8H8, was isolated in a yield of 50% (2.988 g) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 24, except that the amount of THF used was changed from 200 mL to 100 mL.
- A colorless solid, which was a composition including 37% by mass of Q8H8, was isolated in a yield of 43% (2.552 g) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 24, except that the stirring time was changed from 5 minutes to 30 minutes.
- A colorless solid, which was a composition including 43% by mass of Q8H8, was isolated in a yield of 63% (3.237 g) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 25, except that the stirring time was changed from 5 minutes to 30 minutes.
- A colorless solid, which was a composition including 36% by mass of Q8H8, was isolated in a yield of 47% (2.872 g) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 27, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 2.53 mL (40.0 mmol).
- A colorless solid, which was a composition including 41% by mass of Q8H8, was isolated in a yield of 86% (4.717 g) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 27, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 3.04 mL (48.0 mmol).
- A colorless solid, which was a composition including 37% by mass of Q8H8, was isolated in a yield of 99% (5.889 g) in the same manner as in Example 27, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 3.55 mL (56.0 mmol). The 29Si-NMR measurement results of this solid are shown in
FIG. 5 (29Si-NMR (Acetone-d6): −100.2 ppm). Further, the measurement results of thermogravimetric differential thermal analysis of this solid are shown inFIG. 6 . - A colorless solid, which was a composition including 37% by mass of Q8H8, was isolated in a yield of 85% (5.135 g) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 28, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 3.04 mL (48.0 mmol).
- A colorless solid, which was a composition including 37% by mass of Q8H8, was isolated in a yield of 84% (4.926 g) (29Si-NMR (Acetone-d6): −100.1 ppm) in the same manner as in Example 26, except that the amount of nitric acid used was changed from 2.12 mL (33.5 mmol) to 3.04 mL (48.0 mmol).
- 333 mg (3.29 mmol) of sulfuric acid was added to a dispersion of 845 mg (0.40 mmol) of Q8(TMA)8.54H2O suspended in 20 mL of THF. The mixture was stirred for 5 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 5 mL of THF). After adding 8 mL of DMAc to the filtrate, the mixture was concentrated by distilling under reduced pressure, and recrystallized at −5° C. by a poor solvent method to isolate a colorless solid, which was a composition including 36% by mass of Q8H8, in a yield of 55% (333 mg) (1H-NMR (Acetone-d6): 7.32 ppm, 29Si-NMR (Acetone-d6): −100.2 ppm).
- 3.066 g (30.3 mmol) of sulfuric acid was added to a dispersion of 8.062 g (4.00 mmol) of Q8(TMA)8.48.7H2O suspended in 200 mL of THF. The mixture was stirred for 30 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 50 mL of THF). After adding 80 mL of DMAc to the filtrate, the mixture was concentrated by distilling under reduced pressure, and recrystallized at −5° C. by a poor solvent method to isolate a colorless solid, which was a composition including 32% by mass of Q8H8, in a yield of 47% (3.294 g) (1H-NMR (Acetone-d6): 6.67 ppm, 29Si-NMR (Acetone-d6): −100.2 ppm).
- A colorless solid, which was a composition including 37% by mass of Q8H8, was isolated in a yield of 70% (4.168 g) (1H-NMR (Acetone-d6): 6.67 ppm, 29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 35, except that the amount of sulfuric acid used was changed from 3.066 g (30.3 mmol) to 3.274 g (32.4 mmol).
- A colorless solid, which was a composition including 39% by mass of Q8H8, was isolated in a yield of 91% (5.099 g) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 35, except that the amount of sulfuric acid used was changed from 3.066 g (30.3 mmol) to 3.492 g (34.5 mmol).
- A colorless solid, which was a composition including 38% by mass of Q8H8, was isolated in a yield of 87% (5.104 g) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 35, except that the amount of sulfuric acid used was changed from 3.066 g (30.3 mmol) to 3.642 g (36.0 mmol).
- 369 mg (3.20 mmol) of phosphoric acid was added to a dispersion of 845 mg (0.40 mmol) of Q8(TMA)8.54H2O suspended in 20 mL of THF. The mixture was stirred for 5 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 5 mL of THF). After adding 8 mL of DMAc to the suspension, the mixture was concentrated by distilling under reduced pressure, and recrystallized at −5° C. by a poor solvent method to isolate a paste-like solid, which was a composition including 11% by mass of Q8H8, in a yield of 7% (143 mg) (29Si-NMR (Acetone-d6): −100.2 ppm).
- 0.212 mL (3.35 mmol) of nitric acid was added to a dispersion of 845 mg (0.40 mmol) of Q8(TMA)8.54H2O suspended in 20 mL of THF, and a suspension was obtained by stirring for 5 minutes. This suspension was filtered using a filter (washed with 5 mL of THF). The filtrate was distilled under reduced pressure to isolate a colorless solid, which was a composition including 69% by mass of Q8H8 and 24% by mass of H2O, in a yield of 64% (207 mg) (29Si-NMR (MeOD-d4): −100.1 ppm).
- 3.04 mL (48.0 mmol) of nitric acid was added to a dispersion of 8.062 g (4.00 mmol) of Q8(TMA)8.48.7H2O suspended in 200 mL of THF. The mixture was stirred for 30 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 50 mL of THF). The filtrate was distilled under reduced pressure to isolate a colorless solid, which was a composition including 80% by mass of Q8H8 and 1% by mass of H2O, in a yield of 95% (2.493 g). The 1H-NMR measurement results of this solid are shown in
FIG. 7(a) (1H-NMR (DMSO-d6): 7.87 ppm). Further, the 29Si-NMR measurement results of this solid are shown inFIG. 7(b) (29Si-NMR (DMSO-d6): −100.6 ppm). In addition, the measurement results of thermogravimetric differential thermal analysis of this solid are shown inFIG. 8 . - 0.212 mL (3.35 mmol) of nitric acid was added to a dispersion of 845 mg (0.40 mmol) of Q8(TMA)8.54H2O suspended in 20 mL of THF. The mixture was stirred for 5 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 5 mL of THF). The filtrate was distilled under reduced pressure and concentrated to about ⅓ of the original volume thereof. This concentrated solution was further concentrated under a condition of a reduced pressure of 23331 Pa (175 Torr) to isolate a colorless solid (plate-like crystals), which was a composition including 70% by mass of Q8H8 and 2% by mass of H2O. The 1H-NMR measurement results of this solid are shown in
FIG. 9(a) (1H-NMR (DMF-d7): 7.73 ppm). Further, the 29Si-NMR measurement results of this solid are shown inFIG. 9(b) (29Si-NMR (DMF-d7): −100.1 ppm). In addition, the measurement results of thermogravimetric differential thermal analysis of this solid are shown inFIG. 10 . - 0.212 mL (3.35 mmol) of nitric acid was added to a dispersion of 845 mg (0.40 mmol) of Q8(TMA)8.54H2O suspended in 20 mL of THF. The mixture was stirred for 5 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 5 mL of THF). The filtrate was charged with 3 mL of diethylene glycol dimethyl ether, then concentrated by distilling under reduced pressure to isolate a paste-like solid, which was a composition including 33% by mass of Q8H8, in a yield of 86% (573 mg) (29Si-NMR (Acetone-d6): −100.2 ppm).
- A paste-like solid, which was a composition including 31% by mass of Q8H8, was isolated in a yield of 87% (615 mg) (29Si-NMR (Acetone-d6): −100.2 ppm) in the same manner as in Example 43, except that the 3 mL of diethylene glycol dimethyl ether was changed to 2 mL of triethylene glycol dimethyl ether.
- 3.04 mL (48.0 mmol) of nitric acid was added to a dispersion of 8.062 g (4.00 mmol) of Q8(TMA)8.48.7H2O suspended in 150 mL of THF. The mixture was stirred for 30 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 50 mL of THF). The filtrate was charged with 30 mL of diethylene glycol dimethyl ether, then concentrated by distilling under reduced pressure to isolate a paste-like solid, which was a composition including 26% by mass of Q8H8, in a yield of 95% (8.103 g) (29Si-NMR (Acetone-d6): -100.2 ppm).
- 0.212 mL (3.35 mmol) of nitric acid was added to a dispersion of 845 mg (0.40 mmol) of Q8(TMA)8.54H2O suspended in 20 mL of THF. The mixture was stirred for 5 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 5 mL of THF). The filtrate was charged with 3 mL of diethylene glycol dimethyl ether, then concentrated by distilling under reduced pressure, and recrystallized at room temperature by a poor solvent method (vapor diffusion) to isolate a colorless solid (plate-like crystals), which was a composition including 78.9% by mass of Q8H8, in a yield of 65% (176 mg) (1H-NMR (DMF-d7): 7.73 ppm, 29Si-NMR (DMF-d7): −100.0 ppm). Further, it was revealed by single crystal X-ray crystal structure analysis that the obtained crystals had a crystal structure formed with one molecule of Q8H8 and two molecules of Et2O.
- 2.12 mL (33.5 mmol) of nitric acid was added to a dispersion of 8.062 g (4.00 mmol) of Q8(TMA)8.48.7H2O suspended in 200 mL of THF. The mixture was stirred for 30 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 50 mL of THF). The filtrate was charged with 30 mL of diethylene glycol dimethyl ether, then concentrated by distilling under reduced pressure, and recrystallized at room temperature by a poor solvent method (vapor diffusion) to isolate a colorless solid, which was a composition including 77% by mass of Q8H8, in a yield of 80% (2.309 g). The 1H-NMR measurement results of this solid are shown in
FIG. 11(a) (1H-NMR (DMF-d7): 7.73 ppm). Further, the 29Si-NMR measurement results of this solid are shown inFIG. 11(b) (29Si-NMR (DMF-d7): −99.8 ppm). In addition, the measurement results of thermogravimetric differential thermal analysis of this solid are shown inFIG. 12 . - A solution of 605 mg (4.20 mmol) of Meldrum's acid dissolved in 100 mL of acetonitrile was added to a solution of 1055 mg (0.50 mmol) of Q8(TMA)8.54H2O dissolved in 100 mL of ethanol. The mixture was stirred for 5 minutes, and a clear, colorless solution was obtained. 10 g of anhydrous magnesium sulfate was added to this solution, and the mixture was stirred for 10 minutes, and then filtered using a filter to obtain a solution. A silica gel column (ethanol/acetonitrile (1/1 volume ratio) mixed solvent as a developing solvent) of this solution was used to collect the peak portion including the dimerized component of Q8H8.
- The collected solution was charged with 10 mL of DMAc, then concentrated and recrystallized at 2° C. by a poor solvent method to obtain a colorless solid of Q8H8 and a dimer of a dehydrated condensation product of Q8H8 in a yield of 46% (127 mg) (29Si-NMR (Acetone-d6): −100.3 ppm, −109.7 ppm). Further, a part of the obtained colorless solid was dissolved in acetonitrile, and high-resolution mass spectrometry (TOF-MS) was performed (theoretical value: H13O39Si16[M−H]−1084.5337, actual value: 1084.5336). The results are shown in
FIG. 13 . - As shown in the following chemical reaction formula, 0.0117 mL (0.18 mmol) of nitric acid was added to a dispersion of 48.5 mg (0.02 mmol) of hexakis(tetraethylammonium)tetracyclo[5.5.1.13,11.15,9]hexa siloxane-1,3,5,7,9,11-hexakis(yloxide)hydrate (CAS No. 73697-41-3: hereinafter sometimes abbreviated as “Q6(TEA)6.nH2O”) suspended in 0.8 mL of DMAc. The mixture was stirred for 10 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 2 mL of DMAc).
- The 29Si-NMR measurement results of this filtrate are shown in
FIG. 14 (29Si-NMR (Acetone-d6): −90.9 ppm). Further, the measurement results of high-resolution mass spectrometry (TOF-MS) are shown inFIG. 15 (theoretical value: H6NO18Si6[M+NO3]−475.8206, actual value: 475.8207). It was confirmed by various NMR and mass spectrometry that a proton-exchanged basket-shaped hexaol (composition formula Si6O15H6 (hereinafter sometimes abbreviated as “Q6H6”)) was formed in the solution. - 76 mg (0.75 mmol) of sulfuric acid was added to a dispersion of 243 mg (0.10 mmol) of Q6(TEA)6.68.8H2O suspended in 8.0 mL of DMAc. The mixture was stirred for 10 minutes, a suspension was obtained. The suspension was filtered using a filter (washed with 1 mL of DMAc). The peak portion corresponding to Q6H6 was collected from the filtrate by GPC, and concentrated by distilling under reduced pressure to isolate a colorless liquid, which was a composition including 15% by mass of Q6H6, in a yield of 55% (150 mg). The 1H-NMR measurement results of this liquid are shown in
FIG. 16(a) (1H-NMR (DMF-d7): 8.32 ppm). Further, the 29Si-NMR measurement results of this solid are shown inFIG. 16(b) (29Si-NMR (DMF-d7): −90.8 ppm). - 76 mg (0.75 mmol) of sulfuric acid was added to a dispersion of 240 mg (0.10 mmol) of Q6(TEA)6.68.8H2O suspended in 8.0 mL of DMAc and 12 mL of THF. The mixture was stirred for 10 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 3 mL of THF). 1.0 g of silica gel (
Silica Gel 60, pH 6 (Kanto Chemical)) was added to the filtrate, and the mixture was stirred for 5 minutes. The silica gel was separated by filtration using a filter (washed with 3 mL of THF). The filtrate was concentrated by distilling under reduced pressure to obtain a colorless liquid, which was a composition including 0.3% by mass of Q6H6, in a yield of 41% (29Si-NMR (Acetone-d6): −91.0 ppm). - 76 mg (0.75 mmol) of sulfuric acid was added to a dispersion of 243 mg (0.10 mmol) of Q6(TEA)6.68.8H2O suspended in 8.0 mL of DMAc and 12 mL of THF. The mixture was stirred for 10 minutes, and a suspension was obtained. This suspension was filtered using a filter (washed with 3 mL of THF). The filtrate was concentrated by distilling under reduced pressure to obtain a colorless liquid, which was a composition including 0.5% by mass of Q6H6, in a yield of 66% (29Si-NMR (Acetone-d6): −91.0 ppm).
- A colorless liquid, which was a composition including 0.6% by mass of Q6H6, was obtained in a yield of 81% (29Si-NMR (Acetone-d6): −91.0 ppm) in the same manner as in Example 52, except that the amount of THF used was changed from 12 mL to 8 mL.
- A colorless liquid, which was a composition including 0.5% by mass of Q6H6, was obtained in a yield of 88% (29Si-NMR (Acetone-d6): −91.0 ppm) in the same manner as in Example 52, except that the amount of THF used was changed from 12 mL to 4 mL.
- 76 mg (0.75 mmol) of sulfuric acid was added to a dispersion of 243 mg (0.10 mmol) of Q6(TEA)6.68.8H2O suspended in 8.0 mL of DMAc. The mixture was stirred for 10 minutes, and a suspension was obtained. The suspension was filtered using a filter (washed with 1 mL of DMAc). The peak portion corresponding to Q6H6 was collected from the filtrate by GPC, and concentrated by distilling under reduced pressure to obtain 243 mg of a colorless liquid including Q6H6. To this colorless liquid, 0.22 mL of diethyl ether was added, and the mixture was cooled at −40° C. to isolate 18 mg of a colorless solid (crystals).
- In this way, silanol compounds represented by following formula (F) can be obtained.
- In the formula, n represents an integer of 1 to 3.
- This silanol compound is Q6H6 when n=1 and is Q8H8 when n=2.
- The silanol compound produced by the production method of the present invention is useful as a raw material and the like of a siloxane compound to be used in a wide range of fields, such as automobiles, construction, electronics, and medicine.
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JP7141140B2 (en) * | 2018-10-24 | 2022-09-22 | 国立研究開発法人産業技術総合研究所 | Crystal, method for producing crystal, and method for self-organizing silanol compound |
JP7360697B2 (en) * | 2019-10-31 | 2023-10-13 | 国立研究開発法人産業技術総合研究所 | Compound and its manufacturing method |
JP2023130962A (en) * | 2022-03-08 | 2023-09-21 | 国立研究開発法人産業技術総合研究所 | Silanol compound, method for producing silanol compound and composition containing silanol compound |
US11999625B2 (en) * | 2022-03-29 | 2024-06-04 | Nissan Chemical Corporation | Method of producing layered silicate, and application thereof in production of silica nanosheet and so on |
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WO2015128496A1 (en) | 2014-02-28 | 2015-09-03 | Katholieke Universiteit Leuven | Highly reactive oligosiloxysilane compound |
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JP2017075128A (en) | 2015-10-16 | 2017-04-20 | 国立大学法人群馬大学 | Cage silsesquioxane having 4 different substituents in confrontation |
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