JP6940241B2 - ビス(アシル)ホスフィン酸シリルエステルの調製方法 - Google Patents
ビス(アシル)ホスフィン酸シリルエステルの調製方法 Download PDFInfo
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- JP6940241B2 JP6940241B2 JP2019565401A JP2019565401A JP6940241B2 JP 6940241 B2 JP6940241 B2 JP 6940241B2 JP 2019565401 A JP2019565401 A JP 2019565401A JP 2019565401 A JP2019565401 A JP 2019565401A JP 6940241 B2 JP6940241 B2 JP 6940241B2
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- alkyl
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- -1 phosphinic acid silyl ester Chemical class 0.000 title claims description 92
- 238000000034 method Methods 0.000 title claims description 91
- 125000002252 acyl group Chemical group 0.000 title claims description 86
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 73
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 72
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 60
- 229910052736 halogen Inorganic materials 0.000 claims description 54
- 150000002367 halogens Chemical class 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 45
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 36
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 35
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 32
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 31
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 27
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 101100240518 Caenorhabditis elegans nhr-12 gene Proteins 0.000 claims description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- AQQVTZBWWYVEGR-UHFFFAOYSA-N [NH4+].[O-][PH2]=O Chemical compound [NH4+].[O-][PH2]=O AQQVTZBWWYVEGR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 125000001246 bromo group Chemical group Br* 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000006884 silylation reaction Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 13
- 125000000623 heterocyclic group Chemical group 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 6
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- GBRQRVSRWHUNAZ-UHFFFAOYSA-N bis(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(O)(=O)C(=O)C1=C(C)C=C(C)C=C1C GBRQRVSRWHUNAZ-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UKRQMDIFLKHCRO-UHFFFAOYSA-N 2,4,6-trimethylbenzoyl chloride Chemical compound CC1=CC(C)=C(C(Cl)=O)C(C)=C1 UKRQMDIFLKHCRO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 125000002346 iodo group Chemical group I* 0.000 description 3
- 238000010915 one-step procedure Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- KUXCXXKTVFHHNN-UHFFFAOYSA-N [PH2](OC(C1=C(C=C(C=C1C)C)C)=O)=O Chemical compound [PH2](OC(C1=C(C=C(C=C1C)C)C)=O)=O KUXCXXKTVFHHNN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 description 2
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000012144 step-by-step procedure Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WDYVUKGVKRZQNM-UHFFFAOYSA-N 6-phosphonohexylphosphonic acid Chemical compound OP(O)(=O)CCCCCCP(O)(O)=O WDYVUKGVKRZQNM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N CCCCCCCN Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- UCKORWKZRPKRQE-UHFFFAOYSA-N bromo(triethyl)silane Chemical compound CC[Si](Br)(CC)CC UCKORWKZRPKRQE-UHFFFAOYSA-N 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ACTAPAGNZPZLEF-UHFFFAOYSA-N chloro(tripropyl)silane Chemical compound CCC[Si](Cl)(CCC)CCC ACTAPAGNZPZLEF-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000005356 cycloalkylalkenyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003113 cycloheptyloxy group Chemical group C1(CCCCCC1)O* 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000000131 cyclopropyloxy group Chemical group C1(CC1)O* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000005805 dimethoxy phenyl group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010189 synthetic method Methods 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000723 toxicological property Toxicity 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/307—Acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5086—Preparation; Separation; Purification; Stabilisation from phosphonium salts as starting materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
Description
当該方法は、
a)ビス(シリルエーテル)ホスフィンを得るために、ホスフィン酸アンモニウムをシリル化剤と共に加熱する工程と、
b)工程a)で得られた上記ビス(シリルエーテル)ホスフィンを一般式IIa及び/又は一般式IIbの化合物と反応させる工程であって、
を備える。
a)ビス(シリルエーテル)ホスフィンを得るために、ホスフィン酸アンモニウムをシリル化剤と共に加熱する工程と、
b)工程a)で得られたビス(シリルエーテル)ホスフィンを一般式IIa及び/又は一般式IIbの化合物と反応させる工程であって、
を備えることを特徴とする。
A−SiR14R15R16 Va
上記一般式Va中、R14、R15及びR16は同じであるか又は異なり、独立に、直鎖状若しくは分枝状のC1−C20−アルキル又はC6−C12−アリールから選択され、Aは、ハロゲン、トリフラート(OSO2CF3)、シアニド、アジド及び1−イミダゾリルから選択される。
R16R15R14Si−B−SiR14R15R16 Vb
上記一般式Vb中、R14、R15及びR16は同じであるか又は異なり、独立に、直鎖状若しくは分枝状のC1−C20−アルキル又はC6−C12−アリールから選択され、Bは、O、NH、NCH3、OC(CH3)=N、OC(CF3)=N、NH(C=O)NH、及びNH(C=O)Oから選択される。
i)得られた一般式Iのビス(アシル)ホスフィン酸シリルエステルを副生成物及び/又は遊離体及び/又は溶媒から分離する工程、及び/又は
ii)得られた一般式Iのビス(アシル)ホスフィン酸シリルエステルを洗浄する工程
によってさらに処理されてもよいことが理解される。
i)得られた一般式IIIのビス(アシル)ホスフィン酸を溶媒から分離する工程、及び/又は
ii)得られた一般式IIIのビス(アシル)ホスフィン酸を洗浄する工程
をさらに備えてもよい。
i)得られた一般式IIIのビス(アシル)ホスフィン酸を溶媒から分離する工程、及び
ii)得られた一般式IIIのビス(アシル)ホスフィン酸を洗浄する工程
をさらに備える。
ホスフィン酸アンモニウム(20.0g、0.241mol、1当量)を1,1,1,3,3,3−ヘキサメチルジシラザン68.04g(0.422mol、1.75当量)に懸濁させ、これを、アンモニアの発生が止み、ホスフィン酸アンモニウムが完全に溶解するまで110〜120℃で撹拌した。反応混合物を、氷浴中5℃まで冷却し、200mLのジクロロメタンで希釈した。塩化2,4,6−トリメチルベンゾイル44.44g(0.243mol、1.01当量)を滴下し、反応混合物を室温で一晩撹拌した。フラスコを再度氷浴中で冷却し、さらに1,1,1,3,3,3−ヘキサメチルジシラザン68.04g(0.422mol、1.75当量)を素早く加えた。5℃で3時間撹拌した後、塩化2,4,6−トリメチルベンゾイル44.44g(0.243mol、1.01当量)を滴下し、撹拌しながら室温で一晩放置した。次いで反応物を0〜5℃まで冷却し、温度が15℃を超えないようにしてエタノール200mLの滴下により加水分解した。濾過後、残渣をエタノールで十分に洗浄し、濾液を乾固するまで蒸発させた。この黄色の粘性が高い油状物にTBME:ヘキサン 1:1を加えた。生成物が結晶化した後、淡黄色固体を濾過し、冷ヘキサンで洗浄し、乾燥した。
1H−NMR(400.13MHz;CDCl3):δ(ppm)=2.13(s,12H),2.26(s,6H),6.77(s,4H),9.53(bs,1H)
31P−NMR(161.89MHz;CDCl3):δ(ppm)=−3.67
13C−NMR(100.62MHz;CDCl3):(ppm)δ=19.25,21.15,128.70,135.15,136.23(d,3JPC45.5Hz),140.23,216.80(d,1JPC101.2Hz)
ホスフィン酸アンモニウム(20.0g、0.241mol、1当量)を1,1,1,3,3,3−ヘキサメチルジシラザン136.07g(0.843mol、3.5当量)に懸濁させ、これを、アンモニアの発生が止み、ホスフィン酸アンモニウムが完全に溶解するまで110〜120℃で撹拌した。反応混合物を、氷浴中で5℃まで冷却し、200mLのジクロロメタンで希釈した。塩化2,4,6−トリメチルベンゾイル90.19g(0.494mol、2.05当量)を滴下し、反応混合物を、31P−NMRが完全変換を示すまで室温で一晩撹拌した。その後、反応物を0〜5℃に冷却し、温度が25℃を超えないようにしてエタノール300mLの滴下により加水分解した。濾過後、残渣をジクロロメタン:エタノール 1:1で十分に洗浄し、濾液を乾固するまで蒸発させた。残渣を酢酸エチルに溶解し、希塩酸で2回洗浄した。有機相を乾燥し、蒸発させた。粗製固体生成物をヘプタン:トルエン 1:4の混合物から再結晶し、濾過し、ヘプタンで洗浄し、乾燥して、ビス(2,4,6−トリメチルベンゾイル)ホスフィン酸を淡黄色固体として得た。
1H−NMR(400.13MHz;CDCl3):δ=2.13(s,12H),2.32(s,6H),6.97(s,4H),12.65(bs,1H)
31P−NMR(161.89MHz;CDCl3):δ=−2.97
13C−NMR(100.62MHz;CDCl3):δ=19.14,21.27,128.79,135.26(d,2JPC46.5Hz),135.46,140.67,213.72(d,1JPC98.7Hz)
Claims (15)
- 一般式Iのビス(アシル)ホスフィン酸シリルエステルの調製方法であって、
前記方法が、
a)ビス(シリルエーテル)ホスフィンを得るために、ホスフィン酸アンモニウムをシリル化剤と共に加熱する工程と、
b)工程a)で得られた前記ビス(シリルエーテル)ホスフィンを一般式IIa及び/又は一般式IIbの化合物と反応させる工程であって、
を備える方法。 - R1、R3及びR5並びに/又はR7、R9及びR11が同じであることを特徴とする請求項1に記載の方法。
- R1、R3及びR5並びに/又はR7、R9及びR11が同じであり、直鎖状若しくは分枝状のC1−C20−アルキルから選択されることを特徴とする請求項2に記載の方法。
- R2及びR4並びに/又はR8及びR10が同じであることを特徴とする請求項1から請求項3のいずれか1項に記載の方法。
- R2及びR4並びに/又はR8及びR10が同じであり、Hであることを特徴とする請求項1から請求項4のいずれか1項に記載の方法。
- Zが、クロロ、ブロモ及びヨードから選択されることを特徴とする請求項1から請求項5のいずれか1項に記載の方法。
- 工程a)が、不活性ガス雰囲気下で、及び/又は溶媒を添加せずに実施されることを特徴とする請求項1から請求項5のいずれか1項に記載の方法。
- 工程a)で得られた前記ビス(シリルエーテル)ホスフィンが、有機溶媒と混合され、その後で工程b)が実施されることを特徴とする請求項1から請求項5のいずれか1項に記載の方法。
- 工程a)で得られた前記ビス(シリルエーテル)ホスフィンが、工程a)で得られた前記シリル化生成物の精製及び単離をせずに、工程b)に供されることを特徴とする請求項1から請求項8のいずれか1項に記載の方法。
- 工程a)が、100〜130℃の範囲の温度で実施され、かつ/又は工程b)が、−5〜50℃の範囲の温度で実施されることを特徴とする請求項1から請求項9のいずれか1項に記載の方法。
- 工程b)が、一般式IIa及び/又は一般式IIbの前記化合物対工程a)の前記ホスフィン酸アンモニウムの当量重量比[IIa及び/又はIIb:P化合物]が、3.5:1〜1.5:1の範囲にあるように実施されることを特徴とする請求項1から請求項10のいずれか1項に記載の方法。
- 工程a)及び/又は工程b)が、1回以上繰り返されることを特徴とする請求項1から請求項11のいずれか1項に記載の方法。
- 工程b)で得られた前記ビス(アシル)ホスフィン酸シリルエステルを加水分解して、一般式IIIのビス(アシル)ホスフィン酸を得るさらなる工程c)であって、
を備える請求項1から請求項12のいずれか1項に記載の方法。 - 工程c)が、−5〜50℃の範囲の温度で実施されることを特徴とする請求項13に記載の方法。
- 一般式Iのビス(アシル)ホスフィン酸シリルエステルであって、
ビス(アシル)ホスフィン酸シリルエステル。
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