JP5555919B2 - Novel sulfonium salt, production method thereof and use thereof - Google Patents
Novel sulfonium salt, production method thereof and use thereof Download PDFInfo
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- JP5555919B2 JP5555919B2 JP2010537801A JP2010537801A JP5555919B2 JP 5555919 B2 JP5555919 B2 JP 5555919B2 JP 2010537801 A JP2010537801 A JP 2010537801A JP 2010537801 A JP2010537801 A JP 2010537801A JP 5555919 B2 JP5555919 B2 JP 5555919B2
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- trifluoromethyl
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- 238000004519 manufacturing process Methods 0.000 title claims description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title description 7
- -1 tetrafluoroborate group Chemical group 0.000 claims description 178
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 88
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 150000003839 salts Chemical class 0.000 claims description 38
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 125000003944 tolyl group Chemical group 0.000 claims description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 150000001408 amides Chemical class 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 13
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 claims description 12
- 150000003949 imides Chemical class 0.000 claims description 11
- 125000001624 naphthyl group Chemical group 0.000 claims description 11
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 10
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 claims description 10
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims description 9
- SBUXRMKDJWEXRL-ROUUACIJSA-N cis-body Chemical group O=C([C@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ROUUACIJSA-N 0.000 claims description 9
- SBUXRMKDJWEXRL-ZWKOTPCHSA-N trans-body Chemical compound O=C([C@@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ZWKOTPCHSA-N 0.000 claims description 9
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 7
- NVSYANRBXPURRQ-UHFFFAOYSA-N naphthalen-1-ylmethanamine Chemical compound C1=CC=C2C(CN)=CC=CC2=C1 NVSYANRBXPURRQ-UHFFFAOYSA-N 0.000 claims description 6
- DZBHNPJZCQWUCG-UHFFFAOYSA-N (3,5-dimethylphenyl)methanamine Chemical compound CC1=CC(C)=CC(CN)=C1 DZBHNPJZCQWUCG-UHFFFAOYSA-N 0.000 claims description 5
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 claims description 5
- DHVHORCFFOSRBP-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenyl]methanamine Chemical compound NCC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 DHVHORCFFOSRBP-UHFFFAOYSA-N 0.000 claims description 4
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- SIIWTWXTZDDNTI-UHFFFAOYSA-N n-(2-hydroxyethyl)-4-methylbenzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)NCCO)C=C1 SIIWTWXTZDDNTI-UHFFFAOYSA-N 0.000 claims description 4
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 4
- QKBKGNDTLQFSEU-UHFFFAOYSA-N 2-bromo-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Br)=C QKBKGNDTLQFSEU-UHFFFAOYSA-N 0.000 claims description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical group 0.000 claims description 3
- NTNZTEQNFHNYBC-UHFFFAOYSA-N ethyl 2-aminoacetate Chemical group CCOC(=O)CN NTNZTEQNFHNYBC-UHFFFAOYSA-N 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000012454 non-polar solvent Substances 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims 9
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 claims 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 claims 1
- LIUMVPGQWWSINV-UHFFFAOYSA-N S(=O)(=O)(C1=CC=C(C)C=C1)NC(CC)O Chemical compound S(=O)(=O)(C1=CC=C(C)C=C1)NC(CC)O LIUMVPGQWWSINV-UHFFFAOYSA-N 0.000 claims 1
- 238000005481 NMR spectroscopy Methods 0.000 description 57
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 54
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- 125000003118 aryl group Chemical group 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 22
- 239000012043 crude product Substances 0.000 description 14
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 14
- 150000002894 organic compounds Chemical class 0.000 description 14
- 239000012044 organic layer Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000011780 sodium chloride Substances 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000012230 colorless oil Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000003480 eluent Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- RLNKDIHPDADNOR-UHFFFAOYSA-M (2-methylphenyl)-phenyl-(3,3,3-trifluoroprop-1-enyl)sulfanium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=CC=CC=C1[S+](C=CC(F)(F)F)C1=CC=CC=C1 RLNKDIHPDADNOR-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 150000003018 phosphorus compounds Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- YVRLZZAZRUAIFE-UHFFFAOYSA-M diphenyl(3,3,3-trifluoroprop-1-enyl)sulfanium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[S+](C=CC(F)(F)F)C1=CC=CC=C1 YVRLZZAZRUAIFE-UHFFFAOYSA-M 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 125000001188 haloalkyl group Chemical group 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 150000003141 primary amines Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 150000001541 aziridines Chemical class 0.000 description 4
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- 150000003456 sulfonamides Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 3
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 0 C1CC*CC1 Chemical compound C1CC*CC1 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- GQZXWVCKGQAHTQ-UHFFFAOYSA-M [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=NC=1[S+](C=CC(F)(F)F)C1=CC=CC=C1 Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=NC=1[S+](C=CC(F)(F)F)C1=CC=CC=C1 GQZXWVCKGQAHTQ-UHFFFAOYSA-M 0.000 description 3
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QBPUUVJGICIHLG-UHFFFAOYSA-N n-(1-hydroxy-2-methylpropan-2-yl)-4-methylbenzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)NC(C)(C)CO)C=C1 QBPUUVJGICIHLG-UHFFFAOYSA-N 0.000 description 3
- BYLGOANRRSXVAA-UHFFFAOYSA-M naphthalen-2-yl-phenyl-(3,3,3-trifluoroprop-1-enyl)sulfanium trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=C2C=CC=CC2=CC=1[S+](C=CC(F)(F)F)C1=CC=CC=C1 BYLGOANRRSXVAA-UHFFFAOYSA-M 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 2
- KWTSXDURSIMDCE-MRVPVSSYSA-N (R)-amphetamine Chemical compound C[C@@H](N)CC1=CC=CC=C1 KWTSXDURSIMDCE-MRVPVSSYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- LMWAYGNFIDXQTQ-UHFFFAOYSA-N 1-[(3,5-dimethylphenyl)methyl]-2-(trifluoromethyl)aziridine Chemical compound CC1=CC(C)=CC(CN2C(C2)C(F)(F)F)=C1 LMWAYGNFIDXQTQ-UHFFFAOYSA-N 0.000 description 2
- OAQILXBENFAJCY-UHFFFAOYSA-N 1-[[3,5-bis(trifluoromethyl)phenyl]methyl]-2-(trifluoromethyl)aziridine Chemical compound FC(F)(F)C1CN1CC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 OAQILXBENFAJCY-UHFFFAOYSA-N 0.000 description 2
- YZVWKHVRBDQPMQ-UHFFFAOYSA-N 1-aminopyrene Chemical compound C1=C2C(N)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 YZVWKHVRBDQPMQ-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical compound CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- WFRBDWRZVBPBDO-UHFFFAOYSA-N 2-methyl-2-pentanol Chemical compound CCCC(C)(C)O WFRBDWRZVBPBDO-UHFFFAOYSA-N 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- NGDNVOAEIVQRFH-UHFFFAOYSA-N 2-nonanol Chemical compound CCCCCCCC(C)O NGDNVOAEIVQRFH-UHFFFAOYSA-N 0.000 description 2
- GYSCXPVAKHVAAY-UHFFFAOYSA-N 3-Nonanol Chemical compound CCCCCCC(O)CC GYSCXPVAKHVAAY-UHFFFAOYSA-N 0.000 description 2
- GTGMNHFXEJCMHC-UHFFFAOYSA-N 3-ethyl-1,1,1-trifluoropent-2-ene Chemical compound CCC(CC)=CC(F)(F)F GTGMNHFXEJCMHC-UHFFFAOYSA-N 0.000 description 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 2
- FRDAATYAJDYRNW-UHFFFAOYSA-N 3-methyl-3-pentanol Chemical compound CCC(C)(O)CC FRDAATYAJDYRNW-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- HTSABYAWKQAHBT-UHFFFAOYSA-N 3-methylcyclohexanol Chemical compound CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 2
- ZFAGOADKDXXTSV-UHFFFAOYSA-N 3-methylpentan-2-amine Chemical compound CCC(C)C(C)N ZFAGOADKDXXTSV-UHFFFAOYSA-N 0.000 description 2
- YVBCULSIZWMTFY-UHFFFAOYSA-N 4-Heptanol Natural products CCCC(O)CCC YVBCULSIZWMTFY-UHFFFAOYSA-N 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- AESCOZABNOGYJR-UHFFFAOYSA-N 4-methyl-N-[2-methyl-1-(3,3,3-trifluoroprop-1-en-2-yloxy)propan-2-yl]benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)NC(C)(C)COC(=C)C(F)(F)F)C=C1 AESCOZABNOGYJR-UHFFFAOYSA-N 0.000 description 2
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 2
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 2
- HZZLWSFAPDJVLT-UHFFFAOYSA-N 4-methylhexan-1-amine Chemical compound CCC(C)CCCN HZZLWSFAPDJVLT-UHFFFAOYSA-N 0.000 description 2
- XJGFWWJLMVZSIG-UHFFFAOYSA-N 9-aminoacridine Chemical compound C1=CC=C2C(N)=C(C=CC=C3)C3=NC2=C1 XJGFWWJLMVZSIG-UHFFFAOYSA-N 0.000 description 2
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- HAKWQWVHDYQMBY-UHFFFAOYSA-N n-cyclohexyl-3-(5-nitrofuran-2-yl)propanamide Chemical compound O1C([N+](=O)[O-])=CC=C1CCC(=O)NC1CCCCC1 HAKWQWVHDYQMBY-UHFFFAOYSA-N 0.000 description 1
- NSBIQPJIWUJBBX-UHFFFAOYSA-N n-methoxyaniline Chemical compound CONC1=CC=CC=C1 NSBIQPJIWUJBBX-UHFFFAOYSA-N 0.000 description 1
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 1
- XAUGWFWQVYXATQ-UHFFFAOYSA-N n-phenylbenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NC1=CC=CC=C1 XAUGWFWQVYXATQ-UHFFFAOYSA-N 0.000 description 1
- AZTGEJBZSFKULT-UHFFFAOYSA-N n-phenylcyclohexanecarboxamide Chemical compound C1CCCCC1C(=O)NC1=CC=CC=C1 AZTGEJBZSFKULT-UHFFFAOYSA-N 0.000 description 1
- JBTCHCWUNMZNEO-UHFFFAOYSA-N n-phenylhexanamide Chemical compound CCCCCC(=O)NC1=CC=CC=C1 JBTCHCWUNMZNEO-UHFFFAOYSA-N 0.000 description 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- FCBBRODPXVPZAH-UHFFFAOYSA-N nonan-5-ol Chemical compound CCCCC(O)CCCC FCBBRODPXVPZAH-UHFFFAOYSA-N 0.000 description 1
- 229960002748 norepinephrine Drugs 0.000 description 1
- SFLSHLFXELFNJZ-UHFFFAOYSA-N norepinephrine Natural products NCC(O)C1=CC=C(O)C(O)=C1 SFLSHLFXELFNJZ-UHFFFAOYSA-N 0.000 description 1
- LRCXRAABFLIVAI-UHFFFAOYSA-N norfenefrine Chemical compound NCC(O)C1=CC=CC(O)=C1 LRCXRAABFLIVAI-UHFFFAOYSA-N 0.000 description 1
- 229960001856 norfenefrine Drugs 0.000 description 1
- SOFXQTNEGHNRMN-BNHYGAARSA-N norloline Chemical compound C1C[C@@H]2O[C@H]3[C@H](N)[C@@H]2N1C3 SOFXQTNEGHNRMN-BNHYGAARSA-N 0.000 description 1
- AQFWNELGMODZGC-UHFFFAOYSA-N o-ethylhydroxylamine Chemical compound CCON AQFWNELGMODZGC-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 description 1
- SERHXTVXHNVDKA-UHFFFAOYSA-N pantolactone Chemical compound CC1(C)COC(=O)C1O SERHXTVXHNVDKA-UHFFFAOYSA-N 0.000 description 1
- 229940115458 pantolactone Drugs 0.000 description 1
- SIEVQTNTRMBCHO-UHFFFAOYSA-N pantolactone Natural products CC1(C)OC(=O)CC1O SIEVQTNTRMBCHO-UHFFFAOYSA-N 0.000 description 1
- VEDDBHYQWFOITD-UHFFFAOYSA-N para-bromobenzyl alcohol Chemical compound OCC1=CC=C(Br)C=C1 VEDDBHYQWFOITD-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- IGEIPFLJVCPEKU-UHFFFAOYSA-N pentan-2-amine Chemical compound CCCC(C)N IGEIPFLJVCPEKU-UHFFFAOYSA-N 0.000 description 1
- PQPFFKCJENSZKL-UHFFFAOYSA-N pentan-3-amine Chemical compound CCC(N)CC PQPFFKCJENSZKL-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229960003562 phentermine Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- 150000003012 phosphoric acid amides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- INDBQLZJXZLFIT-UHFFFAOYSA-N primaquine Chemical compound N1=CC=CC2=CC(OC)=CC(NC(C)CCCN)=C21 INDBQLZJXZLFIT-UHFFFAOYSA-N 0.000 description 1
- 229960005179 primaquine Drugs 0.000 description 1
- BNZYRKVSCLSXSJ-IOSLPCCCSA-N psicofuranin Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@]1(CO)O[C@H](CO)[C@@H](O)[C@H]1O BNZYRKVSCLSXSJ-IOSLPCCCSA-N 0.000 description 1
- YJYIDNNTUMEKSG-UHFFFAOYSA-N pteridin-6-amine Chemical compound N1=CN=CC2=NC(N)=CN=C21 YJYIDNNTUMEKSG-UHFFFAOYSA-N 0.000 description 1
- MFUFBSLEAGDECJ-UHFFFAOYSA-N pyren-2-ylamine Natural products C1=CC=C2C=CC3=CC(N)=CC4=CC=C1C2=C43 MFUFBSLEAGDECJ-UHFFFAOYSA-N 0.000 description 1
- HDOUGSFASVGDCS-UHFFFAOYSA-N pyridin-3-ylmethanamine Chemical compound NCC1=CC=CN=C1 HDOUGSFASVGDCS-UHFFFAOYSA-N 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical group SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 description 1
- ZRKGTINFVOLLNT-UHFFFAOYSA-N pyrrolo[3,4-b]pyridine-5,7-dione Chemical compound C1=CC=C2C(=O)NC(=O)C2=N1 ZRKGTINFVOLLNT-UHFFFAOYSA-N 0.000 description 1
- SJSABZBUTDSWMJ-UHFFFAOYSA-N pyrrolo[3,4-c]pyridine-1,3-dione Chemical compound N1=CC=C2C(=O)NC(=O)C2=C1 SJSABZBUTDSWMJ-UHFFFAOYSA-N 0.000 description 1
- HSIPLPKNLDWHSE-UHFFFAOYSA-N quinazosin Chemical compound N=1C(N)=C2C=C(OC)C(OC)=CC2=NC=1N1CCN(CC=C)CC1 HSIPLPKNLDWHSE-UHFFFAOYSA-N 0.000 description 1
- 229950009223 quinazosin Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229960004181 riluzole Drugs 0.000 description 1
- 229960000581 salicylamide Drugs 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 229960001153 serine Drugs 0.000 description 1
- 229940076279 serotonin Drugs 0.000 description 1
- 238000005055 short column chromatography Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229960001462 sodium cyclamate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- YLJREFDVOIBQDA-UHFFFAOYSA-N tacrine Chemical compound C1=CC=C2C(N)=C(CCCC3)C3=NC2=C1 YLJREFDVOIBQDA-UHFFFAOYSA-N 0.000 description 1
- 229960001685 tacrine Drugs 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- ARZGWBJFLJBOTR-UHFFFAOYSA-N tetradecanamide Chemical compound CCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCC(N)=O ARZGWBJFLJBOTR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical compound NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 description 1
- 229960002898 threonine Drugs 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- 125000004360 trifluorophenyl group Chemical group 0.000 description 1
- HDZZVAMISRMYHH-KCGFPETGSA-N tubercidin Chemical compound C1=CC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O HDZZVAMISRMYHH-KCGFPETGSA-N 0.000 description 1
- 229960003732 tyramine Drugs 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 229950008148 xinomiline Drugs 0.000 description 1
- 229950006967 zoxazolamine Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/38—Oxygen atoms in positions 2 and 3, e.g. isatin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
- C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4015—Esters of acyclic unsaturated acids
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- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、新規なスルホニウム塩に関し、特に、トリフルオロメチル基を含有する各種の有用化合物の合成等に利用できるスルホニウム塩、その製造方法及びその用途に関する。 The present invention relates to a novel sulfonium salt, and more particularly to a sulfonium salt that can be used for the synthesis of various useful compounds containing a trifluoromethyl group, a production method thereof, and an application thereof.
スルホニウム塩は、主に、各種の有機化合物の合成中間体として用いられている化合物であり、医薬及び農薬分野をはじめとして、極めて広範な有機合成に利用されている重要な化合物である。このように、利用価値が高く、その利用範囲が広範に及ぶことから、多くの研究者が、新規なスルホニウム塩の合成に取り組んでいる。(例えば、非特許文献1〜非特許文献6など)
また、近年、トリフルオロメチル基を含有する有機化合物が、その有用な特性から注目を集めている。これは、有機化合物に含まれる1つ又は複数の水素原子をフッ素原子に置換した有機化合物の一般的な性質として、高脂溶性、抗分解性といった化学的及び物理的な特性が、有意に変化するためであり、特に、有機化合物に含有されるメチル基をトリフルオロメチル基に置換した化合物の多くが、生理活性等の有用な性質を示しているためである。例えば、トリフルオロメチル基を導入した化合物は、医薬としての有用性が示唆されている(例えば、特許文献1参照)。The sulfonium salt is a compound that is mainly used as a synthetic intermediate for various organic compounds, and is an important compound that is used in an extremely wide range of organic syntheses including the pharmaceutical and agricultural chemical fields. Thus, because of its high utility value and wide range of utilization, many researchers are working on the synthesis of novel sulfonium salts. (For example, Non-Patent Document 1 to Non-Patent Document 6)
In recent years, organic compounds containing a trifluoromethyl group have attracted attention because of their useful properties. This is because, as a general property of an organic compound in which one or more hydrogen atoms contained in the organic compound are replaced with fluorine atoms, the chemical and physical properties such as high fat solubility and anti-degradability are significantly changed. This is because many of the compounds in which the methyl group contained in the organic compound is substituted with a trifluoromethyl group exhibit useful properties such as physiological activity. For example, a compound in which a trifluoromethyl group is introduced has been suggested to be useful as a pharmaceutical (see, for example, Patent Document 1).
このような特性から、トリフルオロメチル基を含有する有機化合物は、医薬若しくは農薬の原料、又は液晶若しくは有機ELの光学材料をはじめとして広く利用されており、その適用分野もさらに拡大している。 From such characteristics, organic compounds containing a trifluoromethyl group are widely used, including raw materials for pharmaceuticals or agricultural chemicals, or optical materials for liquid crystals or organic EL, and their application fields are further expanded.
有機化合物中にトリフルオロメチル基を導入するには、当該トリフルオロメチル基を有機化合物中に直接導入する方法が知られているが、導入操作が複雑であるという問題があった。 In order to introduce a trifluoromethyl group into an organic compound, a method of directly introducing the trifluoromethyl group into the organic compound is known, but there is a problem that the introduction operation is complicated.
このような問題があるため、有機化合物を構築するための合成中間体(いわゆるビルディングブロック剤)を、トリフルオロメチル基を含有した状態で予め生成しておき、当該ビルディングブロック剤を用いた反応により、有機化合物にトリフルオロメチル基を導入する手法がある。 Because of these problems, a synthetic intermediate for building an organic compound (a so-called building block agent) is produced in advance in a state containing a trifluoromethyl group, and a reaction using the building block agent is performed. There is a method of introducing a trifluoromethyl group into an organic compound.
例えば、非特許文献7には、次の(A)式によりトリフルオロメチル基を含有するスルホン化合物を生成し得ることが開示されており、このスルホン化合物を、ビルディングブロック剤として、次の(B)式のように、マロン酸ジエチルにトリフルオロメチル基を導入することができることが開示されている。 For example, Non-Patent Document 7 discloses that a sulfone compound containing a trifluoromethyl group can be produced according to the following formula (A). Using this sulfone compound as a building block agent, the following (B It is disclosed that a trifluoromethyl group can be introduced into diethyl malonate as shown in the formula.
(A)式の反応に従えば、所定量の1-クロロ-3,3,3-トリフルオロプロペンとベンゼンチオールとを水酸化ナトリウムを含有するエタノール溶液中に投入し、50℃で一日撹拌した後、更に100℃で一日撹拌することにより、トリフルオロメチル基を含有するスルフィド化合物が、シス体及びトランス体の混合物として、約80%の収率で得られていた。 According to the reaction of formula (A), a predetermined amount of 1-chloro-3,3,3-trifluoropropene and benzenethiol are put into an ethanol solution containing sodium hydroxide and stirred at 50 ° C. for one day. Then, by further stirring for one day at 100 ° C., a sulfide compound containing a trifluoromethyl group was obtained in a yield of about 80% as a mixture of a cis isomer and a trans isomer.
さらに、この得られたスルフィド化合物を、30%過酸化水素水を所要量混合させた酢酸溶液中に投入し、40℃で40時間反応させることにより、トリフルオロメチル基を含有するスルホン化合物が、トランス体の様態で、約82%の収率で得られていた。 Further, the obtained sulfide compound is put into an acetic acid solution in which a required amount of 30% hydrogen peroxide water is mixed and reacted at 40 ° C. for 40 hours, whereby a sulfone compound containing a trifluoromethyl group is obtained. The product was obtained in a yield of about 82% in a trans form.
このようにして得たスルホン化合物を、適宜量分取し、上述の(B)式に示すように、THF(テトラヒドロフラン)溶液に溶解させ、10mol%のNaOHの存在下で、適宜量のマロン酸ジエチルと室温で5分間反応させることにより、トリフルオロメチル基を含む部分構造が、マロン酸ジエチルに導入されていた。 The sulfone compound thus obtained is fractionated in an appropriate amount, dissolved in a THF (tetrahydrofuran) solution as shown in the above formula (B), and an appropriate amount of malonic acid in the presence of 10 mol% NaOH. A partial structure containing a trifluoromethyl group was introduced into diethyl malonate by reacting with diethyl at room temperature for 5 minutes.
しかしながら、上記文献に示されるように、従来のスルホニウム塩をビルディングブロック剤として使用する場合には、トリフルオロメチル基を導入し得る有機化合物の種類が限られることから、汎用性が低いということに加え、(B)式に示したように、当該ビルディングブロック剤に含有されるトリフルオロメチル基以外の官能基(原子団)も、最終生成物に導入され、残存してしまうという課題もある。
特に、このように残存した官能基が、最終生成物に悪影響をもたらす場合(例えば、立体的な障害など)には、当該官能基を除去するための別段の化学反応を、追加で実施する必要があり、製造コストの増加を招くという課題がある。However, as shown in the above document, when a conventional sulfonium salt is used as a building block agent, since the types of organic compounds that can introduce a trifluoromethyl group are limited, the versatility is low. In addition, as shown in the formula (B), there is a problem that functional groups (atomic groups) other than the trifluoromethyl group contained in the building block agent are also introduced into the final product and remain.
In particular, when the remaining functional group adversely affects the final product (for example, steric hindrance), an additional chemical reaction for removing the functional group needs to be additionally performed. There is a problem that the manufacturing cost is increased.
本発明の目的は、トリフルオロメチル基を含有する広汎な種類の有機化合物を、簡便に合成することのできるビルディングブロック剤等として利用される新しいタイプのスルホニウム塩を提供することにある。 An object of the present invention is to provide a new type of sulfonium salt that can be used as a building block agent or the like that can easily synthesize a wide variety of organic compounds containing a trifluoromethyl group.
かくして、本発明に従えば、上記課題を解決するものとして、下記の一般式(I)で表されるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩、及びその製造方法が提供される。さらに、本発明に従えば、上記β−(トリフルオロメチル)ビニルジアリールスルホニウム塩を、ビルディングブロック剤として、アジリジンをはじめとする各種のトリフルオロメチル基を含有する有機化合物を合成する方法も提供される。 Thus, according to the present invention, there is provided a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the following general formula (I) and a method for producing the same, in order to solve the above problems. Furthermore, according to the present invention, there is also provided a method for synthesizing organic compounds containing various trifluoromethyl groups including aziridine, using the β- (trifluoromethyl) vinyldiarylsulfonium salt as a building block agent. The
本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩は、次の一般式(I)で表すことができる。 The β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention can be represented by the following general formula (I).
上記式(I)中、R1およびR2は、互いに独立して、低級アルキル基、低級ハロアルキル基、低級アルコキシ基、水酸基またはハロゲン原子により置換されていてもよいアリール基を表す。In the above formula (I), R 1 and R 2 each independently represent a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a hydroxyl group or an aryl group which may be substituted with a halogen atom.
ここで、アリール基とは、芳香族炭化水素から1つの水素原子が脱離した構造を表す。上記式(I)中、R1およびR2の構造は、その原料となる芳香族チオール(後述する一般式(VIb)で表される)の構造に由来するため、該芳香族チオールが入手できる限り特に限定されるものではない。Here, the aryl group represents a structure in which one hydrogen atom is eliminated from an aromatic hydrocarbon. In the above formula (I), the structures of R 1 and R 2 are derived from the structure of the aromatic thiol (represented by the general formula (VIb) described later) as the raw material, so that the aromatic thiol can be obtained. There is no particular limitation.
しかしながら、嵩高いアリール基および/または嵩高い置換基を有するアリール基を有する芳香族チオールを用いると、合成の容易性、取り扱い易さ、価格などの観点から利点が少ない。このことは、特に、本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩をビルディングブロック剤としてアジリジン化合物等の製造に用いると、原料となるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を構成する当該アリール基がアジリジン化合物等の最終生成物に含まれずに除去される部位であることからもあてはまる。 However, when an aromatic thiol having a bulky aryl group and / or an aryl group having a bulky substituent is used, there are few advantages from the viewpoints of ease of synthesis, ease of handling, price, and the like. This indicates that, when the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention is used as a building block agent for the production of aziridine compounds and the like, the raw material β- (trifluoromethyl) vinyldiarylsulfonium salt is constituted. This is also true because the aryl group is a site that is removed without being contained in the final product such as an aziridine compound.
このようなことから、該アリール基を構成する芳香環としては、一般に、5員環または6員環からなる芳香環が2つ以内からなるものが望ましい。また、それらのアリール基に置換されていてもよい置換基の低級アルキル基、低級ハロアルキル基および低級アルコキシ基における「低級」とは、炭素数1〜5、好ましくは、炭素数1〜3を有するものを表す。 For this reason, it is generally desirable that the aromatic ring constituting the aryl group comprises no more than two aromatic rings consisting of 5-membered or 6-membered rings. Further, the “lower” in the lower alkyl group, lower haloalkyl group and lower alkoxy group of the substituent which may be substituted on the aryl group has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. Represents a thing.
これらの点からR1およびR2によって表される置換されていてもよいアリール基としては、好ましくは、次のものが挙げられる。(1)フェニル基、ナフチル基、チエニル基 、ピリジル基、ビフェニル基、アンスラニル基等のアリール基;(2)トリル基、2−メチルフェニル基、3−メチルフェニル基、4−メチルフェニル基、2,3−ジメチルフェニル基、2,4−ジメチルフェニル基、2,5−ジメチルフェニル基、2,6−ジメチルフェニル基、3,4−ジメチルフェニル基、3,5−ジメチルフェニル基、3,6−ジメチルフェニル基、2,3,4−トリメチルフェニル基、2,3,5−トリメチルフェニル基、2,3,6−トリメチルフェニル基、2,4,5−トリメチルフェニル基、2,4,6−トリメチルフェニル基、3,4,5−トリメチルフェニル基、2−エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ヘキシルフェニル基、シクロヘキシルフェニル基、オクチルフェニル基、2−メチル−1−ナフチル基、3−メチル−1−ナフチル基、4−メチル−1−ナフチル基、5−メチル−1−ナフチル基、6−メチル−1−ナフチル基、7−メチル−1−ナフチル基、8−メチル−1−ナフチル基、1−メチル−2−ナフチル基、3−メチル−2−ナフチル基、4−メチル−2−ナフチル基、5−メチル−2−ナフチル基、6−メチル−2−ナフチル基、7−メチル−2−ナフチル基、8−メチル−2−ナフチル基、2−エチル−1−ナフチル基等の低級アルキル基により置換されたアリール基;(3)トリフルオロメチルフェニル基、トリフルオロエチルフェニル基等の低級ハロアルキル基が置換したアリール基;(4)3−メトキシフェニル基、4−メトキシフェニル基、2,3−ジメトキシフェニル基、2,4−ジメトキシフェニル基、2,5−ジメトキシフェニル基、2,6−ジメトキシフェニル基、3,4−ジメトキシフェニル基、3,5−ジメトキシフェニル基、3,6−ジメトキシフェニル基、2,3,4−トリメトキシフェニル基、2,3,5−トリメトキシフェニル基、2,3,6−トリメトキシフェニル基、2,4,5−トリメトキシフェニル基、2,4,6−トリメトキシフェニル基、3,4,5−トリメトキシフェニル基、2−エトキシフェニル基、プロポキシフェニル基、2−メトキシ−1−ナフチル基、3−メトキシ−1−ナフチル基、4−メトキシ−1−ナフチル基、5−メトキシ−1−ナフチル基、6−メトキシ−1−ナフチル基、7−メトキシ−1−ナフチル基、8−メトキシ−1−ナフチル基、1−メトキシ−2−ナフチル基、3−メトキシ−2−ナフチル基、4−メトキシ−2−ナフチル基、5−メトキシ−2−ナフチル基、6−メトキシ−2−ナフチル基、7−メトキシ−2−ナフチル基、8−メトキシ−2−ナフチル基、2−エトキシ−1−ナフチル基等の低級アルコキシ基により置換されたアリール基;(5)フェノール基、ナフトール基、クレゾール基等の水酸基により置換されたアリール基;(6)クロロフェニル基、ジクロロフェニル基、トリクロロフェニル基、ブロモフェニル基、ジブロモフェニル基、ヨードフェニル基、フルオロフェニル基、ジフルオロフェニル基、トリフルオロフェニル基、テトラフルオロフェニル基、ペンタフルオロフェニル基等のハロゲン原子により置換されたアリール基等が挙げられるが、これらに限定されるものではない。 From these points, the optionally substituted aryl group represented by R 1 and R 2 preferably includes the following. (1) a phenyl group, a naphthyl group, a thienyl group, pyridine group, a biphenyl group, an aryl group such as anthranyl group; (2) a tolyl group, a 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3, 6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,4 6-trimethylphenyl, 3,4,5-trimethylphenyl, 2-ethylphenyl, propylphenyl, butylphenyl, hexylphenyl, cyclo Hexylphenyl group, octylphenyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1- Naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl group, 5- Substituted by lower alkyl groups such as methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, 2-ethyl-1-naphthyl group (3) aryl groups substituted by lower haloalkyl groups such as trifluoromethylphenyl group and trifluoroethylphenyl group; (4) 3-methoxyphenyl group, 4-methoxyphenyl group, , 3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,6 -Dimethoxyphenyl group, 2,3,4-trimethoxyphenyl group, 2,3,5-trimethoxyphenyl group, 2,3,6-trimethoxyphenyl group, 2,4,5-trimethoxyphenyl group, 2 , 4,6-trimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 2-ethoxyphenyl group, propoxyphenyl group, 2-methoxy-1-naphthyl group, 3-methoxy-1-naphthyl group, 4 -Methoxy-1-naphthyl group, 5-methoxy-1-naphthyl group, 6-methoxy-1-naphthyl group, 7-methoxy-1-naphthyl group, 8-methoxy- -Naphthyl group, 1-methoxy-2-naphthyl group, 3-methoxy-2-naphthyl group, 4-methoxy-2-naphthyl group, 5-methoxy-2-naphthyl group, 6-methoxy-2-naphthyl group, 7 -Aryl groups substituted by lower alkoxy groups such as methoxy-2-naphthyl group, 8-methoxy-2-naphthyl group, 2-ethoxy-1-naphthyl group; (5) phenol group, naphthol group, cresol group, etc. Aryl group substituted by hydroxyl group; (6) chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, dibromophenyl group, iodophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group , Aryl groups substituted by halogen atoms such as pentafluorophenyl groups, etc. However, it is not limited to these.
本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩をビルディングブロック剤として用いる点から好ましいR1およびR2は、フェニル基、トリル基、ナフチル基であり、特に好ましいのは、フェニル基およびトリル基であり、その中でもフェニル基が好ましい。R 1 and R 2 are preferably a phenyl group, a tolyl group, and a naphthyl group from the viewpoint of using the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention as a building block agent, and particularly preferred are a phenyl group and a tolyl Of these, a phenyl group is preferred.
なお、本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を表す上記一般式(I)において、R1およびR2で表されるアリール基は、一般に、芳香環を構成する炭素原子に結合手を有し、該結合手を介してS(硫黄原子)に結合している。In the above general formula (I) representing the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention, the aryl group represented by R 1 and R 2 is generally bonded to the carbon atom constituting the aromatic ring. It has a hand and is bonded to S (sulfur atom) through the bond.
なお、本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を表す上記一般式(I)において、Xーは、対イオンを構成する陰イオン基を表す。該陰イオン基としては、トリフルオロメタンスルホニル基、テトラフルオロボレート基、パーフルオロアルカンスルホニル基、アルカンスルホニル基、テトラアリールボレート基、過塩素酸基、ハロゲン(フッ素、塩素、臭素、もしくはヨウ素)イオン、またはヘキサフルオロリン酸基などを例示することができる。 In the above general formula (I) representing the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention, X− represents an anionic group constituting a counter ion. Examples of the anionic group include a trifluoromethanesulfonyl group, a tetrafluoroborate group, a perfluoroalkanesulfonyl group, an alkanesulfonyl group, a tetraarylborate group, a perchloric acid group, a halogen (fluorine, chlorine, bromine, or iodine) ion, Or a hexafluorophosphate group etc. can be illustrated.
実用上好ましい陰イオン基の例としては、トリフルオロメタンスルホニル基(OTf-)(Tfはトリフラート基を示す)やテトラフルオロボレート基(BF4 -)が挙げられる。Examples of anion groups that are practically preferable include a trifluoromethanesulfonyl group (OTf − ) (Tf represents a triflate group) and a tetrafluoroborate group (BF 4 − ).
かくして、本発明の特に好ましいβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩としては、(3,3,3-トリフルオロプロペン-1-イル)-フェニルトルイルスルホニウム トリフラート、(3,3,3-トリフルオロプロペン-1-イル)-ジフェニルスルホニウム トリフラート、(3,3,3-トリフルオロプロペン-1-イル)-(2-ナフチル)フェニルスルホニウム トリフラート、(3,3,3-トリフルオロプロペン-1-イル)-フェニル(2-ピリジル)スルホニウム トリフラート、(3,3,3-トリフルオロプロペン-1-イル)-フェニルトルイルスルホニウム テトラフルオロボレートを挙げることができる。 Thus, particularly preferred β- (trifluoromethyl) vinyldiarylsulfonium salts of the present invention include (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate, (3,3,3-triflate). Fluoropropen-1-yl) -diphenylsulfonium triflate, (3,3,3-trifluoropropen-1-yl)-(2-naphthyl) phenylsulfonium triflate, (3,3,3-trifluoropropene-1- Yl) -phenyl (2-pyridyl) sulfonium triflate, (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium tetrafluoroborate.
本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩は、次の反応式(VI)及び反応式(VII)で表される反応を用いて、製造することができる。 The β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention can be produced using a reaction represented by the following reaction formula (VI) and reaction formula (VII).
上記反応式中、R1およびR2は、式(I)に関連して既に詳述したものと同じである。
また、R3は、R1およびR2と独立して選ばれ、低級アルキル基、低級ハロアルキル基、低級アルコキシ基または水酸基により置換されていてもよいアリール基を表す。R3で表されるアリール基を構成する芳香環としては、一般に、5員環または6員環からなる芳香環が2つ以内からなるものが望ましい。また、R3に関連して、低級アルキル基、低級ハロアルキル基、低級アルコキシ基における「低級」とは、炭素数1〜5、好ましくは炭素数1〜3を有するものを表す。かくして、実用上、R3として好ましいのはフェニル基またはトリル基であり、フェニル基が特に好ましい。In the above reaction scheme, R 1 and R 2 are the same as those already described in detail in connection with formula (I).
R 3 is independently selected from R 1 and R 2 and represents a lower alkyl group, a lower haloalkyl group, a lower alkoxy group or an aryl group optionally substituted by a hydroxyl group. As the aromatic ring constituting the aryl group represented by R 3 , it is generally desirable that the aromatic ring consist of no more than two 5-membered or 6-membered aromatic rings. In relation to R 3 , “lower” in the lower alkyl group, lower haloalkyl group, and lower alkoxy group represents one having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. Thus, practically, R 3 is preferably a phenyl group or a tolyl group, and a phenyl group is particularly preferable.
上記反応式中、X-は対イオンを構成する陰イオン基を表し、Yはハロゲン基を表す。また、波線はシス体もしくはトランス体またはそれらの混合物であることを表す。In the above reaction formula, X − represents an anion group constituting a counter ion, and Y represents a halogen group. Moreover, a wavy line represents that it is a cis body or a trans body, or those mixtures.
上記の反応式(VI)で表されるように、式(VIa)で表される2−ブロモ−3,3,3−トリフルオロプロペンと、一般式(VIb)で表される芳香族チオールとを、常圧下、80℃〜150℃で反応させて、一般式(VIc)で表されるトリフルオロメチルを含有するビニルスルフィドを生成することができる。 As represented by the above reaction formula (VI), 2-bromo-3,3,3-trifluoropropene represented by the formula (VIa) and an aromatic thiol represented by the general formula (VIb) Can be reacted at 80 ° C. to 150 ° C. under normal pressure to produce vinyl sulfide containing trifluoromethyl represented by the general formula (VIc).
さらに、上記の反応式(VII)で表されるように、該生成されたビニルスルフィドと、一般式(VIIa)で表されるハロゲン化ジアリールとを、常圧下、80℃〜150℃でハロゲン系非極性溶媒下に反応させることにより、一般式(I)で表される本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を生成することができる。 Further, as represented by the above reaction formula (VII), the produced vinyl sulfide and the diaryl halide represented by the general formula (VIIa) are halogenated at 80 ° C. to 150 ° C. under normal pressure. By reacting in a nonpolar solvent, the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention represented by the general formula (I) can be produced.
さらに詳細には、反応式(VI)において、β−(トリフルオロメチル)ビニルジアリールスルフィドは、トランス体を主生成物(トランス体:シス体=約9:1)とする混合物として得られる。 More specifically, in the reaction formula (VI), β- (trifluoromethyl) vinyl diaryl sulfide is obtained as a mixture having the trans isomer as the main product (trans isomer: cis isomer = about 9: 1).
次に、反応式(VII)において、式(I)で表されるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩は、式(VIc)で表されるトランス体のビニルスルフィドからは、トランス体が得られ、式(VIc)で表されるシス体のビニルスルフィドからは、トランス体およびシス体の混合物が得られる。 Next, in the reaction formula (VII), the β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the formula (I) has a trans isomer from the vinyl sulfide of the trans isomer represented by the formula (VIc). A mixture of the trans isomer and the cis isomer can be obtained from the cis vinyl sulfide represented by the formula (VIc).
このようなことから、反応式(VI)で表されるβ−(トリフルオロメチル)ビニルジアリールスルフィド(トランス体:シス=約9:1)を用いて反応式(VII)の反応を行った場合、式(I)で表されるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩が、トランス体を主成分として得られることとなる。 Therefore, when reaction of reaction formula (VII) is performed using β- (trifluoromethyl) vinyl diaryl sulfide (trans form: cis = about 9: 1) represented by reaction formula (VI) The β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the formula (I) can be obtained with the trans isomer as the main component.
なお、式(I)で表されるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩は、合成中間体としての反応性に関しては、シス体とトランス体との差がほとんどない。 The β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the formula (I) has almost no difference between the cis form and the trans form in terms of reactivity as a synthetic intermediate.
このことに加えて、本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を、合成中間体(例えば、ビルディングブロック剤)として各種の化合物を合成する場合には、主としてトランス体が用いられることになるが、下記の各反応式から理解されるように、シス体およびトランス体のいずれを用いても、得られる生成物に変わりは無い。 In addition to this, in the case of synthesizing various compounds using the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention as a synthetic intermediate (for example, a building block agent), a trans isomer is mainly used. However, as will be understood from each of the following reaction formulas, the product to be obtained remains the same regardless of whether the cis isomer or the trans isomer is used.
本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩は、各種の目的に使用することができるが、特にビルディングブロック剤として、各種の有用化合物、例えば、アジリジン化合物、アミド化合物、イミド化合物、アルコキシ化合物およびリン化合物等の製造に使用することができ、得られるアジリジン化合物等は、トリフルオロメチル基を含有するが、原料となるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を構成するアリール基は残存していないという特徴的な構造を有する。 Although the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention can be used for various purposes, various useful compounds such as aziridine compounds, amide compounds, imide compounds, alkoxy compounds can be used as building block agents. The aziridine compound and the like that can be used for the production of a compound and a phosphorus compound contain a trifluoromethyl group, but the aryl group that constitutes the starting β- (trifluoromethyl) vinyldiarylsulfonium salt is It has a characteristic structure that it does not remain.
(アジリジン化合物の製造方法)
例えば、トリフルオロメチル基を含有するアジリジン化合物は、一般式(I)で表されるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を、第1級アミン化合物と反応させて、製造することができる。この製造は、例えば、次の式(VIII)で表すことができる。(Method for producing aziridine compound)
For example, an aziridine compound containing a trifluoromethyl group can be produced by reacting a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) with a primary amine compound. . This production can be represented, for example, by the following formula (VIII).
式(VIII)において、第1級アミン化合物は一般式(VIIIa)で表され、得られるアジリジン化合物は一般式(VIIIb)で表されている。また、反応条件としては、常圧下、常温で、十分に反応を進行させることができる。 In the formula (VIII), the primary amine compound is represented by the general formula (VIIIa), and the resulting aziridine compound is represented by the general formula (VIIIb). As reaction conditions, the reaction can sufficiently proceed at normal temperature under normal pressure.
上記の反応式において、R1、R2およびX-は上記の一般式(I)で定義したものと同じである。また、R4は、従来より知られた合成または天然由来の各種の第1級アミン(アミノ化合物)を構成する官能基または原子団を表す。In the above reaction formula, R 1 , R 2 and X − are the same as those defined in the general formula (I). R 4 represents a functional group or an atomic group constituting various primary amines (amino compounds) derived from conventionally known synthetic or natural origin.
すなわち、本発明において使用できる第1級アミンの具体例としては、特に限定されるものではないが、例えば、N,N−ジエチルエチレンジアミン、グリシンエチル、メチルアミン、エチルアミン、O−エチルヒドロキシルアミン、1−プロピルアミン、2−プロピルアミン、3−メトキシプロピルアミン、n−ブチルアミン、sec−ブチルアミン、tert−ブチルアミン、iso−ブチルアミン、n−ペンチルアミン、sec−ペンチルアミン、neo−ペンチルアミン、3−ペンチルアミン、ヘプチン、2−メチル−1−ブチルアミン、1−ヘキシルアミン、2−ヘキシルアミン、3−ヘキシルアミン、4−メチル−1−ペンチルアミン、4−メチル−2−ペンチルアミン、2−メチル−3−ペンチルアミン、2−エチル−1−ブチルアミン、2−エチル−2−ブチルアミン、3−エチル−2−ブチルアミン、3−エチル−2−ブチルアミン、n−ヘプチルアミン、2−フェニルエチルアミン、 2−フェニルエチルアミン、2−メチル−1−ヘキシルアミン、3−メチル−1−ヘキシルアミン、4−メチル−1−ヘキシルアミン、5−メチル−1−ヘキシルアミン、2−エチル−1−ペンチルアミン、3−エチル−1−ペンチルアミン、4−エチル−1−ペンチルアミン、n−オクチルアミン、2−メチル−1−ヘプチルアミン、3−メチル−1−ヘプチルアミン、4−メチル−1−ヘプチルアミン、5−メチル−1−ヘプチルアミン、6−メチル−1−ヘプチルアミン、2−エチル−1−ヘキシルアミン、3−エチル−1−ヘキシルアミン、4−エチル−1−ヘキシルアミン、ノニルアミン、デシルアミン、ウンデシルアミン、ドデシルアミン、トリデシルアミン、シクロヘプタンアミン、シクロペンチルアミン、シクロヘキシルアミン、シクロオクチルアミン、テトラヒドロフラン‐2‐メタンアミン、チオ硫酸水素S‐(2‐アミノエチル)、2‐アミノエチルホスホン酸、ミダフルル、3‐アミノプロピルメチルジエトキシシランなどのアルキル基にヘテロ原子を含有するか、またはヘテロ原子を含有しないアルキルアミン;ベンジルアミン、2−フェニルエタンアミン、3,5−ジメチルベンジルアミン、3,5−ビス(トリフルオロメチル)ベンジルアミン、1−ナフタレンメチルアミン、p−トルエンスルホンアミド、o−トルイジン、m−トルイジン、アニリン、2,4‐ジメチルアニリン、3,4−ジメチルアニリン、3,5―ビス(トリフルオロメチル)アニリン、2−クロロアニリン、2,4,6−トリクロロアニリン、2‐メトキシ‐4‐ニトロ−5−クロロアニリン、メトキシアニリン、エトキシアニリン、4‐[2‐(メチルアミノ)プロピル]アニリン、2‐フルオロベンジルアミン、4‐ブロモベンジルアミン、3,4‐ジメトキシベンジルアミン、4‐フェニルブチルアミン、2‐フェニルシクロプロパン‐1‐アミン、5‐メチル‐o‐フェネチジン、4‐クロロフェネチルアミン、2‐クロロベンジルアミン、α‐アミノアセトフェノン、α‐アミノ‐α‐フェニルアセトフェノン、1‐ナフチルアミン、2‐ナフチルアミン、1‐ナフチルメチルアミン、ナホミン、2‐アミノビフェニル、4‐アミノビフェニル、ペントレックス、ソアミン、フェンテルミン、クロルフェンテルミン、クロルテルミン、1,3‐ベンゾジオキソール‐5‐メタンアミン、ピペリジン‐1‐エタンアミン、4‐メトキシ‐1H‐インドール‐3‐エタンアミン、9‐アミノアクリジン、2‐アミノピリミジン、4‐メチルチアゾール‐2‐アミン、2‐アミノプリン、2,6‐ジメチルピリミジン‐4‐アミン、2‐アミノ‐4,6‐ジメチルピリミジン、3‐(アミノメチル)ピリジン、アダマンタン‐2‐アミン、2‐クロロ‐9‐メチル‐9H‐プリン‐6‐アミン、フルフリルアミン、9H‐フルオレン‐3‐アミン、4‐アミノ‐9H‐フルオレン、ジベンゾイルチアミン、5‐アミノ‐1H‐ベンゾイミダゾール、1H‐ベンゾイミダゾール‐2‐アミン、2‐アミノアントラセン、1‐アミノアントラセン、1‐アミノピレン、2‐アミノチオフェン、1‐(フェニルアゾ)‐2‐ナフタレンアミン、9‐アミノアクリジン、シペナミン、フルナミン、ハロナミン、5‐ニトロピリミジン‐2‐アミン、4‐アミノビフェニル、2‐アミノチアゾール、セロトニン、ヒスタミン、トリフルタミン、チラミン、ベンズヒドリルアミン、アデニン、プリマキン、ゾキサゾラミン、キシロプロパミン、ベタゾール、タクリン、エチフェルミン、ベナンセリン、ノルフェニレフリン、クリセン‐6‐アミン、2‐クリセンアミン、キナゾシン、キシノミリン、4‐メチルアミノレックス、8‐アザアデニン、デスメチルクロルジアゼポキシド、1‐(3‐アミノプロピル)シラトラン、アゼペキソール、アセナフテン‐5‐アミン、3‐メチルピリジン‐2‐アミン、エピナスチン、リルゾール、d‐アンフェタミン、l‐アンフェタミン、プシコフラニン、d―sec―ブチルアミン、ノルアドレナリン、ジモキサミン、フルクトサミン、メマンチン、ノルロリン、葉酸、メタラミノール、アデノシン、ツベルシジン、コルジセピン、エピヒドリンアミン、6‐アミノプテリジンなどの単環もしくは複素環からなる芳香環にヘテロ原子を含有するか、またはヘテロ原子を含有しない芳香族アミン;グリシン、トリプトファン、メチオニン、フェニルアラニン、トレオニン、L-バリン、イソロイシン、L-ロイシン、ヒスチジン、L-アラニン、アルギニン、アスパラギン、アスパラギン酸、L-セリン、システイン、グルタミン、L-グルタミン酸、チロシンなどのアミノ酸などが挙げられる。 That is, specific examples of the primary amine that can be used in the present invention are not particularly limited. For example, N, N-diethylethylenediamine, glycineethyl, methylamine, ethylamine, O-ethylhydroxylamine, 1 -Propylamine, 2-propylamine, 3-methoxypropylamine, n-butylamine, sec-butylamine, tert-butylamine, iso-butylamine, n-pentylamine, sec-pentylamine, neo-pentylamine, 3-pentylamine , Heptine, 2-methyl-1-butylamine, 1-hexylamine, 2-hexylamine, 3-hexylamine, 4-methyl-1-pentylamine, 4-methyl-2-pentylamine, 2-methyl-3- Pentylamine, 2-ethyl-1-but Ruamine, 2-ethyl-2-butylamine, 3-ethyl-2-butylamine, 3-ethyl-2-butylamine, n-heptylamine, 2-phenylethylamine, 2-phenylethylamine, 2-methyl-1-hexylamine, 3-methyl-1-hexylamine, 4-methyl-1-hexylamine, 5-methyl-1-hexylamine, 2-ethyl-1-pentylamine, 3-ethyl-1-pentylamine, 4-ethyl-1 -Pentylamine, n-octylamine, 2-methyl-1-heptylamine, 3-methyl-1-heptylamine, 4-methyl-1-heptylamine, 5-methyl-1-heptylamine, 6-methyl-1 -Heptylamine, 2-ethyl-1-hexylamine, 3-ethyl-1-hexylamine, 4-ethyl-1-hexyl Min, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, cycloheptaneamine, cyclopentylamine, cyclohexylamine, cyclooctylamine, tetrahydrofuran-2-methanamine, hydrogen thiosulfate S- (2-aminoethyl), 2 -Alkylamines containing or not containing heteroatoms in alkyl groups such as aminoethylphosphonic acid, midafluur, 3-aminopropylmethyldiethoxysilane; benzylamine, 2-phenylethanamine, 3,5- Dimethylbenzylamine, 3,5-bis (trifluoromethyl) benzylamine, 1-naphthalenemethylamine, p-toluenesulfonamide, o-toluidine, m-toluidine, aniline, 2,4-dimethylaniline, , 4-dimethylaniline, 3,5-bis (trifluoromethyl) aniline, 2-chloroaniline, 2,4,6-trichloroaniline, 2-methoxy-4-nitro-5-chloroaniline, methoxyaniline, ethoxyaniline 4- [2- (methylamino) propyl] aniline, 2-fluorobenzylamine, 4-bromobenzylamine, 3,4-dimethoxybenzylamine, 4-phenylbutylamine, 2-phenylcyclopropan-1-amine, 5 -Methyl-o-phenetidine, 4-chlorophenethylamine, 2-chlorobenzylamine, α-aminoacetophenone, α-amino-α-phenylacetophenone, 1-naphthylamine, 2-naphthylamine, 1-naphthylmethylamine, nafomin, 2- Aminobiphenyl, 4-aminobiphenyl , Pentrex, soamine, phentermine, chlorphentermine, chlortermine, 1,3-benzodioxol-5-methanamine, piperidine-1-ethanamine, 4-methoxy-1H-indole-3-ethanamine, 9- Aminoacridine, 2-aminopyrimidine, 4-methylthiazol-2-amine, 2-aminopurine, 2,6-dimethylpyrimidine-4-amine, 2-amino-4,6-dimethylpyrimidine, 3- (aminomethyl) Pyridine, adamantane-2-amine, 2-chloro-9-methyl-9H-purine-6-amine, furfurylamine, 9H-fluorene-3-amine, 4-amino-9H-fluorene, dibenzoylthiamine, 5-amino -1H-benzimidazole, 1H-benzimidazol-2-amine 2-aminoanthracene, 1-aminoanthracene, 1-aminopyrene, 2-aminothiophene, 1- (phenylazo) -2-naphthaleneamine, 9-aminoacridine, cipenamine, flunamine, halonamamine, 5-nitropyrimidin-2-amine, 4-aminobiphenyl, 2-aminothiazole, serotonin, histamine, triflutamine, tyramine, benzhydrylamine, adenine, primaquine, zoxazolamine, xylpropamine, betazole, tacrine, ethifermine, benanserin, norphenylephrine, chrysen-6-amine, 2-chrysenamine, quinazosin, xinomiline, 4-methylaminorex, 8-azaadenine, desmethylchlordiazepoxide, 1- (3-aminopropyl) silatrane, azepexol Acenaphthen-5-amine, 3-methylpyridin-2-amine, epinastine, riluzole, d-amphetamine, l-amphetamine, psicofuranine, d-sec-butylamine, noradrenaline, dimoxamine, fructosamine, memantine, norloline, folic acid, metallaminol, adenosine , Tubercidine, cordycepin, epihydrinamine, 6-aminopteridine and other aromatic rings containing a heteroatom or non-heteroatom such as glycine, tryptophan, methionine, phenylalanine , Threonine, L-valine, isoleucine, L-leucine, histidine, L-alanine, arginine, asparagine, aspartic acid, L-serine, cysteine, glutamine, L-glutamic acid, thi Such as amino acids, such as Shin and the like.
特に、上述したようなアルキルアミン、芳香族アミンまたはアミノ酸の中で上記式(VIIIa)におけるR4で表される官能基または原子団を構成する炭素数が12以下の第1級アミンが、一般的な溶媒に対して溶け易く製造(合成)が容易であるという観点から好ましく、例えば、ベンジルアミン、2−フェニルエタンアミン、3,5−ジメチルベンジルアミン、3,5−ビス(トリフルオロメチル)ベンジルアミン、1−ナフタレンメチルアミン、N,N−ジエチルエチレンジアミン、グリシンエチル、p−トルエンスルホンアミドなどを好ましい例として挙げることができる。In particular, among the alkylamines, aromatic amines or amino acids as described above, primary amines having 12 or less carbon atoms constituting the functional group or atomic group represented by R 4 in the above formula (VIIIa) are generally used. From the viewpoint of being easily soluble in a typical solvent and easy to produce (synthesize), for example, benzylamine, 2-phenylethanamine, 3,5-dimethylbenzylamine, 3,5-bis (trifluoromethyl) Preferred examples include benzylamine, 1-naphthalenemethylamine, N, N-diethylethylenediamine, glycine ethyl, p-toluenesulfonamide, and the like.
また、上述したような第1級アミンのうち、光学活性を有するものを用いれば、トリフルオロメチル基を含有する光学活性アジリジン化合物の合成が可能となる。すなわち、光学活性を有する第1級アミンを用いることにより、R体およびS体のそれぞれのトリフルオロメチル基を含有する光学活性アジリジン化合物を合成することができる。 Moreover, if the primary amine as described above has optical activity, an optically active aziridine compound containing a trifluoromethyl group can be synthesized. That is, by using a primary amine having optical activity, it is possible to synthesize optically active aziridine compounds containing trifluoromethyl groups of R and S isomers.
上記式(VIII)から理解されるように、本発明により得られるアジリジン化合物は、その原料となるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を構成するアリール基(すなわち、R1およびR2)は、いずれも残存しないという特徴を有する。As understood from the above formula (VIII), the aziridine compound obtained by the present invention is an aryl group constituting the β- (trifluoromethyl) vinyldiarylsulfonium salt as a raw material (that is, R 1 and R 2 ). Has a feature that none of them remain.
このため、従来のトリフルオロメチル基を含有するアジリジン合成(例えば、特開2009−512687、WO2006−71609、Izvestiya Akademii Nauk, Seriya Khimicheskaya, (2) 282-4, (1994)など)では、トリフルオロメチル基を導入する際に、中間体に含まれるトリフルオロメチル基以外の官能基(原子団)が残存してしまうが、本発明によれば、トリフルオロメチル基を含む三炭素からなるオレフィン部位を他の化合物に一挙に導入できるという従来例のない全く新規な反応を行うことができる。さらに、常圧下、常温で十分に反応が進むという、従来にない容易な反応条件で、反応させることができる。 For this reason, in conventional aziridine synthesis containing a trifluoromethyl group (for example, JP2009-512687, WO2006-71609, Izvestiya Akademii Nauk, Seriya Khimicheskaya, (2) 282-4, (1994), etc.) When a methyl group is introduced, functional groups (atomic groups) other than the trifluoromethyl group contained in the intermediate remain, but according to the present invention, an olefin moiety consisting of three carbons containing a trifluoromethyl group Can be introduced into other compounds all at once, and a completely new reaction that does not have a conventional example can be performed. Furthermore, the reaction can be carried out under normal and easy reaction conditions that the reaction proceeds sufficiently at normal temperature under normal pressure.
(アミド化合物の製造方法)
また、例えば、トリフルオロメチル基を含有するアミド化合物は、一般式(I)で表されるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を、カルボン酸アミド、スルホンアミド等のアミドと反応させて、製造することができる。この製造は、例えば、次の式(IX)及び(X)で表すことができ、各々の式は、アミドとして、カルボン酸アミド及びスルホンアミドの場合を示している。(Method for producing amide compound)
For example, an amide compound containing a trifluoromethyl group is obtained by reacting a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) with an amide such as a carboxylic acid amide or a sulfonamide. Can be manufactured. This preparation can be represented, for example, by the following formulas (IX) and (X), each formula showing the case of a carboxylic acid amide and a sulfonamide as the amide.
式(IX)において、カルボン酸アミドは、一般式(IXa)で表され、得られるアミド化合物は一般式(IXb)で表されている。また、式(X)において、スルホンアミドは、一般式(Xa)で表され、得られるアミド化合物は一般式(Xb)で表されている。また、反応条件に関しては、多くの場合、常圧下、常温で十分に反応を進行させることができる。 In the formula (IX), the carboxylic acid amide is represented by the general formula (IXa), and the resulting amide compound is represented by the general formula (IXb). In the formula (X), the sulfonamide is represented by the general formula (Xa), and the resulting amide compound is represented by the general formula (Xb). As for the reaction conditions, in many cases, the reaction can sufficiently proceed at normal temperature under normal pressure.
上記の反応式において、R1、R2およびX-は上記の一般式(I)にて定義したものと同じである。R4、R5およびR6は、従来より知られた合成または天然由来の各種のアミドを構成する官能基または原子団を表す。In the above reaction formula, R 1 , R 2 and X − are the same as those defined in the above general formula (I). R 4 , R 5, and R 6 represent functional groups or atomic groups constituting various amides derived from conventionally known synthetic or natural sources.
すなわち、本発明において使用できるアミドの具体例としては、特に限定されるものではないが、例えば、イサチン、ピバルアミド、ベンズアミド、N-フェニルヘキサンアミド、N-フェニルシクロヘキサンカルボキサミド、2‐ブロモベンズアミド、4‐ブロモベンズアミド、3‐クロロプロピオンアミド、N‐メチルプロピオンアミド、2‐クロロニコチンアミド、2-クロロ-N-(4-クロロフェニル)アセトアミド、6‐クロロニコチンアミド、ジブロモアセトアミド、1‐ナフタレンアセトアミド、N‐(7‐ヒドロキシ‐9H‐フルオレン‐2‐イル)アセトアミド、N‐(5‐ヒドロキシ‐9H‐フルオレン‐2‐イル)アセトアミド、N‐(3‐ヒドロキシ‐9H‐フルオレン‐2‐イル)アセトアミド、デカンアミド、N‐メチルデカンアミド、N,N‐ジメチルデカンアミド、ドデカンアミド、N,N‐ジエチルドデカンアミド、オクタデカンアミド、N,N‐ジメチルステアロアミド、リグノセリン酸アミド、N,N‐ジメチルリグノセリン酸アミド、N‐ヒドロキシメチルカプリンアミド、N‐ヒドロキシメチルドデカンアミド、N‐ヒドロキシメチルステアリン酸アミド、N‐ヒドロキシメチルリグノセリン酸アミド、N‐[2‐[ビス(2‐ヒドロキシエチル)アミノ]エチル]ドデカンアミド、N‐[2‐[ビス(2‐ヒドロキシエチル)アミノ]エチル]ステアリン酸アミド、N‐(2‐ヒドロキシエチル)デカンアミド、N‐(2‐ヒドロキシエチル)ドデカンアミド、N‐シクロヘキシル‐5‐ニトロ‐2‐フランプロパンアミド、2,2,2‐トリフルオロ‐N‐[4‐(5‐ニトロ‐2‐フリル)‐2‐チアゾリル]アセトアミド、2‐フェニル‐3‐(5‐ニトロ‐2‐フリル)アクリルアミド、N‐[4‐[2‐(5‐ニトロ‐2‐フリル)ビニル]‐2‐チアゾリル]ホルムアミド、N-フェニルベンズアミド、N‐[(エチルニトロソアミノ)メチル]ベンズアミド、N‐(9H‐フルオレン‐2‐イル)‐N‐(テトラデカノイルオキシ)テトラデカンアミド、(R)‐N,N‐ジエチル‐2‐(1‐ナフタレニルオキシ)プロパンアミド、ホルムアミド、ジメチルホルムアミド、N‐メチルアセトアミド、サリチルアミド、クロロアセトアミド等のカルボン酸アミド;2-(トシルアミノ)エタノール、シクラミン酸ナトリウム、N-フェニルベンゼンスルホンアミド等のスルホンアミド;N,N′,N′′‐トリフェニルリン酸トリアミド、リン酸トリアミド等のリン酸アミドなどが挙げられる。 That is, specific examples of amides that can be used in the present invention are not particularly limited. For example, isatin, pivalamide, benzamide, N-phenylhexaneamide, N-phenylcyclohexanecarboxamide, 2-bromobenzamide, 4- Bromobenzamide, 3-chloropropionamide, N-methylpropionamide, 2-chloronicotinamide, 2-chloro-N- (4-chlorophenyl) acetamide, 6-chloronicotinamide, dibromoacetamide, 1-naphthaleneacetamide, N- (7-hydroxy-9H-fluoren-2-yl) acetamide, N- (5-hydroxy-9H-fluoren-2-yl) acetamide, N- (3-hydroxy-9H-fluoren-2-yl) acetamide, decanamide N-methyldecane Amide, N, N-dimethyldecanamide, dodecanamide, N, N-diethyldodecanamide, octadecanamide, N, N-dimethylstearoamide, lignoceramic acid amide, N, N-dimethyllignoceramide, N-hydroxy Methylcaprinamide, N-hydroxymethyldodecanamide, N-hydroxymethyl stearamide, N-hydroxymethyllignoceramide, N- [2- [bis (2-hydroxyethyl) amino] ethyl] dodecanamide, N- [2- [Bis (2-hydroxyethyl) amino] ethyl] stearic amide, N- (2-hydroxyethyl) decanamide, N- (2-hydroxyethyl) dodecanamide, N-cyclohexyl-5-nitro-2- Furanpropanamide, 2,2,2-trifluoro -N- [4- (5-nitro-2-furyl) -2-thiazolyl] acetamide, 2-phenyl-3- (5-nitro-2-furyl) acrylamide, N- [4- [2- (5- Nitro-2-furyl) vinyl] -2-thiazolyl] formamide, N-phenylbenzamide, N-[(ethylnitrosoamino) methyl] benzamide, N- (9H-fluoren-2-yl) -N- (tetradecanoyl) Oxy) tetradecanamide, (R) -N, N-diethyl-2- (1-naphthalenyloxy) propanamide, formamide, dimethylformamide, N-methylacetamide, salicylamide, chloroacetamide and other carboxylic acid amides; 2 Sulfonamides such as-(tosylamino) ethanol, sodium cyclamate, N-phenylbenzenesulfonamide N, N ', N' '- triphenyl triamide, phosphoric acid amides such as triamide phosphoric acid.
また、上記の一般式(IXa)および(Xa)で表されるアミドは、鎖状または環状のいずれでもよいが、環状のアミドが、一般的に取り扱いが容易であるという観点から好ましい。さらに、上述したようなアミドの中で上記式(IXa)および(Xa)におけるR4、R5およびR6で表される官能基または原子団を構成する炭素数が12以下のアミドが、一般的な溶媒に対して溶け易く製造(合成)が容易であるという観点から好ましく、例えば、イサチン、2−(トシルアミノ)エタノールなどを好ましい例として挙げることができる。The amides represented by the above general formulas (IXa) and (Xa) may be either chain or cyclic, but cyclic amides are preferred from the viewpoint that they are generally easy to handle. Furthermore, among the amides as described above, amides having 12 or less carbon atoms constituting the functional groups or atomic groups represented by R 4 , R 5 and R 6 in the above formulas (IXa) and (Xa) From the viewpoint of being easily soluble in a typical solvent and easy to produce (synthesize), for example, isatin, 2- (tosylamino) ethanol and the like can be mentioned as preferred examples.
また、上述したようなアミドのうち、光学活性を有するものを用いれば、トリフルオロメチル基を含有する光学活性アミド化合物の合成が可能となる。すなわち、光学活性を有するアミドを用いることにより、R体およびS体のそれぞれのトリフルオロメチル基を含有する光学活性アミド化合物を合成することができる。 In addition, if an amide having optical activity is used among the amides as described above, an optically active amide compound containing a trifluoromethyl group can be synthesized. That is, by using an amide having optical activity, it is possible to synthesize an optically active amide compound containing each trifluoromethyl group of R-form and S-form.
(イミド化合物の製造方法)
また、例えば、トリフルオロメチル基を含有するイミド化合物は、一般式(I)で表されるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を、イミドと反応させて、製造することができる。この製造は、例えば、次の式(XI)で表すことができる。(Method for producing imide compound)
Moreover, for example, an imide compound containing a trifluoromethyl group can be produced by reacting a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) with an imide. This manufacture can be represented by the following formula (XI), for example.
式(XI)において、イミドは、一般式(XIa)で表され、得られるイミド化合物は一般式(XIb)で表されている。また、反応条件に関しては、多くの場合、常圧下、常温で十分に反応を進行させることができる。 In formula (XI), the imide is represented by general formula (XIa), and the resulting imide compound is represented by general formula (XIb). As for the reaction conditions, in many cases, the reaction can sufficiently proceed at normal temperature under normal pressure.
上記の反応式において、R1、R2およびX-は上記の一般式(I)にて定義したものと同じである。R4およびR5は、従来より知られた合成または天然由来の各種のイミドを構成する官能基または原子団を表す。また、Mは、水素原子またはアルカリ金属原子を表す。In the above reaction formula, R 1 , R 2 and X − are the same as those defined in the above general formula (I). R 4 and R 5 each represent a functional group or an atomic group constituting various conventionally known synthetic or natural imides. M represents a hydrogen atom or an alkali metal atom.
すなわち、本発明において使用できるイミドの具体例としては、特に限定されるものではないが、例えば、イミノ二酢酸、アセチル(ベンゾイル)アミン、ビス(シクロヘキサンカルボニル)アミン、N-シクロペンチルジアセトアミド、アセチル(ベンゾイル)(3-クロロプロパノイル)アミン等の鎖状のイミド;フタルイミド、ナフタルイミド、マレイミド、N‐ポタシオフタルイミド、4‐ニトロフタルイミド、N-ヒドロキシフタルイミド、1,4,5,8‐テトラヒドロ‐4a,8a‐ナフタレンジカルボイミド、3,6‐ジヒドロキシフタルイミド、2‐(4‐メチルフェニル)‐3‐(4‐クロロフェニル)マレインイミド、2,3‐ジフェニルマレインイミド、2‐(3‐メトキシフェニル)‐3‐フェニルマレインイミド、2‐(4‐クロロフェニル)‐3‐フェニルマレインイミド、2‐(3‐クロロフェニル)‐3‐フェニルマレインイミド、2‐(4‐ブロモフェニル)‐3‐フェニルマレインイミド、2‐(4‐フルオロフェニル)‐3‐フェニルマレインイミド、2‐(3,5‐ジメチルフェニル)‐3‐フェニルマレインイミド、3‐メトキシフェナントレン‐9,10‐ジカルボイミド、2‐メトキシフェナントレン‐9,10‐ジカルボイミド、3‐クロロフェナントレン‐9,10‐ジカルボイミド、2‐クロロフェナントレン‐9,10‐ジカルボイミド、3‐ブロモフェナントレン‐9,10‐ジカルボイミド、3‐フルオロフェナントレン‐9,10‐ジカルボイミド、2,4‐ジメチルフェナントレン‐9,10‐ジカルボイミド、3‐メトキシ‐6‐クロロフェナントレン‐9,10‐ジカルボイミド、3‐メトキシ‐9,10‐ジヒドロフェナントレン‐9,10‐ジカルボイミド、2‐メトキシ‐9,10‐ジヒドロフェナントレン‐9,10‐ジカルボイミド、3‐クロロ‐9,10‐ジヒドロフェナントレン‐9,10‐ジカルボイミド、2‐クロロ‐9,10‐ジヒドロフェナントレン‐9,10‐ジカルボイミド、3‐ブロモ‐9,10‐ジヒドロフェナントレン‐9,10‐ジカルボイミド、3‐フルオロ‐9,10‐ジヒドロフェナントレン‐9,10‐ジカルボイミド、2,4‐ジメチル‐9,10‐ジヒドロフェナントレン‐9,10‐ジカルボイミド、3‐メトキシ‐6‐クロロ‐9,10‐ジヒドロフェナントレン‐9,10‐ジカルボイミド、スクシンイミド、2,3‐ジブチルスクシンイミド、2‐クロロ‐3‐メチルスクシンイミド、2,3‐ジクロロ‐2‐メチルスクシンイミド、2,2,3,3‐テトラフルオロスクシンイミド、2,2,3,3‐テトラメチルスクシンイミド、ヘキサヒドロフタルイミド、2,3‐ジクロロマレインイミド、3‐エチルグルタジン、アジピミド、1,2,3,4‐テトラヒドロフタルイミド、3,4,5,6‐テトラヒドロフタルイミド、2‐(m‐フルオロフェニル)スクシンイミド、N‐(2,6‐ジオキソピペリジン‐3‐イル)‐5
,6‐ジヒドロ‐1,4‐ジチイン‐2,3‐ジカルボイミド、2‐(α,α,α‐トリフルオロ‐m‐トリル)スクシンイミド、3,3‐ジメチルグルタルイミド、2‐メチルスクシンイミド、グルタルイミド、3,3,4‐トリメチルピロリジン‐2,5‐ジオン、3,4‐ジブロモ‐3‐ピロリン‐2,5‐ジオン、3‐メチル‐4‐ビニル‐1H‐ピロール‐2,5‐ジオン、6‐アミノ‐1H‐ベンゾ[de]イソキノリン‐1,3(2H)‐ジオン、3‐メチル‐4‐エチル‐1H‐ピロール‐2,5‐ジオン、3aα,4,5,6,7,7aα‐ヘキサヒドロ‐2H‐イソインドール‐1,3‐ジオン、α‐メチル‐2‐エチルスクシンイミド、9H‐フルオレン‐4,5‐ジカルボイミド、ベンゼチミド、2H‐ピロロ[3,4‐c]ピリジン‐1,3‐ジオン、ピリミジン‐4,5‐ジカルボイミド、2,3‐ピリジンジカルボイミド、5,6‐ジヒドロ‐1,4‐ジチイン‐2,3‐ジカルボキシミド、5,6‐ジヒドロ‐1,4‐ジチイン‐2,3‐ジカルボキシミド等の環状のイミドなどが挙げられる。That is, specific examples of the imide that can be used in the present invention are not particularly limited. For example, iminodiacetic acid, acetyl (benzoyl) amine, bis (cyclohexanecarbonyl) amine, N-cyclopentyldiacetamide, acetyl ( Chain imides such as benzoyl) (3-chloropropanoyl) amine; phthalimide, naphthalimide, maleimide, N-potatiophthalimide, 4-nitrophthalimide, N-hydroxyphthalimide, 1,4,5,8-tetrahydro- 4a, 8a-naphthalene dicarboimide, 3,6-dihydroxyphthalimide, 2- (4-methylphenyl) -3- (4-chlorophenyl) maleimide, 2,3-diphenylmaleimide, 2- (3-methoxyphenyl) ) -3-Phenylmaleimide, 2- (4-chloro) Phenyl) -3-phenylmaleimide, 2- (3-chlorophenyl) -3-phenylmaleimide, 2- (4-bromophenyl) -3-phenylmaleimide, 2- (4-fluorophenyl) -3-phenyl Maleimide, 2- (3,5-dimethylphenyl) -3-phenylmaleimide, 3-methoxyphenanthrene-9,10-dicarboimide, 2-methoxyphenanthrene-9,10-dicarboimide, 3-chlorophenanthrene-9,10 -Dicarbimide, 2-chlorophenanthrene-9,10-dicarbomide, 3-bromophenanthrene-9,10-dicarbomido, 3-fluorophenanthrene-9,10-dicarbomido, 2,4-dimethylphenanthrene-9,10-dicarbomido, 3, -Methoxy-6- Chlorophenanthrene-9,10-dicarbimide, 3-methoxy-9,10-dihydrophenanthrene-9,10-dicarbomido, 2-methoxy-9,10-dihydrophenanthrene-9,10-dicarbomido, 3-chloro-9,10 -Dihydrophenanthrene-9,10-dicarbimide, 2-chloro-9,10-dihydrophenanthrene-9,10-dicarbomido, 3-bromo-9,10-dihydrophenanthrene-9,10-dicarbomido, 3-fluoro-9, 10-dihydrophenanthrene-9,10-dicarbimide, 2,4-dimethyl-9,10-dihydrophenanthrene-9,10-dicarbomide, 3-methoxy-6-chloro-9,10-dihydrophenanthrene-9,10-dicarboximide Succinimide, , 3-dibutylsuccinimide, 2-chloro-3-methylsuccinimide, 2,3-dichloro-2-methylsuccinimide, 2,2,3,3-tetrafluorosuccinimide, 2,2,3,3-tetramethylsuccinimide, Hexahydrophthalimide, 2,3-dichloromaleimide, 3-ethylglutazine, adipimide, 1,2,3,4-tetrahydrophthalimide, 3,4,5,6-tetrahydrophthalimide, 2- (m-fluorophenyl) Succinimide, N- (2,6-dioxopiperidin-3-yl) -5
, 6-Dihydro-1,4-dithiin-2,3-dicarbimide, 2- (α, α, α-trifluoro-m-tolyl) succinimide, 3,3-dimethylglutarimide, 2-methylsuccinimide, glutarimide 3,3,4-trimethylpyrrolidine-2,5-dione, 3,4-dibromo-3-pyrroline-2,5-dione, 3-methyl-4-vinyl-1H-pyrrole-2,5-dione, 6-amino-1H-benzo [de] isoquinoline-1,3 (2H) -dione, 3-methyl-4-ethyl-1H-pyrrole-2,5-dione, 3aα, 4,5,6,7,7aα -Hexahydro-2H-isoindole-1,3-dione, α-methyl-2-ethylsuccinimide, 9H-fluorene-4,5-dicarboximide, benzethimide, 2H-pyrrolo [3,4 c] pyridine-1,3-dione, pyrimidine-4,5-dicarbomide, 2,3-pyridinedicarboximide, 5,6-dihydro-1,4-dithiin-2,3-dicarboximide, 5,6 And cyclic imides such as -dihydro-1,4-dithiin-2,3-dicarboximide.
また、上記の一般式(XIa)で表されるイミドは、鎖状または環状のいずれでもよいが、環状のイミドが、一般的に取り扱いが容易であるという観点から好ましい。さらに、上述したようなイミドの中で、上記式(XIa)におけるR4およびR5で表される官能基または原子団を構成する炭素数が12以下のイミドが、一般的な溶媒に対して溶け易く製造(合成)が容易であるという観点から好ましく、例えば、フタルイミド、ナフタルイミドなどを好ましい例として挙げることができる。In addition, the imide represented by the general formula (XIa) may be either a chain or a ring, but a cyclic imide is generally preferable from the viewpoint of easy handling. Further, among the imides as described above, the imide having 12 or less carbon atoms constituting the functional group or atomic group represented by R 4 and R 5 in the formula (XIa) is less than a general solvent. It is preferable from the viewpoint that it is easily soluble and easy to manufacture (synthesize), and preferred examples include phthalimide and naphthalimide.
また、上述したようなイミドのうち、光学活性を有するものを用いれば、トリフルオロメチル基を含有する光学活性イミド化合物の合成が可能となる。すなわち、光学活性を有するイミドを用いることにより、R体およびS体のそれぞれのトリフルオロメチル基を含有する光学活性イミド化合物を合成することができる。 Moreover, if what has optical activity among the imides mentioned above is used, the synthesis | combination of the optically active imide compound containing a trifluoromethyl group will be attained. That is, by using an imide having optical activity, it is possible to synthesize an optically active imide compound containing trifluoromethyl groups of R and S isomers.
(アルコキシ化合物の製造方法)
また、例えば、トリフルオロメチル基を含有するアルコキシ化合物は、一般式(I)で表されるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を、アルコール類と反応させて、製造することができる。この製造は、例えば、次の式(XII)で表すことができる。(Method for producing alkoxy compound)
Further, for example, an alkoxy compound containing a trifluoromethyl group can be produced by reacting a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) with an alcohol. This production can be represented, for example, by the following formula (XII).
式(XII)において、アルコール類は、一般式(XIIa)で表され、得られるアルコキシ化合物は一般式(XIIb)で表されている。また、反応条件に関しては、多くの場合、常圧下、常温で十分に反応を進行させることができる。 In the formula (XII), the alcohol is represented by the general formula (XIIa), and the resulting alkoxy compound is represented by the general formula (XIIb). As for the reaction conditions, in many cases, the reaction can sufficiently proceed at normal temperature under normal pressure.
上記の反応式において、R1、R2およびX-は上記の一般式(I)にて定義したものと同じである。R4は、従来より知られた合成または天然由来の各種のアルコール類を構成する官能基または原子団を表す。In the above reaction formula, R 1 , R 2 and X − are the same as those defined in the above general formula (I). R 4 represents a functional group or an atomic group constituting various alcohols derived from conventionally known synthetic or natural origin.
すなわち、本発明において使用できるアルコール類の具体例としては、特に限定されるものではないが、例えば、メタノール、エタノール、1−プロパノール、1−ブタノール、1−ペンタノール、1−ヘキサノール、1−ヘプタノール、1−オクタノール、1−ノナノール、1−デカノール、1−トリデカノール、1−エイコサノール、2−メチル−1−ヘキサノール、3−メチル−1−ヘキサノール、4−メチル−1−ヘキサノール、5−メチル−1−ヘキサノール、2−エチル−1−ヘキサノール、3−エチル−1−ヘキサノール、4−エチル−1−ヘキサノール、2,2−ジメチル−1−プロパノール、アリルアルコール、ベンジルアルコール、フェネチルアルコール、ケイヒアルコール、2−フルオロベンジルアルコール、3−フルオロベンジルアルコール、4−フルオロベンジルアルコール、2−クロロベンジルアルコール、4−クロロベンジルアルコール、4−ブロモベンジルアルコール、4−メトキシベンジルアルコール、4−アセチルベンジルアルコール、2,2−ジメチル−1,3−ジオキソラン−4−メタノール、2−メチルブタノール、シクロヘキシルメタノール、2-フェニルエチルアルコール、2−メチル−2−(トシルアミノ)プロパン−1−オール等の第1級アルコール;2−プロパノール、2−ブタノール、2−ペンタノール、3−ペンタノール、2−ヘキサノール、3−ヘキサノール、2−ヘプタノール、3−ヘプタノール、4−ヘプタノール、2−オクタノール、3−オクタノール、4−オクタノール、2−ノナノール、3−ノナノール、4−ノナノール、5−ノナノール、2−デカノール、3−デカノール、4−デカノール、5−デカノール、2−トリデカノール、2−エイコサノール、シクロブタノール、シクロペンチルアルコール、シクロヘキシルアルコール、シクロヘプタノール、ベンソヒドロール、パントラクトン、シクロオクタノール、シクロドデカノール、2−メチルシクロヘキサノール、3−メチルシクロヘキサノール、4−メチルシクロヘキサノール、2−tert−ブチルシクロヘキサノール、3−tert−ブチルシクロヘキサノール、4−tert−ブチルシクロヘキサノール、1−フェニルエタノール、1−(2−フルオロフェニル)エタノール、1−(3−フルオロフェニル)エタノール、1−(4−フルオロフェニル)エタノール、1−(2−クロロフェニル)エタノール、1−(2−ブロモフェニル)エタノール、1−(4−メトキシフェニル)エタノール、1−(4−アセチルフェニル)エタノール、ベンゾイン、1,3,5−トリ−O−ベンゾイル−α−D−リボフラノース、2,3:4,5−ジ−O−イソプロピリデン−α−D−マンノフラノース、メントール、2−アダマンタノール等の第2級アルコール;t−ブタノール、2−メチル−2−ブタノール、2,3−ジメチル−2−ブタノール、2−メチル−2−ペンタノール、3−メチル−3−ペンタノール、3−エチル−3−ペンタノール、2,3−ジメチル−2−ペンタノール、2,3−ジメチル−3−ペンタノール、2,2,3−トリメチル−3−ペンタノール、2−メチル−2−ヘキサノールまたは3−メチル−3−ヘキサノール等の第3級アルコールなどが挙げられる。 That is, specific examples of alcohols that can be used in the present invention are not particularly limited, and examples thereof include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol. 1-octanol, 1-nonanol, 1-decanol, 1-tridecanol, 1-eicosanol, 2-methyl-1-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1 -Hexanol, 2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl-1-hexanol, 2,2-dimethyl-1-propanol, allyl alcohol, benzyl alcohol, phenethyl alcohol, cinnamon alcohol, 2 -Fluorobenzyl alcohol, 3-F Orobenzyl alcohol, 4-fluorobenzyl alcohol, 2-chlorobenzyl alcohol, 4-chlorobenzyl alcohol, 4-bromobenzyl alcohol, 4-methoxybenzyl alcohol, 4-acetylbenzyl alcohol, 2,2-dimethyl-1,3- Primary alcohols such as dioxolane-4-methanol, 2-methylbutanol, cyclohexylmethanol, 2-phenylethyl alcohol, 2-methyl-2- (tosylamino) propan-1-ol; 2-propanol, 2-butanol, 2 -Pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-octanol, 3-octanol, 4-octanol, 2-nonanol, 3-nonanol, 4 − Nonanol, 5-nonanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-tridecanol, 2-eicosanol, cyclobutanol, cyclopentyl alcohol, cyclohexyl alcohol, cycloheptanol, benzohydrol, pantolactone, Cyclooctanol, cyclododecanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 2-tert-butylcyclohexanol, 3-tert-butylcyclohexanol, 4-tert-butylcyclohexanol, 1 -Phenylethanol, 1- (2-fluorophenyl) ethanol, 1- (3-fluorophenyl) ethanol, 1- (4-fluorophenyl) ethanol, 1- (2-chloro Enyl) ethanol, 1- (2-bromophenyl) ethanol, 1- (4-methoxyphenyl) ethanol, 1- (4-acetylphenyl) ethanol, benzoin, 1,3,5-tri-O-benzoyl-α- Secondary alcohols such as D-ribofuranose, 2,3: 4,5-di-O-isopropylidene-α-D-mannofuranose, menthol, 2-adamantanol; t-butanol, 2-methyl-2 -Butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 2,3-dimethyl-2-pentanol 2,3-dimethyl-3-pentanol, 2,2,3-trimethyl-3-pentanol, 2-methyl-2-hexanol or 3-methyl-3-hex Such as tertiary alcohols Knoll and the like.
特に、上述したようなアルコール類の中で、上記式(XIIa)におけるR4で表される官能基または原子団を構成する炭素数が12以下のアルコール類が、一般的な溶媒に対して溶け易く製造(合成)が容易であるという観点から好ましく、例えば、2−メチル−2−(トシルアミノ)プロパン−1−オールなどを好ましい例として挙げることができる。
また、上述したようなアルコキシ化合物のうち、光学活性を有するものを用いれば、トリフルオロメチル基を含有する光学活性アルコキシ化合物の合成が可能となる。すなわち、光学活性を有するアルコキシを用いることにより、R体およびS体のそれぞれのトリフルオロメチル基を含有する光学活性アルコキシ化合物を合成することができる。In particular, among the alcohols as described above, alcohols having 12 or less carbon atoms constituting the functional group or atomic group represented by R 4 in the above formula (XIIa) are soluble in general solvents. It is preferable from the viewpoint that it is easy to produce (synthesize) and, for example, 2-methyl-2- (tosylamino) propan-1-ol and the like can be mentioned as preferable examples.
Further, if an alkoxy compound having an optical activity is used among the alkoxy compounds as described above, an optically active alkoxy compound containing a trifluoromethyl group can be synthesized. That is, by using alkoxy having optical activity, it is possible to synthesize optically active alkoxy compounds containing trifluoromethyl groups of R and S isomers.
(リン化合物の製造方法)
また、例えば、トリフルオロメチル基を含有するリン化合物は、一般式(I)で表されるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を、リン化合物と反応させて、製造することができる。この製造は、例えば、次の式(XIII)で表すことができる。(Method for producing phosphorus compound)
For example, a phosphorus compound containing a trifluoromethyl group can be produced by reacting a β- (trifluoromethyl) vinyldiarylsulfonium salt represented by the general formula (I) with a phosphorus compound. This production can be represented, for example, by the following formula (XIII).
式(XIII)において、リン化合物は、一般式(XIIIa)で表され、得られるリン化合物は一般式(XIIIb)で表されている。また、反応条件に関しては、多くの場合、常圧下、常温で十分に反応を進行させることができる。 In the formula (XIII), the phosphorus compound is represented by the general formula (XIIIa), and the obtained phosphorus compound is represented by the general formula (XIIIb). As for the reaction conditions, in many cases, the reaction can sufficiently proceed at normal temperature under normal pressure.
上記の反応式において、R1、R2およびX-は上記の一般式(I)にて定義したものと同じである。R4及びR5は、従来より知られた合成または天然由来の各種のリン化合物を構成する官能基または原子団を表す。また、Mは、水素原子またはアルカリ金属原子を表す。In the above reaction formula, R 1 , R 2 and X − are the same as those defined in the above general formula (I). R 4 and R 5 represent functional groups or atomic groups constituting various conventionally known synthetic or natural phosphorus compounds. M represents a hydrogen atom or an alkali metal atom.
すなわち、本発明において使用できるリン化合物の具体例としては、特に限定されるものではないが、例えば、ジエチルホスホナート、ビス−(3−トリエトキシシリル−1−プロピル)メチルジチオホスホナ−ト;ビス−(3−トリエトキシシリル−1−プロピル)エチルジチオホスホナ−ト、ビス−(3−トリエトキシシリル−1−プロピル)メチルトリチオホスホナ−ト、ビス−(3−トリエトキシシリル−1−プロピル)エチルトリチオホスホナ−ト、ビス−(3−メチルジメトキシシリル−1−プロピル)メチルジチオホスホナ−ト、ビス−(3−メチルジメトキシシリル−1−プロピル)エチルジチオホスホナ−トなどが挙げられる。 That is, specific examples of the phosphorus compound that can be used in the present invention are not particularly limited. For example, diethylphosphonate, bis- (3-triethoxysilyl-1-propyl) methyldithiophosphonate; Bis- (3-triethoxysilyl-1-propyl) ethyldithiophosphonate, bis- (3-triethoxysilyl-1-propyl) methyltrithiophosphonate, bis- (3-triethoxysilyl- 1-propyl) ethyl trithiophosphonate, bis- (3-methyldimethoxysilyl-1-propyl) methyldithiophosphonate, bis- (3-methyldimethoxysilyl-1-propyl) ethyldithiophosphonate And so on.
特に、上述したようなリン化合物の中で上記式(XIIIa)におけるR4及びR5で表される官能基または原子団を構成する炭素数が12以下のリン化合物が、一般的な溶媒に対して溶け易く製造(合成)が容易であるという観点から好ましく、例えば、ジエチルホスホナートなどを好ましい例として挙げることができる。In particular, among the phosphorus compounds as described above, the phosphorus compound having 12 or less carbon atoms constituting the functional group or atomic group represented by R 4 and R 5 in the above formula (XIIIa) From the viewpoint of easy dissolution and easy production (synthesis), for example, diethylphosphonate can be cited as a preferred example.
また、以下の式(XIV)に示すように、式(XIIIa)で表されるリン化合物の他に、一般式(XIVa)で表されるリン化合物を使用することで、一般式(XIVb)で表されるリン化合物を得ることもできる。しかし、式(XIVa)で表されるリン化合物は、毒性が非常に強く、各種の使用規制を受けるために、上記の式(XIVa)で表されるリン化合物を使用することが好ましい。 Further, as shown in the following formula (XIV), in addition to the phosphorus compound represented by the formula (XIIIa), by using the phosphorus compound represented by the general formula (XIVa), the general formula (XIVb) The phosphorus compound represented can also be obtained. However, the phosphorus compound represented by the formula (XIVa) is very toxic, and it is preferable to use the phosphorus compound represented by the above formula (XIVa) in order to be subjected to various usage regulations.
上記の反応式において、R1、R2およびX-は上記の一般式(I)にて定義したものと同じである。R4、R5およびR6は、従来より知られた合成または天然由来の各種のリン化合物を構成する官能基または原子団を表す。また、Mは、水素原子またはアルカリ金属原子を表す。In the above reaction formula, R 1 , R 2 and X − are the same as those defined in the above general formula (I). R 4 , R 5 and R 6 represent functional groups or atomic groups constituting various conventionally known synthetic or naturally derived phosphorus compounds. M represents a hydrogen atom or an alkali metal atom.
また、上述したようなリン化合物のうち、光学活性を有するものを用いれば、トリフルオロメチル基を含有する光学活性リン化合物の合成が可能となる。すなわち、光学活性を有するリンを用いることにより、R体およびS体のそれぞれのトリフルオロメチル基を含有する光学活性リン化合物を合成することができる。 Moreover, if what has optical activity among the phosphorus compounds as mentioned above is used, the synthesis | combination of the optically active phosphorus compound containing a trifluoromethyl group will be attained. That is, by using phosphorus having optical activity, it is possible to synthesize optically active phosphorus compounds containing trifluoromethyl groups of R and S isomers.
上記式(VIII)〜(XIV)から理解されるように、本発明により得られる各種の有用化合物、例えば、アジリジン化合物、アミド化合物、イミド化合物、アルコキシ化合物およびリン化合物等は、その原料となるβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を構成するアリール基(すなわち、R1およびR2)は、いずれも残存しないという特徴を有する。
このため、本発明によれば、トリフルオロメチル基を含む三炭素からなるオレフィン部位を他の化合物に一挙に導入できるという従来例のない全く新規な反応を行うことができる。As understood from the above formulas (VIII) to (XIV), various useful compounds obtained by the present invention, such as aziridine compounds, amide compounds, imide compounds, alkoxy compounds, and phosphorus compounds, are the raw materials for β The aryl group (that is, R 1 and R 2 ) constituting the — (trifluoromethyl) vinyldiarylsulfonium salt has a feature that none remains.
For this reason, according to the present invention, it is possible to carry out a completely new reaction that is unprecedented in that an olefin moiety consisting of three carbons containing a trifluoromethyl group can be introduced into other compounds all at once.
以上の記載から分かるように、本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩は、その用途の好ましい例として、ビルディングブロック剤として、各種の有用化合物の合成に利用することができる。ここで、ビルディングブロック剤とは、よく知られているように、有機化合物を構築するための合成中間体を意味する。 As can be seen from the above description, the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention can be used as a building block agent for the synthesis of various useful compounds as a preferred example of its use. Here, the building block agent means a synthetic intermediate for constructing an organic compound, as is well known.
なお、本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩は、別の観点では、下記の式(XVa)または式(XVb)で表されるようなシントン(synthon)に対応するものとして、逆合成解析に利用することもできる。ここで、シントンとは、よく知られているように、化合物の結合を切断したときに生じる断片(fragment)一般を指し、通常はイオンの形態である。 In addition, the β- (trifluoromethyl) vinyldiarylsulfonium salt of the present invention, in another aspect, corresponds to a synthon represented by the following formula (XVa) or (XVb): It can also be used for reverse synthesis analysis. Here, as is well known, a synthon generally refers to a fragment generated when a compound bond is cleaved, and is usually in the form of an ion.
例えば、下記の式(XVIa)で表されるアリル(1‐トリフルオロメチルビニル)エーテルを逆合成解析する場合に、式(XVa)で表されるシントンに対応するものとして、本発明のβ−(トリフルオロメチル)ビニルジアリールスルホニウム塩を使用することができる。また、式(XVIb)で表されるシントンに対応するものとしては、例えば、アリルアルコールなどが挙げられる。 For example, when the allyl (1-trifluoromethylvinyl) ether represented by the following formula (XVIa) is subjected to reverse synthesis analysis, the β- of the present invention corresponds to the synthon represented by the formula (XVa). (Trifluoromethyl) vinyldiarylsulfonium salts can be used. Moreover, as a thing corresponding to the synthon represented by a formula (XVIb), an allyl alcohol etc. are mentioned, for example.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。
なお分析は下記装置で実施した。
融点:Yanako製MP-S3。
1H-NMR、13C-NMR、19F-NMR:JEOL製AL-300。
IR:Perkin Elmer製SPECTRUM 2000 FT-IR。
GC-MS:JEOL製JMS-AWII15。
HRMS : JEOL製JMS-HX100A。EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.
The analysis was conducted with the following equipment.
Melting point: MP-S3 from Yanako.
1 H-NMR, 13 C-NMR, 19 F-NMR: AL-300 manufactured by JEOL.
IR: SPECTRUM 2000 FT-IR from Perkin Elmer.
GC-MS: JMS-AWII15 manufactured by JEOL.
HRMS: JEOL JMS-HX100A.
(1.β-(トリフルオロメチル)ビニルジアリールスルホニウム塩の製造)
(実施例1)
トリルβ-(トリフルオロメチル)ビニルスルフィドの調製(1. Production of β- (trifluoromethyl) vinyldiarylsulfonium salt)
Example 1
Preparation of tolyl β- (trifluoromethyl) vinyl sulfide
撹拌子を備えた100mLの丸底フラスコにエタノール(30mL)及び水酸化カリウム(2.1g,37mmol)を入れ、撹拌しながら0℃とした後、これに式(XVIIa)で示される4-メチルベンゼンチオール(3.7g, 30mmol)、および式(VIa)で示される3,3,3-トリフルオロ-2-ブロモプロペン(3.7mL, 36mmol)を添加し、室温下、一晩撹拌した。 Ethanol (30 mL) and potassium hydroxide (2.1 g, 37 mmol) were placed in a 100 mL round bottom flask equipped with a stir bar, and the temperature was adjusted to 0 ° C. with stirring. Then, 4-methylbenzene represented by the formula (XVIIa) was added thereto. Thiol (3.7 g, 30 mmol) and 3,3,3-trifluoro-2-bromopropene represented by formula (VIa) (3.7 mL, 36 mmol) were added, and the mixture was stirred overnight at room temperature.
反応終了後、飽和の塩化アンモニウム水を添加、有機層を分離、水層をヘキサンで3回抽出し、得られた有機層及びヘキサン抽出液を合わせて、硫酸ナトリウム上で乾燥、ろ過、減圧濃縮することにより、粗製物を油状残渣として得た。当該粗製物を、シリカゲルカラムクロマトグラフィー(溶離液:ヘキサン)により精製したところ、式(XVIIb)で示されるトリルβ-(トリフルオロメチル)ビニルスルフィドが、無色のオイル(E体5.2g、E/Z体混合物=0.8g、Z体 0.4g、合計収率 98%)として得られた。
E体
1H-NMR (CDCl3, 300 MHz) d 2.38 (3H, s), 5.32 (1H, dq, J = 15.2, 6.4 Hz), 7.11 (1H, dq, J = 15.2 Hz, 2.0 Hz), 7.20-7.40 (4H, m);
13C-NMR (CDCl3, 75 MHz) d 21.2, 112.6 (q, J = 34.3 Hz), 123.0 (q, J = 269.1 Hz),
126.3, 130.6, 133.6, 139.0 (q, J = 6.9 Hz), 139.7;
19F-NMR (CDCl3, 283 MHz) d -63.4 (dd, J = 6.6, 2.7 Hz);
IR (NaCl) 1619, 1300, 1279, 1119, 938, 832 cm-1;
GC-MS (EI, m/z, 70 eV) 218 (84, M+), 217 (18), 134 (80), 123 (37), 91 (100), 77 (51), 69 (47), 65 (79);
元素分析 C10H9F3S 計算値 C; 55.03, H; 4.16 測定値 C; 55.12, H; 4.16. After completion of the reaction, saturated aqueous ammonium chloride was added, the organic layer was separated, the aqueous layer was extracted three times with hexane, and the resulting organic layer and hexane extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure As a result, a crude product was obtained as an oily residue. The crude product was purified by silica gel column chromatography (eluent: hexane). As a result, tolyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XVIIb) was a colorless oil (5.2 g of E form, E / Z body mixture = 0.8 g, Z body 0.4 g, total yield 98%).
E body
1 H-NMR (CDCl 3 , 300 MHz) d 2.38 (3H, s), 5.32 (1H, dq, J = 15.2, 6.4 Hz), 7.11 (1H, dq, J = 15.2 Hz, 2.0 Hz), 7.20- 7.40 (4H, m);
13 C-NMR (CDCl 3 , 75 MHz) d 21.2, 112.6 (q, J = 34.3 Hz), 123.0 (q, J = 269.1 Hz),
126.3, 130.6, 133.6, 139.0 (q, J = 6.9 Hz), 139.7;
19 F-NMR (CDCl 3 , 283 MHz) d -63.4 (dd, J = 6.6, 2.7 Hz);
IR (NaCl) 1619, 1300, 1279, 1119, 938, 832 cm -1 ;
GC-MS (EI, m / z, 70 eV) 218 (84, M + ), 217 (18), 134 (80), 123 (37), 91 (100), 77 (51), 69 (47) , 65 (79);
Elemental analysis C 10 H 9 F 3 S Calculated value C; 55.03, H; 4.16 Measured value C; 55.12, H; 4.16.
(実施例2)
2-ナフチル β-(トリフルオロメチル)ビニルスルフィドの調製(Example 2)
Preparation of 2-naphthyl β- (trifluoromethyl) vinyl sulfide
実施例1で用いた式(XVIIa)で示される4-メチルベンゼンチオールを、式(XVIIIa)で示される2-ナフタレンチオールに代替し、実施例1と同じ操作を行ったところ、式(XVIIIb)で示される2-ナフチル β-(トリフルオロメチル)ビニルスルフィドが、無色液体(収率60%)として得られた。
E体
1H-NMR (CDCl3, 300 MHz) d 5.44 (1H, dq, J = 15.2, 6.5 Hz), 7.24 (1H, dq, J = 15.2, 2.0 Hz), 7.48-7.58 (3H, m), 7.80-7.89 (3H, m), 7.99 (1H, d, J = 1.7 Hz);
19F-NMR (CDCl3, 283 MHz) d -63.6 (d, J = 6.3 Hz).The 4-methylbenzenethiol represented by the formula (XVIIa) used in Example 1 was replaced with 2-naphthalenethiol represented by the formula (XVIIIa), and the same operation as in Example 1 was performed. As a result, the formula (XVIIIb) 2-naphthyl β- (trifluoromethyl) vinyl sulfide represented by the formula (1) was obtained as a colorless liquid (yield 60%).
E body
1 H-NMR (CDCl 3 , 300 MHz) d 5.44 (1H, dq, J = 15.2, 6.5 Hz), 7.24 (1H, dq, J = 15.2, 2.0 Hz), 7.48-7.58 (3H, m), 7.80 -7.89 (3H, m), 7.99 (1H, d, J = 1.7 Hz);
19 F-NMR (CDCl 3 , 283 MHz) d -63.6 (d, J = 6.3 Hz).
(実施例3)
2-ピリジル β-(トリフルオロメチル)ビニルスルフィドの調製(Example 3)
Preparation of 2-pyridyl β- (trifluoromethyl) vinyl sulfide
実施例1で用いた式(XVIIa)で示される4-メチルベンゼンチオールを、式(XIXa)で示される2-ピリジンチオールに代替し、実施例1と同じ操作を行ったところ、式(XIXb)で示される2-ピリジル β-(トリフルオロメチル)ビニルスルフィドが、薄い黄色液体(収率48%)として得られた。
E/Z混合体
1H-NMR (CDCl3, 300 MHz) d Z体: 5.83 (1H, dq, J = 16.0, 6.4 Hz), E体: 5.95 (1H, dq, J = 11.2, 8.4 Hz), 7.11-7.16 (1H, m), 7.22-7.27 (1H, m), 7.57-7.62 (1H, m), 8.05-8.12 (1H, m), 8.50-8.53 (1H, m);
19F-NMR (CDCl3, 283 MHz) d E体: -64.2 (dd, J = 6.4, 2.1 Hz), Z体: -61.74 (d, J = 8.5 Hz).When 4-methylbenzenethiol represented by the formula (XVIIa) used in Example 1 was replaced with 2-pyridinethiol represented by the formula (XIXa) and the same operation as in Example 1 was performed, the formula (XIXb) 2-pyridyl β- (trifluoromethyl) vinyl sulfide was obtained as a pale yellow liquid (48% yield).
E / Z mixture
1 H-NMR (CDCl 3 , 300 MHz) d Z form: 5.83 (1H, dq, J = 16.0, 6.4 Hz), E form: 5.95 (1H, dq, J = 11.2, 8.4 Hz), 7.11-7.16 ( 1H, m), 7.22-7.27 (1H, m), 7.57-7.62 (1H, m), 8.05-8.12 (1H, m), 8.50-8.53 (1H, m);
19 F-NMR (CDCl 3 , 283 MHz) d E form: -64.2 (dd, J = 6.4, 2.1 Hz), Z form: -61.74 (d, J = 8.5 Hz).
(実施例4)
(3,3,3-トリフルオロプロペン-1-イル)-フェニルトルイルスルホニウム トリフラートの調製(Example 4)
Preparation of (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate
撹拌子を備えた25mLの二口フラスコに、実施例1で調製した式(XVIIb)で示されるトリルβ-(トリフルオロメチル)ビニルスルフィド(514mg, 2.36mmol)、テトラクロロエタン(1.5mL)、式(XXa)で示されるジフェニルヨードニウムトリフラート(1.26g, 2.83mmol)、塩化銅(I)(23.4 mg, 0.24mmol)及び少量の銅線を加え、100℃で2時間反応させた。 In a 25 mL two-necked flask equipped with a stir bar, tolyl β- (trifluoromethyl) vinyl sulfide (514 mg, 2.36 mmol) represented by the formula (XVIIb) prepared in Example 1, tetrachloroethane (1.5 mL), formula Diphenyliodonium triflate (1.26 g, 2.83 mmol), copper (I) chloride (23.4 mg, 0.24 mmol) and a small amount of copper wire represented by (XXa) were added and reacted at 100 ° C. for 2 hours.
反応温度を室温まで冷却後、反応混合物をそのままシリカゲルクロマトグラフィー(溶離液:最初ジクロロメタン、その後ジクロロメタン:アセトン = 2:1)で精製することにより、式(IIa)で示される(3,3,3-トリフルオロプロペン-1-イル)-フェニルトルイルスルホニウム トリフラートが、薄い黄色のオイル(973mg, 収率 92%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 2.47 (3H, s), 6.97 (1H, dq, J = 14.7, 5.7 Hz), 7.51 (2H, d, J = 8.3 Hz), 7.67-7.79 (3H, m), 7.82 (2H, d, J = 8.4 Hz), 7.89-7.96 (3H, m);
13C NMR (CDCl3, 75 MHz) δ 21.6, 119.6, 120.2 (q, J = 273.4 Hz), 120.6 (q, J = 320.1 Hz), 124.0, 127.2 (q, J = 6.9 Hz), 130.7, 131.0, 131.8, 132.6, 135.0, 136.6(q, J = 37.4 Hz), 147.2;
19F NMR (CDCl3, 283 MHz) δ -66.3 (d, J = 6.4Hz), -80.1 (s);
IR (NaCl) 3046, 1645, 1592, 1449, 1279, 1225, 1151, 1031, 872, 810, 749, 684, cm-1;
元素分析 C17H14F6O3S2 計算値 C; 45.94, H; 3.18 測定値 C; 46.10, H; 3.33. After cooling the reaction temperature to room temperature, the reaction mixture is directly purified by silica gel chromatography (eluent: first dichloromethane, then dichloromethane: acetone = 2: 1) to give (3,3,3) represented by the formula (IIa) -Trifluoropropen-1-yl) -phenyltoluylsulfonium triflate was obtained as a pale yellow oil (973 mg, 92% yield).
1 H NMR (CDCl 3 , 300 MHz) δ 2.47 (3H, s), 6.97 (1H, dq, J = 14.7, 5.7 Hz), 7.51 (2H, d, J = 8.3 Hz), 7.67-7.79 (3H, m), 7.82 (2H, d, J = 8.4 Hz), 7.89-7.96 (3H, m);
13 C NMR (CDCl 3 , 75 MHz) δ 21.6, 119.6, 120.2 (q, J = 273.4 Hz), 120.6 (q, J = 320.1 Hz), 124.0, 127.2 (q, J = 6.9 Hz), 130.7, 131.0 , 131.8, 132.6, 135.0, 136.6 (q, J = 37.4 Hz), 147.2;
19 F NMR (CDCl 3 , 283 MHz) δ -66.3 (d, J = 6.4Hz), -80.1 (s);
IR (NaCl) 3046, 1645, 1592, 1449, 1279, 1225, 1151, 1031, 872, 810, 749, 684, cm -1 ;
Elemental analysis C 17 H 14 F 6 O 3 S 2 Calculated C; 45.94, H; 3.18 Measured C; 46.10, H; 3.33.
(実施例5)
(3,3,3-トリフルオロプロペン-1-イル)-ジフェニルスルホニウム トリフラートの調製(Example 5)
Preparation of (3,3,3-trifluoropropen-1-yl) -diphenylsulfonium triflate
実施例4で用いた式(XVIIb)で示されるトリル β-(トリフルオロメチル)ビニルスルフィドを、式(XXIa)で示されるフェニル β-(トリフルオロメチル)ビニルスルフィドに代替し、実施例4と同じ操作を行ったところ、式(IIIa)で示される(3,3,3-トリフルオロプロペン-1-イル)-ジフェニルスルホニウム トリフラートが、白色固体(収率93%)として得られた。
融点 68.1-70.5 ℃
1H NMR (CDCl3, 300 MHz) δ 6.98 (1H, dq, J = 14.7, 5.7 Hz), 7.71-7.83 (6H, m), 7.88-7.93 (5H, m);
13C NMR (CDCl3, 75 MHz) δ 120.0 (q, J = 273.4 Hz), 120.6 (q, J = 320.1 Hz), 123.6, 126.7 (q, J = 6.9 Hz), 130.9, 131.8, 135.2, 137.3 (q, J = 37.4 Hz);
19F NMR (CDCl3, 283 MHz) δ -66.3 (d, J = 6.5 Hz), -79.9 (s)
IR (NaCl) 3066, 3047, 1645, 1583, 1478, 1449, 1279, 1226, 1152, 1031, 999, 873, 748, 683, cm-1;
元素分析 C16H12F6O3S2 計算値 C; 44.65, H; 2.81 測定値 C; 44.66, H; 2.92.The tolyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XVIIb) used in Example 4 was replaced with phenyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XXIa). When the same operation was performed, (3,3,3-trifluoropropen-1-yl) -diphenylsulfonium triflate represented by the formula (IIIa) was obtained as a white solid (yield 93%).
Melting point 68.1-70.5 ℃
1 H NMR (CDCl 3 , 300 MHz) δ 6.98 (1H, dq, J = 14.7, 5.7 Hz), 7.71-7.83 (6H, m), 7.88-7.93 (5H, m);
13 C NMR (CDCl 3 , 75 MHz) δ 120.0 (q, J = 273.4 Hz), 120.6 (q, J = 320.1 Hz), 123.6, 126.7 (q, J = 6.9 Hz), 130.9, 131.8, 135.2, 137.3 (q, J = 37.4 Hz);
19 F NMR (CDCl 3 , 283 MHz) δ -66.3 (d, J = 6.5 Hz), -79.9 (s)
IR (NaCl) 3066, 3047, 1645, 1583, 1478, 1449, 1279, 1226, 1152, 1031, 999, 873, 748, 683, cm -1 ;
Elemental analysis C 16 H 12 F 6 O 3 S 2 Calculated value C; 44.65, H; 2.81 Measured value C; 44.66, H; 2.92.
(実施例6)
(3,3,3-トリフルオロプロペン-1-イル)-(2-ナフチル)フェニルスルホニウム トリフラートの調製(Example 6)
Preparation of (3,3,3-trifluoropropen-1-yl)-(2-naphthyl) phenylsulfonium triflate
実施例4で用いた式(XVIIb)で示されるトリル β-(トリフルオロメチル)ビニルスルフィドを、式(XVIIIb)で示される(2-ナフチル) β-(トリフルオロメチル)ビニルスルフィドに代替し、実施例4と同じ操作を行ったところ、式(IVa)で示される(3,3,3-トリフルオロプロペン-1-イル)-(2-ナフチル)フェニルスルホニウム トリフラートを薄い黄色のオイル(収率93%)として得た。
1H NMR (CDCl3, 300 MHz) δ 7.07 (1H, dq, J = 14.9, 5.7 Hz), 7.66-7.78 (6H, m), 7.92-7.97 (3H, m), 8.03 (1H, dq, J = 14.9, 1.8 Hz), 8.05-8.15 (2H, m), 8.72 (1H, d, J = 2.0 Hz);
19F NMR (CDCl3, 283 MHz) δ -66.2 (d, J = 5.3 Hz), -79.9 (s).The tolyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XVIIb) used in Example 4 was replaced with (2-naphthyl) β- (trifluoromethyl) vinyl sulfide represented by the formula (XVIIIb). When the same operation as in Example 4 was performed, (3,3,3-trifluoropropen-1-yl)-(2-naphthyl) phenylsulfonium triflate represented by the formula (IVa) was converted to a pale yellow oil (yield 93%).
1 H NMR (CDCl 3 , 300 MHz) δ 7.07 (1H, dq, J = 14.9, 5.7 Hz), 7.66-7.78 (6H, m), 7.92-7.97 (3H, m), 8.03 (1H, dq, J = 14.9, 1.8 Hz), 8.05-8.15 (2H, m), 8.72 (1H, d, J = 2.0 Hz);
19 F NMR (CDCl 3 , 283 MHz) δ -66.2 (d, J = 5.3 Hz), -79.9 (s).
(実施例7)
(3,3,3-トリフルオロプロペン-1-イル)-フェニル(2-ピリジル)スルホニウム トリフラートの調製(Example 7)
Preparation of (3,3,3-trifluoropropen-1-yl) -phenyl (2-pyridyl) sulfonium triflate
実施例4で用いた式(XVIIb)で示されるトリル β-(トリフルオロメチル)ビニルスルフィドを、式(XIXb)で示される2-ピリジル β-(トリフルオロメチル)ビニルスルフィドに代替し、実施例4と同じ操作を行ったところ、式(Va)で示される(3,3,3-トリフルオロプロペン-1-イル)-フェニル(2-ピリジル)スルホニウム トリフラートが、薄い黄色のオイル(収率17%)として得られた。
1H NMR (acetone-d6, 300 MHz) δ 6.73 (1H, dq, J = 15.2, 6.4 Hz), 7.69 (1H, dq, J= 15.2, 1.8 Hz), 7.79-7.89 (5H, m), 8.23-8.27 (1H, m), 8.53 (1H, d, J = 8.1 Hz), 8.78-8.84 (1H, m), 9.16-9.19 (1H, m);
19F NMR (CDCl3, 283 MHz) δ -65.9 (d, J = 6.0 Hz), -79.8 (s).The tolyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XVIIb) used in Example 4 was replaced with 2-pyridyl β- (trifluoromethyl) vinyl sulfide represented by the formula (XIXb). When the same operation as 4 was performed, (3,3,3-trifluoropropen-1-yl) -phenyl (2-pyridyl) sulfonium triflate represented by the formula (Va) was converted into a pale yellow oil (yield 17 %).
1 H NMR (acetone-d 6 , 300 MHz) δ 6.73 (1H, dq, J = 15.2, 6.4 Hz), 7.69 (1H, dq, J = 15.2, 1.8 Hz), 7.79-7.89 (5H, m), 8.23-8.27 (1H, m), 8.53 (1H, d, J = 8.1 Hz), 8.78-8.84 (1H, m), 9.16-9.19 (1H, m);
19 F NMR (CDCl 3 , 283 MHz) δ -65.9 (d, J = 6.0 Hz), -79.8 (s).
(実施例8)
(3,3,3-トリフルオロプロペン-1-イル)-フェニルトルイルスルホニウム テトラフルオロボレートの調製(Example 8)
Preparation of (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium tetrafluoroborate
撹拌子を備えた25mLの二口フラスコに、実施例4で調製した式(IIa)で示される(3,3,3-トリフルオロプロペン-1-イル)-フェニルトルイルスルホニウム トリフラート(109.7mg, 0.247mmol)、式(XXIVa)で示されるAgBF4(66.2mg, 0.34mmol)及びジクロロメタン(1mL)を加え、超音波洗浄機中で1時間、その後超音波洗浄機から出して室温で2時間反応させた。In a 25 mL two-necked flask equipped with a stir bar, (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate (109.7 mg, 0.247) represented by the formula (IIa) prepared in Example 4 was prepared. mmol), AgBF 4 (66.2 mg, 0.34 mmol) represented by the formula (XXIVa) and dichloromethane (1 mL) are added, and the mixture is allowed to react in an ultrasonic cleaner for 1 hour, then removed from the ultrasonic cleaner and allowed to react at room temperature for 2 hours. It was.
反応混合物を、セライトを充填した短いカラムクロマトグラフィーを用いてろ過後、ろ液を濃縮したところ、式(IIIb)で示される(3,3,3-トリフルオロプロペン-1-イル)-フェニルトルイルスルホニウム テトラフルオロボレートが、薄い茶色のオイルとして得られた。(収率79%)
1H NMR (CDCl3, 300 MHz) δ 2.47 (3H, s), 6.95 (1H, dq, J = 14.7, 5.7Hz), 7.52 (2H, d, J = 8.6 Hz), 7.67-7.77 (4H, m), 7.80 (2H, d, J = 8.4 Hz), 7.86-7.89 (2H, m);
13C NMR (CDCl3, 75 MHz) δ 21.5, 119.7, 120.1 (q, J = 273.4 Hz), 124.0, 126.5 (q, J = 6.9 Hz), 130.6, 131.0, 131.7, 132.5, 135.0, 136.9 (q, J = 37.4 Hz), 147.0;19F NMR (CDCl3, 283 MHz) δ -66.5 (d, J = 6.5 Hz), -151.3 (s);
IR (NaCl) 3065, 1645, 1592, 1494, 1478, 1449, 1303, 1283, 1151, 1059, 872, 811 cm-1;
元素分析 C16H14BF7S 計算値 C; 50.29, H; 3.69 測定値 C; 50.36, H; 3.89.The reaction mixture was filtered using short column chromatography packed with celite, and the filtrate was concentrated to obtain (3,3,3-trifluoropropen-1-yl) -phenyltoluyl represented by the formula (IIIb). Sulphonium tetrafluoroborate was obtained as a light brown oil. (Yield 79%)
1 H NMR (CDCl 3 , 300 MHz) δ 2.47 (3H, s), 6.95 (1H, dq, J = 14.7, 5.7 Hz), 7.52 (2H, d, J = 8.6 Hz), 7.67-7.77 (4H, m), 7.80 (2H, d, J = 8.4 Hz), 7.86-7.89 (2H, m);
13 C NMR (CDCl 3 , 75 MHz) δ 21.5, 119.7, 120.1 (q, J = 273.4 Hz), 124.0, 126.5 (q, J = 6.9 Hz), 130.6, 131.0, 131.7, 132.5, 135.0, 136.9 (q , J = 37.4 Hz), 147.0; 19 F NMR (CDCl 3 , 283 MHz) δ -66.5 (d, J = 6.5 Hz), -151.3 (s);
IR (NaCl) 3065, 1645, 1592, 1494, 1478, 1449, 1303, 1283, 1151, 1059, 872, 811 cm -1 ;
Elemental analysis C 16 H 14 BF 7 S Calculated value C; 50.29, H; 3.69 Measured value C; 50.36, H; 3.89.
(2.アジリジン化合物の製造)
(実施例9)
1-ベンジル-2-(トリフルオロメチル)アジリジンの調製(2. Production of aziridine compound)
Example 9
Preparation of 1-benzyl-2- (trifluoromethyl) aziridine
撹拌子を備えた25mLの二口フラスコに、実施例4で調製した式(IIa)で示される(3,3,3-トリフルオロプロペン-1-イル)-フェニルトルイルスルホニウム トリフラート(122.7mg, 0.28mmol)、DMSO(1mL)、式(XXVa)で示されるベンジルアミン(36mL, 0.33mmol)、tert-ブチルアミン(87mL, 0.83mmol)を加え、室温で2.5時間反応させた。反応混合物に水を加え、さらに抽出溶媒としてヘキサン:酢酸エチル=3/1混合溶媒を加えて有機層を分離した。 A 25 mL two-necked flask equipped with a stir bar was charged with (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate (122.7 mg, 0.28) of the formula (IIa) prepared in Example 4. mmol), DMSO (1 mL), benzylamine (36 mL, 0.33 mmol) represented by the formula (XXVa), and tert-butylamine (87 mL, 0.83 mmol) were added and reacted at room temperature for 2.5 hours. Water was added to the reaction mixture, and a mixed solvent of hexane: ethyl acetate = 3/1 was added as an extraction solvent to separate the organic layer.
水層をヘキサン:酢酸エチル=3/1混合溶媒で3回抽出し、得られた有機層及び混合抽出液を合わせて、硫酸ナトリウム上で乾燥、ろ過、減圧濃縮することにより、粗製物を油状残渣として得た。得られた粗製物を、シリカゲルカラムクロマトグラフィー(溶離液:ヘキサン:酢酸エチル=10/1、その後ヘキサン:酢酸エチル=3/1)で精製することにより、式(XXVb)で示される1-ベンジル-2-(トリフルオロメチル)アジリジンが、無色のオイル(収率 78%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 1.66 (1H, d, J = 5.9 Hz), 2.10-2.19 (2H, m), 3.78 (2H, s), 7.28-7.36 (5H, m);
13C NMR (CDCl3, 75 MHz) δ 30.0 (q, J = 2.5 Hz), 37.3 (q, J = 39.8 Hz), 63.4, 124.1 (q, J = 272.8 Hz), 127.5, 128.0, 128.5, 137.3;
19F NMR (CDCl3, 283 MHz) δ -72.5 (d, J = 4.7 Hz);
IR (NaCl) 3067, 3033, 2935, 2843, 1498, 1456, 1362, 1286, 1142, 1070, 1028, 847, 736, 698 cm-1;
GC-MS (EI, m/z, 70 eV) 201 (0.4, M+), 132 (1), 110 (2), 92 (9), 91 (100), 90 (9) , 65 (13), 51 (7);
元素分析 C10H10F3N 計算値 C; 59.70, H; 5.01, N; 6.96 測定値 C; 59.81, H; 5.03,N; 7.08.The aqueous layer was extracted three times with a mixed solvent of hexane: ethyl acetate = 3/1. The obtained organic layer and the mixed extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as an oil. Obtained as a residue. The obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 10/1, then hexane: ethyl acetate = 3/1) to give 1-benzyl represented by the formula (XXVb). -2- (Trifluoromethyl) aziridine was obtained as a colorless oil (78% yield).
1 H NMR (CDCl 3 , 300 MHz) δ 1.66 (1H, d, J = 5.9 Hz), 2.10-2.19 (2H, m), 3.78 (2H, s), 7.28-7.36 (5H, m);
13 C NMR (CDCl 3 , 75 MHz) δ 30.0 (q, J = 2.5 Hz), 37.3 (q, J = 39.8 Hz), 63.4, 124.1 (q, J = 272.8 Hz), 127.5, 128.0, 128.5, 137.3 ;
19 F NMR (CDCl 3 , 283 MHz) δ -72.5 (d, J = 4.7 Hz);
IR (NaCl) 3067, 3033, 2935, 2843, 1498, 1456, 1362, 1286, 1142, 1070, 1028, 847, 736, 698 cm -1 ;
GC-MS (EI, m / z, 70 eV) 201 (0.4, M + ), 132 (1), 110 (2), 92 (9), 91 (100), 90 (9), 65 (13) , 51 (7);
Elemental analysis C 10 H 10 F 3 N Calculated C; 59.70, H; 5.01, N; 6.96 Measured C; 59.81, H; 5.03, N; 7.08.
(実施例10)
2-(トリフルオロメチル)-1-フェネチルアジリジンの調製(Example 10)
Preparation of 2- (trifluoromethyl) -1-phenethylaziridine
実施例9で用いた式(XXVa)で示されるベンジルアミンを、式(XXVIa)で示される2-フェニルエタンアミンに代替し、実施例9と同じ操作を行ったところ、式(XXVIb)で示される2-(トリフルオロメチル)-1-フェネチルアジリジンが、無色のオイル(収率77%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 1.47 (1H, d, J = 6.2 Hz), 1.96-2.04 (1H, m), 2.08 (1H, d, J = 3.1 Hz), 2.52-2.66 (2H, m), 2.84-2.99 (2H, m), 7.18-7.29 ppm (5H, m);
13C NMR (CDCl3, 75 MHz) δ 30.2 (q, J = 2.3 Hz), 35.9, 37.4 (q, J = 39.5 Hz), 62.0, 124.1 (q, J = 272.5 Hz), 126.3, 128.5, 128.7, 139.1;
19F NMR (CDCl3, 283 MHz) δ -72.5 (d, J = 4.8 Hz);
IR (NaCl) 3060, 3027, 2940, 2833, 1497, 1453, 1363, 1286, 1143, 1074, 860, 748, 699 cm-1;
GC-MS (EI, m/z, 70 eV) 215 (1.8, M+), 124 (100), 91 (28), 77 (20), 74 (23), 65 (17), 60 (35), 51 (11);
元素分析 C11H12F3N 計算値 C; 61.39, H; 5.62, N; 6.51 測定値 C; 61.59, H; 5.76,N; 6.59.The same operation as in Example 9 was performed by replacing the benzylamine represented by the formula (XXVa) used in Example 9 with 2-phenylethanamine represented by the formula (XXVIa). 2- (trifluoromethyl) -1-phenethylaziridine was obtained as a colorless oil (77% yield).
1 H NMR (CDCl 3 , 300 MHz) δ 1.47 (1H, d, J = 6.2 Hz), 1.96-2.04 (1H, m), 2.08 (1H, d, J = 3.1 Hz), 2.52-2.66 (2H, m), 2.84-2.99 (2H, m), 7.18-7.29 ppm (5H, m);
13 C NMR (CDCl 3 , 75 MHz) δ 30.2 (q, J = 2.3 Hz), 35.9, 37.4 (q, J = 39.5 Hz), 62.0, 124.1 (q, J = 272.5 Hz), 126.3, 128.5, 128.7 , 139.1;
19 F NMR (CDCl 3 , 283 MHz) δ -72.5 (d, J = 4.8 Hz);
IR (NaCl) 3060, 3027, 2940, 2833, 1497, 1453, 1363, 1286, 1143, 1074, 860, 748, 699 cm -1 ;
GC-MS (EI, m / z, 70 eV) 215 (1.8, M + ), 124 (100), 91 (28), 77 (20), 74 (23), 65 (17), 60 (35) , 51 (11);
Elemental analysis C 11 H 12 F 3 N Calculated C; 61.39, H; 5.62, N; 6.51 Measured C; 61.59, H; 5.76, N; 6.59.
(実施例11)
2-(トリフルオロメチル)-1-(3,5-ジメチルベンジル)アジリジンの調製(Example 11)
Preparation of 2- (trifluoromethyl) -1- (3,5-dimethylbenzyl) aziridine
実施例9で用いた式(XXVa)で示されるベンジルアミンを、式(XXVIIa)で示される3,5-ジメチルベンジルアミンに代替し、実施例9と同じ操作を行ったところ、式(XXVIIb)で示される2-(トリフルオロメチル)-1-(3,5-ジメチルベンジル)アジリジンが、無色のオイル(収率72%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 1.65 (1H, brd, J = 5.9 Hz), 2.13-2.16 (2H, m), 2.311 (3H,s), 2.312 (3H, s), 3.42 (1H, d, J = 13.2 Hz), 3.55 (1H, d, J = 13.2 Hz), 6.93 (1H, s), 6.94 (2H, s);
13C NMR (CDCl3, 75 MHz) δ 21.2, 29.9 (q, J = 1.9 Hz), 37.3 (q, J = 39.9 Hz), 63.4, 124.2 (q, J = 272.8 Hz), 125.9, 129.1, 137.1, 138.0;
19F NMR (CDCl3, 283 MHz) δ -72.5 (d, J = 4.8 Hz);
IR (NaCl) 3015, 2921, 2843, 1609, 1429, 1285, 1153, 1072, 1040, 961, 854, 827 cm-1;
GC-MS (EI, m/z, 70 eV) 229 (4, M+), 132 (1), 120 (12), 119 (100), 118 (7), 104 (4), 91 (19), 77 (9), 65 (3);
元素分析 C12H14F3N 計算値 C; 62.87, H; 6.16, N; 6.11 測定値 C; 62.85, H; 6.25,N; 6.17.The same operation as in Example 9 was performed by replacing the benzylamine represented by the formula (XXVa) used in Example 9 with 3,5-dimethylbenzylamine represented by the formula (XXVIIa), and the formula (XXVIIb) 2- (trifluoromethyl) -1- (3,5-dimethylbenzyl) aziridine represented by the formula (1) was obtained as a colorless oil (yield 72%).
1 H NMR (CDCl 3 , 300 MHz) δ 1.65 (1H, brd, J = 5.9 Hz), 2.13-2.16 (2H, m), 2.311 (3H, s), 2.312 (3H, s), 3.42 (1H, d, J = 13.2 Hz), 3.55 (1H, d, J = 13.2 Hz), 6.93 (1H, s), 6.94 (2H, s);
13 C NMR (CDCl 3 , 75 MHz) δ 21.2, 29.9 (q, J = 1.9 Hz), 37.3 (q, J = 39.9 Hz), 63.4, 124.2 (q, J = 272.8 Hz), 125.9, 129.1, 137.1 , 138.0;
19 F NMR (CDCl 3 , 283 MHz) δ -72.5 (d, J = 4.8 Hz);
IR (NaCl) 3015, 2921, 2843, 1609, 1429, 1285, 1153, 1072, 1040, 961, 854, 827 cm -1 ;
GC-MS (EI, m / z, 70 eV) 229 (4, M + ), 132 (1), 120 (12), 119 (100), 118 (7), 104 (4), 91 (19) , 77 (9), 65 (3);
Elemental analysis C 12 H 14 F 3 N Calculated C; 62.87, H; 6.16, N; 6.11 Measured C; 62.85, H; 6.25, N; 6.17.
(実施例12)
1-(3,5-ビス(トリフルオロメチル)ベンジル) -2-(トリフルオロメチル)アジリジンの調製(Example 12)
Preparation of 1- (3,5-bis (trifluoromethyl) benzyl) -2- (trifluoromethyl) aziridine
実施例9で用いた式(XXVa)で示されるベンジルアミンを、式(XXVIIIa)で示される3,5-ビス(トリフルオロメチル)ベンジルアミンに代替し、実施例9と同じ操作を行ったところ、式(XXVIIIb)で示される1-(3,5-ビス(トリフルオロメチル)ベンジル)-2-(トリフルオロメチル)アジリジンが、無色のオイル(収率40%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 1.74 (1H, d, J = 6.4 Hz), 2.18-2.22 (1H, m), 2.28 (1H, d, J = 3.1 Hz), 3.64 (1H, d, J = 14.3 Hz), 3.71 (1H, d, J = 14.3 Hz), 7.82 (1H, s), 7.85 (2H, s);
13C NMR (CDCl3, 75 MHz) δ 30.4 (q, J = 1.9 Hz), 37.9 (q, J = 39.9 Hz), 62.3, 121.5 (sep, J = 3.7 Hz), 123.8 (q, J = 272.7 Hz), 127.8, 131.8 (q, J = 33.4 Hz), 140.2;
19F NMR (CDCl3, 283 MHz) δ -72.7 (d, J = 4.9 Hz);
IR (NaCl) 3006, 2933, 2853, 1624, 1433, 1386, 1351, 1280, 1246, 1136, 1076, 1040, 956, 911, 891, 837, 706, 683 cm-1;
GC-MS (EI, m/z, 70 eV) 336 (0.1, M+-1), 227 (13), 226 (4), 177 (2), 110 (100), 95 (2), 77 (2), 69 (4), 60 (15);
元素分析 C12H8F9N 計算値 C; 42.74, H; 2.39, N; 4.15 測定値 C; 42.76, H; 2.45,N; 4.22.The same operation as in Example 9 was performed by replacing the benzylamine represented by the formula (XXVa) used in Example 9 with 3,5-bis (trifluoromethyl) benzylamine represented by the formula (XXVIIIa). 1- (3,5-bis (trifluoromethyl) benzyl) -2- (trifluoromethyl) aziridine represented by the formula (XXVIIIb) was obtained as a colorless oil (yield 40%).
1 H NMR (CDCl 3 , 300 MHz) δ 1.74 (1H, d, J = 6.4 Hz), 2.18-2.22 (1H, m), 2.28 (1H, d, J = 3.1 Hz), 3.64 (1H, d, J = 14.3 Hz), 3.71 (1H, d, J = 14.3 Hz), 7.82 (1H, s), 7.85 (2H, s);
13 C NMR (CDCl 3 , 75 MHz) δ 30.4 (q, J = 1.9 Hz), 37.9 (q, J = 39.9 Hz), 62.3, 121.5 (sep, J = 3.7 Hz), 123.8 (q, J = 272.7 Hz), 127.8, 131.8 (q, J = 33.4 Hz), 140.2;
19 F NMR (CDCl 3 , 283 MHz) δ -72.7 (d, J = 4.9 Hz);
IR (NaCl) 3006, 2933, 2853, 1624, 1433, 1386, 1351, 1280, 1246, 1136, 1076, 1040, 956, 911, 891, 837, 706, 683 cm -1 ;
GC-MS (EI, m / z, 70 eV) 336 (0.1, M + -1), 227 (13), 226 (4), 177 (2), 110 (100), 95 (2), 77 ( 2), 69 (4), 60 (15);
Elemental analysis C 12 H 8 F 9 N Calculated C; 42.74, H; 2.39, N; 4.15 Measured C; 42.76, H; 2.45, N; 4.22.
(実施例13)
2-(トリフルオロメチル)-1-((ナフタレン-2-イル)メチル)アジリジンの調製(Example 13)
Preparation of 2- (trifluoromethyl) -1-((naphthalen-2-yl) methyl) aziridine
実施例9で用いた式(XXVa)で示されるベンジルアミンを、式(XXIXa)で示される1-ナフタレンメチルアミンに代替し、実施例9と同じ操作を行ったところ、式(XXIXb)で示される2-(トリフルオロメチル)-1-((ナフタレン-2-イル)メチル)アジリジンが、無色のオイル(収率86%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 1.73 (1H, d, J = 5.9 Hz), 2.21-2.25 (2H, m), 3.90 (1H, d, J = 13.9 Hz), 4.14 (1H, d, J = 13.9 Hz), 7.43-7.57 (4H, m), 7.80 (2H, m), 8.08 (1H, d, J = 8.1 Hz);
13C NMR (CDCl3, 75 MHz) δ 30.2 (q, J = 1.9 Hz), 37.6 (q, J = 39.9 Hz), 61.1, 123.5, 124.2 (q, J = 272.3Hz), 125.3, 125.7, 125.8, 126.8, 128.3, 128.6, 131.5, 133.0, 133.6;
19F NMR (CDCl3, 283 MHz) δ -72.2 (d, J = 4.6 Hz);
IR (NaCl) 3051, 3011, 2849, 1599, 1510, 1430, 1287, 1239, 1152, 796, 775 cm-1;
GC-MS (EI, m/z, 70 eV) 251 (4, M+), 154 (2), 141 (100), 139 (6), 127 (5), 115 (29), 89 (3), 77 (3), 63 (3), 51 (2);
HRMS C14H12F3N 計算値 251.0943 測定値 251.0922.The same operation as in Example 9 was performed by replacing the benzylamine represented by the formula (XXVa) used in Example 9 with 1-naphthalenemethylamine represented by the formula (XXIXa). 2- (trifluoromethyl) -1-((naphthalen-2-yl) methyl) aziridine was obtained as a colorless oil (yield 86%).
1 H NMR (CDCl 3 , 300 MHz) δ 1.73 (1H, d, J = 5.9 Hz), 2.21-2.25 (2H, m), 3.90 (1H, d, J = 13.9 Hz), 4.14 (1H, d, J = 13.9 Hz), 7.43-7.57 (4H, m), 7.80 (2H, m), 8.08 (1H, d, J = 8.1 Hz);
13 C NMR (CDCl 3 , 75 MHz) δ 30.2 (q, J = 1.9 Hz), 37.6 (q, J = 39.9 Hz), 61.1, 123.5, 124.2 (q, J = 272.3 Hz), 125.3, 125.7, 125.8 , 126.8, 128.3, 128.6, 131.5, 133.0, 133.6;
19 F NMR (CDCl 3 , 283 MHz) δ -72.2 (d, J = 4.6 Hz);
IR (NaCl) 3051, 3011, 2849, 1599, 1510, 1430, 1287, 1239, 1152, 796, 775 cm -1 ;
GC-MS (EI, m / z, 70 eV) 251 (4, M + ), 154 (2), 141 (100), 139 (6), 127 (5), 115 (29), 89 (3) , 77 (3), 63 (3), 51 (2);
HRMS C 14 H 12 F 3 N Calculated value 251.0943 Measured value 251.0922.
(実施例14)
N,N-ジエチル-2-(2-(トリフルオロメチル)アジリジン-1-イル)エタンアミンの調製(Example 14)
Preparation of N, N-diethyl-2- (2- (trifluoromethyl) aziridin-1-yl) ethanamine
実施例9で用いた式(XXVa)で示されるベンジルアミンを、式(XXXa)で示されるN,N-ジエチルエチレンジアミンに代替し、実施例9と同じ操作を行ったところ、式(XXXb)で示されるN,N-ジエチル-2-(2-(トリフルオロメチル)アジリジン-1-イル)エタンアミンが、無色のオイル(収率63%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 1.10-1.06 (6H, m), 1.56 (1H, d, J = 6.2 Hz), 2.02-2.05 (1H, m), 2.09 (1H, d, J = 3.1 Hz), 2.34-2.40 (1H, m), 2.50-2.70 (6H, m), 2.76-2.81 (1H, m);
13C NMR (CDCl3, 75 MHz) δ 11.6, 29.7 (q, J = 1.9 Hz), 37.2 (q, J = 39.9 Hz), 47.3, 52.0, 58.6, 125.8 (q, J = 272.2 Hz);
19F NMR (CDCl3, 283 MHz) δ -72.8 (d, J = 4.6 Hz);
IR (NaCl) 2972, 2933, 2873, 2806, 1431, 1383, 1336, 1287, 1240, 1196, 1141, 1066, 960, 853, 756 cm-1;
GC-MS (EI, m/z, 70 eV) 210 (0.1, M+), 138 (1), 100 (2), 87 (10), 86 (100), 85 (14), 70 (2), 58 (12), 56 (5).The same operation as in Example 9 was performed by replacing the benzylamine represented by the formula (XXVa) used in Example 9 with N, N-diethylethylenediamine represented by the formula (XXXa). The indicated N, N-diethyl-2- (2- (trifluoromethyl) aziridin-1-yl) ethanamine was obtained as a colorless oil (63% yield).
1 H NMR (CDCl 3 , 300 MHz) δ 1.10-1.06 (6H, m), 1.56 (1H, d, J = 6.2 Hz), 2.02-2.05 (1H, m), 2.09 (1H, d, J = 3.1 Hz), 2.34-2.40 (1H, m), 2.50-2.70 (6H, m), 2.76-2.81 (1H, m);
13 C NMR (CDCl 3 , 75 MHz) δ 11.6, 29.7 (q, J = 1.9 Hz), 37.2 (q, J = 39.9 Hz), 47.3, 52.0, 58.6, 125.8 (q, J = 272.2 Hz);
19 F NMR (CDCl 3 , 283 MHz) δ -72.8 (d, J = 4.6 Hz);
IR (NaCl) 2972, 2933, 2873, 2806, 1431, 1383, 1336, 1287, 1240, 1196, 1141, 1066, 960, 853, 756 cm -1 ;
GC-MS (EI, m / z, 70 eV) 210 (0.1, M + ), 138 (1), 100 (2), 87 (10), 86 (100), 85 (14), 70 (2) , 58 (12), 56 (5).
(実施例15)
エチル 2-(2-(トリフルオロメチル)アジリジン-1-イル)アセテートの調製(Example 15)
Preparation of ethyl 2- (2- (trifluoromethyl) aziridin-1-yl) acetate
撹拌子を備えた25mLの二口フラスコにグリシンエチル塩酸塩(64.6mg, 0.463mmol)、DMSO(1mL)、tert-ブチルアミン(250mL, 2.32mmol)を加え撹拌した。
この混合溶液に水素化ナトリウム(62.7%, 32.4mg, 0.556mmol)、実施例5で調製した式(IIIa)で示される(3,3,3-トリフルオロプロペン-1-イル)-ジフェニルスルホニウム トリフラート(240.0mg, 0.556mmol)を加え、室温で10時間反応させた。To a 25 mL two-necked flask equipped with a stir bar, glycine ethyl hydrochloride (64.6 mg, 0.463 mmol), DMSO (1 mL), tert-butylamine (250 mL, 2.32 mmol) were added and stirred.
To this mixed solution, sodium hydride (62.7%, 32.4 mg, 0.556 mmol), (3,3,3-trifluoropropen-1-yl) -diphenylsulfonium triflate represented by the formula (IIIa) prepared in Example 5 (240.0 mg, 0.556 mmol) was added and reacted at room temperature for 10 hours.
反応混合物に水を加え、さらに抽出溶媒としてヘキサン:酢酸エチル=3/1混合溶媒を加えて有機層を分離した。水層をヘキサン:酢酸エチル=3/1混合溶媒で3回抽出し、得られた有機層及び混合抽出液を合わせて、硫酸ナトリウム上で乾燥、ろ過、減圧濃縮することにより、粗製物を油状残渣として得た。 Water was added to the reaction mixture, and a mixed solvent of hexane: ethyl acetate = 3/1 was added as an extraction solvent to separate the organic layer. The aqueous layer was extracted three times with a mixed solvent of hexane: ethyl acetate = 3/1. The obtained organic layer and the mixed extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as an oil. Obtained as a residue.
得られた粗製物を、シリカゲルカラムクロマトグラフィー(溶離液:ヘキサン:酢酸エチル=3/1)で精製することにより、式(XXXIb)で示されるエチル 2-(2-(トリフルオロメチル)アジリジン-1-イルアセテートが、無色のオイル(収率 54%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 1.30 (3H, t, J = 7.1 Hz), 1.68 (1H, d, J = 6.6 Hz), 2.19-2.24 (1H, m), 2.26 (1H, d, J = 3.1 Hz), 3.12 (1H, d, J = 15.8 Hz), 3.24 (1H, d, J = 16.0 Hz), 4.23 (1H, q, J = 7.2 Hz);
13C NMR (CDCl3, 75 MHz) δ 13.9, 29.7 (q, J = 2.5 Hz), 37.3 (q, J = 39.9 Hz), 59.9, 61.0, 123.7 (q, J = 272.8 Hz), 168.7;
19F NMR (CDCl3, 283 MHz) δ -72.9 (d, J = 4.6 Hz);
IR (NaCl) 2986, 2940, 2913, 1747, 1430, 1286, 1200, 1143, 1080, 1043, 956, 833 cm-1;
GC-MS (EI, m/z, 70 eV) 197 (1, M+), 124 (100), 110 (21), 95 (4), 77 (3), 74 (9), 69 (2), 60 (18), 55 (4).The obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 3/1) to give ethyl 2- (2- (trifluoromethyl) aziridine- represented by the formula (XXXIb) 1-yl acetate was obtained as a colorless oil (54% yield).
1 H NMR (CDCl 3 , 300 MHz) δ 1.30 (3H, t, J = 7.1 Hz), 1.68 (1H, d, J = 6.6 Hz), 2.19-2.24 (1H, m), 2.26 (1H, d, J = 3.1 Hz), 3.12 (1H, d, J = 15.8 Hz), 3.24 (1H, d, J = 16.0 Hz), 4.23 (1H, q, J = 7.2 Hz);
13 C NMR (CDCl 3 , 75 MHz) δ 13.9, 29.7 (q, J = 2.5 Hz), 37.3 (q, J = 39.9 Hz), 59.9, 61.0, 123.7 (q, J = 272.8 Hz), 168.7;
19 F NMR (CDCl 3 , 283 MHz) δ -72.9 (d, J = 4.6 Hz);
IR (NaCl) 2986, 2940, 2913, 1747, 1430, 1286, 1200, 1143, 1080, 1043, 956, 833 cm -1 ;
GC-MS (EI, m / z, 70 eV) 197 (1, M + ), 124 (100), 110 (21), 95 (4), 77 (3), 74 (9), 69 (2) , 60 (18), 55 (4).
(実施例16)
2-(トリフルオロメチル)-1-トシルアジリジンの調製(Example 16)
Preparation of 2- (trifluoromethyl) -1-tosylaziridine
撹拌子を備えた25mLの二口フラスコに、式(XXXIIa)で示されるp-トルエンスルホンアミド(689.8 mg, 4.03mmol)とTHF(13mL)を加えて撹拌し、この溶液に水素化ナトリウム(62.7%, 191.8 mg, 4.83mmol)を加えて15分撹拌した。 To a 25 mL two-necked flask equipped with a stir bar, p-toluenesulfonamide (689.8 mg, 4.03 mmol) represented by the formula (XXXIIa) and THF (13 mL) were added and stirred, and sodium hydride (62.7 %, 191.8 mg, 4.83 mmol) and stirred for 15 minutes.
この混合物に実施例5で調製した式(IIIa)で示される(3,3,3-トリフルオロプロペン-1-イル)-ジフェニルスルホニウム トリフラート(1.839g, 4.23mmol)を加え、室温で15分反応させた。反応混合物に飽和炭酸水素ナトリウム水溶液を加え、さらに抽出溶媒としてヘキサン:酢酸エチル=3/1混合溶媒を加えて有機層を分離した。 To this mixture was added (3,3,3-trifluoropropen-1-yl) -diphenylsulfonium triflate (1.839 g, 4.23 mmol) of the formula (IIIa) prepared in Example 5 and reacted at room temperature for 15 minutes. I let you. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and a hexane: ethyl acetate = 3/1 mixed solvent was further added as an extraction solvent to separate the organic layer.
水層をヘキサン:酢酸エチル=3/1混合溶媒で3回抽出し、得られた有機層及び混合抽出液を合わせて、硫酸ナトリウム上で乾燥、ろ過、減圧濃縮することにより、粗製物を油状残渣として得た。得られた粗製物を、シリカゲルカラムクロマトグラフィー(溶離液:ヘキサン:酢酸エチル=10/1、その後ヘキサン:酢酸エチル=3/1)で精製することにより、式(XXXIIb)で示される2-(トリフルオロメチル)-1-トシルアジリジンが、白色固体(収率 91%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 2.47 (3H, s), 2.52 (1H, d, J = 4.0 Hz), 2.82 (1H, d, J = 7.0 Hz), 3.23-3.31 (1H, m), 7.38 (2H, d, J = 8.4 Hz), 7.85 (2H, d, J = 8.4 Hz);
13C NMR (CDCl3, 75 MHz) δ 21.6, 28.9 (q, J = 2.5 Hz), 36.7 (q, J = 41.7 Hz), 122.1 (q, J = 274.0 Hz), 128.2, 129.9, 133.6, 145.6;
19F NMR (CDCl3, 283 MHz) δ -73.3 (d, J = 4.6 Hz).The aqueous layer was extracted three times with a mixed solvent of hexane: ethyl acetate = 3/1. The obtained organic layer and the mixed extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as an oil. Obtained as a residue. The obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 10/1, then hexane: ethyl acetate = 3/1) to give 2- (2) represented by the formula (XXXIIb). Trifluoromethyl) -1-tosylaziridine was obtained as a white solid (91% yield).
1 H NMR (CDCl 3 , 300 MHz) δ 2.47 (3H, s), 2.52 (1H, d, J = 4.0 Hz), 2.82 (1H, d, J = 7.0 Hz), 3.23-3.31 (1H, m) , 7.38 (2H, d, J = 8.4 Hz), 7.85 (2H, d, J = 8.4 Hz);
13 C NMR (CDCl 3 , 75 MHz) δ 21.6, 28.9 (q, J = 2.5 Hz), 36.7 (q, J = 41.7 Hz), 122.1 (q, J = 274.0 Hz), 128.2, 129.9, 133.6, 145.6 ;
19 F NMR (CDCl 3 , 283 MHz) δ -73.3 (d, J = 4.6 Hz).
(3.イミド化合物の製造)
(実施例17)
2-(1,1,1-トリフルオロプロペ-2-エン-2-イル)イソインドリン-1,3-ジオンの調製(3. Production of imide compound)
(Example 17)
Preparation of 2- (1,1,1-trifluoroprop-2-en-2-yl) isoindoline-1,3-dione
撹拌子を備えた25mLの二口フラスコに、実施例4で調製した式(IIa)で示される(3,3,3-トリフルオロプロペン-1-イル)-フェニルトルイルスルホニウム トリフラート(458mg, 1.03mmol)、ジクロロメタン(2mL)、DMSO(1mL)、式(XXXIIIa)で示されるフタルイミド(136mg, 0.92mmol)、トリエチルアミン(140mL, 0.99mmol)を加え、室温で3時間反応させた。 In a 25 mL two-necked flask equipped with a stir bar, (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate of the formula (IIa) prepared in Example 4 (458 mg, 1.03 mmol) was added. ), Dichloromethane (2 mL), DMSO (1 mL), phthalimide (136 mg, 0.92 mmol) represented by the formula (XXXIIIa) and triethylamine (140 mL, 0.99 mmol) were added, and the mixture was reacted at room temperature for 3 hours.
反応混合物飽和炭酸水素ナトリウム水溶液を加え、さらに抽出溶媒としてエーテルを加えて有機層を分離した。水層をエーテルで3回抽出し、得られた有機層及びエーテル抽出液を合わせて、硫酸ナトリウム上で乾燥、ろ過、減圧濃縮することにより、粗製物を油状残渣として得た。 A saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and ether was further added as an extraction solvent to separate the organic layer. The aqueous layer was extracted three times with ether, and the resulting organic layer and the ether extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as an oily residue.
得られた粗製物を、シリカゲルカラムクロマトグラフィー(溶離液:ヘキサン:酢酸エチル=3/1)で精製することにより、式(XXXIIIb)で示される2-(1,1,1-トリフルオロプロペ-2-エン-2-イル)イソインドリン-1,3-ジオンが、白色の固体(収率 91%)として得られた。
融点 92.2-93.9 ℃
1H NMR (CDCl3, 300 MHz) δ 5.87-5.88 (1H, m), 6.42 (1H, q, J = 0.92 Hz),7.80-7.92 (2H, m), 7.93-7.96 (2H, m);
13C NMR (CDCl3, 75 MHz) δ 120.3 (q, J = 274.7 Hz), 124.1, 126.3 (q, J = 3.7 Hz), 129.0 (q, J = 38.0 Hz), 131.5, 134.7, 166.0;
19F NMR (CDCl3, 283 MHz) δ -69.9 (s);
IR (KBr) 3131, 1729, 1401, 1302, 1208, 1182, 1142, 1120, 886, 718, 637 cm-1;
GC-MS (EI, m/z, 70 eV) 241 (24, M+), 197 (6), 172 (6), 144 (2), 118 (9), 104 (52), 76 (100), 66 (20), 50 (38);
元素分析 C11H6F3NO2 計算値 C; 54.78, H; 2.51, N; 5.81 測定値 C; 55.03, H; 2.52, N; 5.81.The obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 3/1) to give 2- (1,1,1-trifluoroprop-propoxide represented by the formula (XXXIIIb). 2-En-2-yl) isoindoline-1,3-dione was obtained as a white solid (91% yield).
Melting point 92.2-93.9 ℃
1 H NMR (CDCl 3 , 300 MHz) δ 5.87-5.88 (1H, m), 6.42 (1H, q, J = 0.92 Hz), 7.80-7.92 (2H, m), 7.93-7.96 (2H, m);
13 C NMR (CDCl 3 , 75 MHz) δ 120.3 (q, J = 274.7 Hz), 124.1, 126.3 (q, J = 3.7 Hz), 129.0 (q, J = 38.0 Hz), 131.5, 134.7, 166.0;
19 F NMR (CDCl 3 , 283 MHz) δ -69.9 (s);
IR (KBr) 3131, 1729, 1401, 1302, 1208, 1182, 1142, 1120, 886, 718, 637 cm -1 ;
GC-MS (EI, m / z, 70 eV) 241 (24, M + ), 197 (6), 172 (6), 144 (2), 118 (9), 104 (52), 76 (100) , 66 (20), 50 (38);
Elemental analysis C 11 H 6 F 3 NO 2 Calculated C; 54.78, H; 2.51, N; 5.81 Measured C; 55.03, H; 2.52, N; 5.81.
(実施例18)
2-(1,1,1-トリフルオロプロペ-2-エン-2-イル)-1,8-ナフタルイミドの調製(Example 18)
Preparation of 2- (1,1,1-trifluoroprop-2-en-2-yl) -1,8-naphthalimide
実施例17で用いた式(XXXIIIa)で示されるフタルイミドを、式(XXXIVa)で示されるナフタルイミドに代替し、実施例17と同じ操作を行ったところ、式(XXXIVb)で示される2-(1,1,1-トリフルオロプロペ-2-エン-2-イル)-1,8-ナフタルイミドが、固体(収率3%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 5.90-5.93 (1H, m), 6.50-6.53 (1H, m), 7.81 (2H, dd, J= 8.4, 7.3 Hz), 8.29 (2H, d, J = 8.4 Hz), 8.66 (2H, d, J = 7.3 Hz);
19F NMR (CDCl3, 283 MHz) δ -68.3 (s).The same operation as in Example 17 was performed by replacing the phthalimide represented by the formula (XXXIIIa) used in Example 17 with the naphthalimide represented by the formula (XXXIVa). 1,1,1-trifluoroprop-2-en-2-yl) -1,8-naphthalimide was obtained as a solid (yield 3%).
1 H NMR (CDCl 3 , 300 MHz) δ 5.90-5.93 (1H, m), 6.50-6.53 (1H, m), 7.81 (2H, dd, J = 8.4, 7.3 Hz), 8.29 (2H, d, J = 8.4 Hz), 8.66 (2H, d, J = 7.3 Hz);
19 F NMR (CDCl 3 , 283 MHz) δ -68.3 (s).
(4.アミド化合物の製造)
(実施例19)
1-(1,1,1-トリフルオロプロペ-2-エン-2-イル)インドリン-2,3-ジオンの調製(4. Production of amide compound)
(Example 19)
Preparation of 1- (1,1,1-trifluoroprop-2-en-2-yl) indoline-2,3-dione
実施例17で用いた式(XXXIIIa)で示されるフタルイミドを、式(XXXVa)で示されるイサチンに代替し、実施例17と同じ操作を行ったところ、式(XXXVb)で示される1-(1,1,1-トリフルオロプロペ-2-エン-2-イル)インドリン-2,3-ジオンが、黄色の固体(収率55%)として得られた。
融点 93.2-94.5 ℃
1H NMR (CDCl3, 300 MHz) δ 5.98-6.03 (1H, m), 6.49-6.51 (1H, m), 6.91 (1H, d, J = 8.1 Hz), 7.22 (1H, d, J = 7.5 Hz), 7.60-7.73 (2H, m);
13C NMR (CDCl3, 75 MHz) δ 111.3 (t, J = 1.3 Hz), 117.4, 120.3 (q, J = 275.3 Hz), 124.8, 125.7, 126.9 (q, J = 3.7 Hz), 129.2 (q, J = 37.4 Hz), 138.8, 150.5, 157.2, 181.0;
19F NMR (CDCl3, 283 MHz) δ -69.5 (s);
IR (KBr) 1790, 1770, 1732, 1714, 1694, 1621, 1615, 1589, 1574, 1480, 1409, 1278, 1189, 1134, 1089, 975, 816, 702 cm-1;
GC-MS (EI, m/z, 70 eV) 241 (3, M+), 213 (31), 165 (15), 144 (40), 116 (100), 104(13), 89 (92), 63 (54)
元素分析 C11H6F3NO2 計算値 C; 54.78, H; 2.51, N; 5.81 測定値 C; 54.86, H; 2.56, N; 5.80.When phthalimide represented by the formula (XXXIIIa) used in Example 17 was replaced with isatin represented by the formula (XXXVa) and the same operation as in Example 17 was performed, 1- (1 represented by the formula (XXXVb) was obtained. , 1,1-trifluoroprop-2-en-2-yl) indoline-2,3-dione was obtained as a yellow solid (55% yield).
Melting point 93.2-94.5 ℃
1 H NMR (CDCl 3 , 300 MHz) δ 5.98-6.03 (1H, m), 6.49-6.51 (1H, m), 6.91 (1H, d, J = 8.1 Hz), 7.22 (1H, d, J = 7.5 Hz), 7.60-7.73 (2H, m);
13 C NMR (CDCl 3 , 75 MHz) δ 111.3 (t, J = 1.3 Hz), 117.4, 120.3 (q, J = 275.3 Hz), 124.8, 125.7, 126.9 (q, J = 3.7 Hz), 129.2 (q , J = 37.4 Hz), 138.8, 150.5, 157.2, 181.0;
19 F NMR (CDCl 3 , 283 MHz) δ -69.5 (s);
IR (KBr) 1790, 1770, 1732, 1714, 1694, 1621, 1615, 1589, 1574, 1480, 1409, 1278, 1189, 1134, 1089, 975, 816, 702 cm -1 ;
GC-MS (EI, m / z, 70 eV) 241 (3, M + ), 213 (31), 165 (15), 144 (40), 116 (100), 104 (13), 89 (92) , 63 (54)
Elemental analysis C 11 H 6 F 3 NO 2 Calculated C; 54.78, H; 2.51, N; 5.81 Measured C; 54.86, H; 2.56, N; 5.80.
(実施例20)
2-(N-(1,1,1-トリフルオロプロペ-2-エン-2-イル)-N-トシル)アミノエタノールの調製(Example 20)
Preparation of 2- (N- (1,1,1-trifluoroprop-2-en-2-yl) -N-tosyl) aminoethanol
撹拌子を備えた25mLの二口フラスコに実施例4で調製した式(IIa)で示される(3,3,3-トリフルオロプロペン-1-イル)-フェニルトルイルスルホニウム トリフラート(111.3mg, 0.25mmol)、ジクロロメタン(1mL)、式(XXXIVa)で示される2-(トシルアミノ)エタノール(66.3mg, 0.30mmol)、DBU(75mL, 0.50mmol)を加え、室温で2時間反応させた。 A (3,3,3-trifluoropropen-1-yl) -phenyltoluylsulfonium triflate of the formula (IIa) prepared in Example 4 (111.3 mg, 0.25 mmol) was prepared in a 25 mL two-necked flask equipped with a stir bar. ), Dichloromethane (1 mL), 2- (tosylamino) ethanol (66.3 mg, 0.30 mmol) represented by the formula (XXXIVa) and DBU (75 mL, 0.50 mmol) were added, and the mixture was reacted at room temperature for 2 hours.
反応混合物に水とジクロロメタンを加えて有機層を分離した。水層をジクロロメタンで3回抽出し、得られた有機層及び抽出液を合わせて、硫酸ナトリウム上で乾燥、ろ過、減圧濃縮することにより、粗製物を油状残渣として得た。 Water and dichloromethane were added to the reaction mixture, and the organic layer was separated. The aqueous layer was extracted three times with dichloromethane, and the obtained organic layer and the extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product as an oily residue.
得られた粗製物を、シリカゲルカラムクロマトグラフィー(溶離液:ヘキサン:酢酸エチル=1/1)で精製することにより、式(XXXIVb)で示される2-(N-(1,1,1-トリフルオロプロペ-2-エン-2-イル)-N-トシル)アミノエタノールが、無色のオイル(収率 78%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 2.12 (1H, t, J = 5.4 Hz), 2.44 (3H, s), 3.56 (2H, t, J = 5.3 Hz), 3.74 (2H, q, J = 5.4 Hz), 5.86 (1H, m), 6.15 (1H, t, J = 0.7 Hz), 7.32 (2H, d, J = 8.1Hz), 7.73 (2H, d, J = 8.3 Hz);
13C NMR (CDCl3, 75 MHz) δ 21.5, 51.7, 59.5, 120.9 (q, J = 276.5 Hz), 125.9 (q, J = 3.3 Hz), 127.8, 129.7, 133.7 (q, J = 34.7 Hz), 135.3, 144.4;
19F NMR (CDCl3, 283 MHz) δ -60.1 (s);
IR (NaCl) 3542, 2930, 1598, 1354, 1165, 974, 684 cm-1;
GC-MS (EI, m/z, 70 eV) 245 (1), 214 (2), 155 (16), 124 (11), 91 (100), 77 (2), 65 (23), 54 (8).
元素分析 C12H14F3NO3S 計算値 C; 46.60, H; 4.56, N; 4.53 測定値 C; 46.74, H; 4.65, N; 4.65.The obtained crude product was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 1/1) to give 2- (N- (1,1,1-trimethyl) represented by the formula (XXXIVb). Fluoroprop-2-en-2-yl) -N-tosyl) aminoethanol was obtained as a colorless oil (78% yield).
1 H NMR (CDCl 3 , 300 MHz) δ 2.12 (1H, t, J = 5.4 Hz), 2.44 (3H, s), 3.56 (2H, t, J = 5.3 Hz), 3.74 (2H, q, J = 5.4 Hz), 5.86 (1H, m), 6.15 (1H, t, J = 0.7 Hz), 7.32 (2H, d, J = 8.1 Hz), 7.73 (2H, d, J = 8.3 Hz);
13 C NMR (CDCl 3 , 75 MHz) δ 21.5, 51.7, 59.5, 120.9 (q, J = 276.5 Hz), 125.9 (q, J = 3.3 Hz), 127.8, 129.7, 133.7 (q, J = 34.7 Hz) , 135.3, 144.4;
19 F NMR (CDCl 3 , 283 MHz) δ -60.1 (s);
IR (NaCl) 3542, 2930, 1598, 1354, 1165, 974, 684 cm -1 ;
GC-MS (EI, m / z, 70 eV) 245 (1), 214 (2), 155 (16), 124 (11), 91 (100), 77 (2), 65 (23), 54 ( 8).
Elemental analysis C 12 H 14 F 3 NO 3 S calculated C; 46.60, H; 4.56, N; 4.53 measured C; 46.74, H; 4.65, N; 4.65.
(5.アルコキシ化合物の製造)
(実施例21)
1-(1,1,1-トリフルオロプロペ-2-エン-2-イルオキシ)-2-メチル-N-トシルプロパン-2-アミンの調製(5. Production of alkoxy compound)
(Example 21)
Preparation of 1- (1,1,1-trifluoroprop-2-en-2-yloxy) -2-methyl-N-tosylpropan-2-amine
実施例20で用いた式(XXXIVa)で示される2-(トシルアミノ)エタノールを、式(XXXVIIa)で示される2-メチル-2-(トシルアミノ)プロパン-1-オールに代替し、実施例20と同じ操作を行ったところ、式(XXXVIIb)で示される1-(1,1,1-トリフルオロプロペ-2-エン-2-イルオキシ)-2-メチル-N-トシルプロパン-2-アミンが、白色の固体(収率65%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 1.27 (6H, s), 2.42 (3H, s), 3.53 (2H, s), 4.29 (1H, m, J = 1.9 Hz), 4.77 (1H, d, J = 4.0 Hz), 4.81 (1H, s), 7.28 (2H, d, J = 8.2 Hz),
7.76 (2H, d, J = 8.4 Hz);
13C NMR (CDCl3, 75 MHz) δ 21.4, 24.6, 55.7, 74.5, 88.0 (q, J = 3.7 Hz), 119.5 (q, J = 273.4 Hz), 126.9, 129.6, 139.8, 143.2, 146.6 (q, J = 34.9 Hz);
19F NMR (CDCl3, 283 MHz) δ -73.8 (s);
IR (KBr) 3259, 1655, 1386, 1326, 1155, 985, 676 cm-1;
GC-MS (EI, m/z, 70 eV) 212 (30), 155 (44), 139 (2), 91(100), 70 (2), 65 (15), 55
(4).
HRMS C14H18F3NO3S 計算値 338.1059 測定値 338.1038.The 2- (tosylamino) ethanol represented by the formula (XXXIVa) used in Example 20 was replaced with 2-methyl-2- (tosylamino) propan-1-ol represented by the formula (XXXVIIa). When the same operation was performed, 1- (1,1,1-trifluoroprop-2-en-2-yloxy) -2-methyl-N-tosylpropan-2-amine represented by the formula (XXXVIIb) Obtained as a white solid (65% yield).
1 H NMR (CDCl 3 , 300 MHz) δ 1.27 (6H, s), 2.42 (3H, s), 3.53 (2H, s), 4.29 (1H, m, J = 1.9 Hz), 4.77 (1H, d, J = 4.0 Hz), 4.81 (1H, s), 7.28 (2H, d, J = 8.2 Hz),
7.76 (2H, d, J = 8.4 Hz);
13 C NMR (CDCl 3 , 75 MHz) δ 21.4, 24.6, 55.7, 74.5, 88.0 (q, J = 3.7 Hz), 119.5 (q, J = 273.4 Hz), 126.9, 129.6, 139.8, 143.2, 146.6 (q , J = 34.9 Hz);
19 F NMR (CDCl 3 , 283 MHz) δ -73.8 (s);
IR (KBr) 3259, 1655, 1386, 1326, 1155, 985, 676 cm -1 ;
GC-MS (EI, m / z, 70 eV) 212 (30), 155 (44), 139 (2), 91 (100), 70 (2), 65 (15), 55
(Four).
HRMS C 14 H 18 F 3 NO 3 S Calculated 338.1059 Measured 338.1038.
(6.リン化合物の製造)
(実施例22)
ジエチル 1,1,1-トリフルオロプロぺ-2-エン?2?イルホスホネート(6. Production of phosphorus compound)
(Example 22)
Diethyl 1,1,1-trifluoroprop-2-ene? 2? Ilphosphonate
撹拌子を備えた25mLの二口フラスコに、実施例5で調製した式(IIIa)で示される(3,3,3-トリフルオロプロペン-1-イル)-ジフェニルスルホニウム トリフラート(138.0mg, 0.32mmol)、モレキュラーシーブス4A(155mg)、ジクロロメタン(1.5mL)を加えて30分撹拌した。 In a 25 mL two-necked flask equipped with a stir bar, (3,3,3-trifluoropropen-1-yl) -diphenylsulfonium triflate (138.0 mg, 0.32 mmol) of the formula (IIIa) prepared in Example 5 was added. ), Molecular sieves 4A (155 mg) and dichloromethane (1.5 mL) were added and stirred for 30 minutes.
この混合物を0 ℃に冷却し、式(XXXVIIIa)で示されるジエチルホスホナート(24mL, 0.19mmol)、ジイソプロピルエチルアミン(126mL, 0.71mmol)を加えた後、室温までゆっくりと温度を上昇させ引き続き室温で12時間反応させた。
反応混合物をセライトのショートカラムを通して沈殿物を除去した。ろ液に水を加え、抽出溶媒としてヘキサン:酢酸エチル=3/1混合溶媒を加えて有機層を分離した。The mixture was cooled to 0 ° C., diethylphosphonate represented by the formula (XXXVIIIa) (24 mL, 0.19 mmol) and diisopropylethylamine (126 mL, 0.71 mmol) were added, and then the temperature was slowly raised to room temperature. The reaction was performed for 12 hours.
The reaction mixture was passed through a short column of celite to remove the precipitate. Water was added to the filtrate, and an organic layer was separated by adding a hexane: ethyl acetate = 3/1 mixed solvent as an extraction solvent.
水層をヘキサン:酢酸エチル=3/1混合溶媒で3回抽出し、得られた有機層及び混合抽出液を合わせて、硫酸ナトリウム上で乾燥、ろ過、減圧濃縮することにより、粗製物を油状残渣として得た。 The aqueous layer was extracted three times with a mixed solvent of hexane: ethyl acetate = 3/1. The obtained organic layer and the mixed extract were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as an oil. Obtained as a residue.
得られた粗製物を、シリカゲルカラムクロマトグラフィー(溶離液:ヘキサン、その後酢酸エチル)で精製することにより、式(XXXVIIIb)で示されるジエチル1,1,1-トリフルオロプロぺ-2-エン?2?イルホスホネートが、薄い黄色のオイル(収率 48%)として得られた。
1H NMR (CDCl3, 300 MHz) δ 1.36 (6H, t, J = 6.8 Hz), 4.06-4.28 (4H, m), 6.63 (1H, dq, J = 40.2, 1.7 Hz), 6.67 (1H, dm, J = 20.6 Hz);
19F NMR (CDCl3, 283 MHz) δ -64.4 (s);
GC-MS (EI, m/z, 70 eV) 232 (M+, 0.4), 205 (40), 177 '73), 164 (65), 159 (70), 157 (61), 105 (55), 81 (66), 65 (100).The obtained crude product was purified by silica gel column chromatography (eluent: hexane, then ethyl acetate) to obtain diethyl 1,1,1-trifluoroprop-2-ene represented by the formula (XXXVIIIb)? 2? The ylphosphonate was obtained as a pale yellow oil (48% yield).
1 H NMR (CDCl 3 , 300 MHz) δ 1.36 (6H, t, J = 6.8 Hz), 4.06-4.28 (4H, m), 6.63 (1H, dq, J = 40.2, 1.7 Hz), 6.67 (1H, dm, J = 20.6 Hz);
19 F NMR (CDCl 3 , 283 MHz) δ -64.4 (s);
GC-MS (EI, m / z, 70 eV) 232 (M +, 0.4), 205 (40), 177 '73), 164 (65), 159 (70), 157 (61), 105 (55), 81 (66), 65 (100).
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JPH10182824A (en) * | 1996-12-27 | 1998-07-07 | Kagaku Gijutsu Shinko Jigyodan | Poly(arylene sulfonum salt) compound |
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JPS54148775A (en) * | 1978-05-15 | 1979-11-21 | Mitsubishi Chem Ind Ltd | Preparation of pyrroline derivative |
JPH0532619A (en) * | 1991-08-01 | 1993-02-09 | Nikko Kyodo Co Ltd | Production of aziridine compound |
JPH10182824A (en) * | 1996-12-27 | 1998-07-07 | Kagaku Gijutsu Shinko Jigyodan | Poly(arylene sulfonum salt) compound |
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