JP2012506842A - ベンゾノルボルネンの製造方法 - Google Patents
ベンゾノルボルネンの製造方法 Download PDFInfo
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- JP2012506842A JP2012506842A JP2011532562A JP2011532562A JP2012506842A JP 2012506842 A JP2012506842 A JP 2012506842A JP 2011532562 A JP2011532562 A JP 2011532562A JP 2011532562 A JP2011532562 A JP 2011532562A JP 2012506842 A JP2012506842 A JP 2012506842A
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- Prior art keywords
- compound
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- cyclopentadiene
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 9
- ILMCRZOMKCLIFZ-UHFFFAOYSA-N benzonorbornene Chemical compound C12=CC=CC=C2C2CCC1C2 ILMCRZOMKCLIFZ-UHFFFAOYSA-N 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims abstract description 22
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 11
- VLBAAZYGJAXMBQ-UHFFFAOYSA-N 9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-amine Chemical compound NC1=CC=CC2=C1C1CCC2C1=C(Cl)Cl VLBAAZYGJAXMBQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052705 radium Inorganic materials 0.000 claims description 2
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- GGKYLHNARFFORH-UHFFFAOYSA-N 2-amino-6-nitrobenzoic acid Chemical compound NC1=CC=CC([N+]([O-])=O)=C1C(O)=O GGKYLHNARFFORH-UHFFFAOYSA-N 0.000 description 3
- BMHUFYBSDMWTOX-UHFFFAOYSA-N 5-(dichloromethylidene)cyclopenta-1,3-diene Chemical compound ClC(Cl)=C1C=CC=C1 BMHUFYBSDMWTOX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl nitrite Chemical compound 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- PNPBGYBHLCEVMK-UHFFFAOYSA-L benzylidene(dichloro)ruthenium;tricyclohexylphosphane Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-L 0.000 description 2
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 1
- CCCGEKHKTPTUHJ-VHSXEESVSA-N (1S,4R)-benzovindiflupyr Chemical group C1([C@@]2([H])CC[C@@]3(C2=C(Cl)Cl)[H])=C3C=CC=C1NC(=O)C1=CN(C)N=C1C(F)F CCCGEKHKTPTUHJ-VHSXEESVSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- HJHFPHJJAKLLES-UHFFFAOYSA-N 1-bromo-2-(trichloromethyl)cyclopentene Chemical compound ClC(Cl)(Cl)C1=C(Br)CCC1 HJHFPHJJAKLLES-UHFFFAOYSA-N 0.000 description 1
- ZCPNFPKXFOVQPM-UHFFFAOYSA-N 1-chloro-1-(trichloromethyl)cyclopentane Chemical compound ClC1(CCCC1)C(Cl)(Cl)Cl ZCPNFPKXFOVQPM-UHFFFAOYSA-N 0.000 description 1
- FZGCRLYBLOGMOI-UHFFFAOYSA-N 1-chloro-2-(trichloromethyl)cyclopentene Chemical compound ClC1=C(C(Cl)(Cl)Cl)CCC1 FZGCRLYBLOGMOI-UHFFFAOYSA-N 0.000 description 1
- FNHZYVWMMOAOIX-UHFFFAOYSA-N 11-(dichloromethylidene)tricyclo[6.2.1.02,7]undeca-2,4,6-triene Chemical compound ClC(Cl)=C1C2CCC1c1ccccc21 FNHZYVWMMOAOIX-UHFFFAOYSA-N 0.000 description 1
- CGCVLTOGUMLHNP-UHFFFAOYSA-N 2,3-dimethylbutane-2,3-diamine Chemical compound CC(C)(N)C(C)(C)N CGCVLTOGUMLHNP-UHFFFAOYSA-N 0.000 description 1
- PTSLUOSUHFGQHV-UHFFFAOYSA-N 2-chloroheptane Chemical compound CCCCCC(C)Cl PTSLUOSUHFGQHV-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical class [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- CCCGEKHKTPTUHJ-UHFFFAOYSA-N N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC2=C1C1CCC2C1=C(Cl)Cl CCCGEKHKTPTUHJ-UHFFFAOYSA-N 0.000 description 1
- ZFYPJJGAUQKRIS-UHFFFAOYSA-N [O-][N+](c1cccc(C2CC3)c1C3C2=C(Cl)Cl)=O Chemical compound [O-][N+](c1cccc(C2CC3)c1C3C2=C(Cl)Cl)=O ZFYPJJGAUQKRIS-UHFFFAOYSA-N 0.000 description 1
- ZZRIKLZFKKNHSS-UHFFFAOYSA-N [O-][N+](c1cccc(C2CC3)c1C3C2=O)=O Chemical compound [O-][N+](c1cccc(C2CC3)c1C3C2=O)=O ZZRIKLZFKKNHSS-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- NQLVCAVEDIGMMW-UHFFFAOYSA-N cyclopenta-1,3-diene;cyclopentane;nickel Chemical compound [Ni].C=1C=C[CH-]C=1.[CH-]1[CH-][CH-][CH-][CH-]1 NQLVCAVEDIGMMW-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011985 first-generation catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CCCGEKHKTPTUHJ-ZJUUUORDSA-N solatenol Chemical group C1([C@]2([H])CC[C@]3(C2=C(Cl)Cl)[H])=C3C=CC=C1NC(=O)C1=CN(C)N=C1C(F)F CCCGEKHKTPTUHJ-ZJUUUORDSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
- A61K31/27—Esters, e.g. nitroglycerine, selenocyanates of carbamic or thiocarbamic acids, meprobamate, carbachol, neostigmine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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Abstract
Description
a)亜硝酸アルキルの存在下、式A
b)好適な金属触媒の存在下、式Cの化合物を水素化し、式D
c)式Dの化合物をオゾン処理後、還元剤で処理し、式E
d)式Eの化合物をトリフェニルホスフィン/四塩化炭素と反応させ、式F
e)金属触媒の存在下、式Fの化合物を水素化し、9−ジクロロメチレン−1,2,3,4−テトラヒドロ−1,4−メタノ−ナフタレン−5−イルアミンとすること、
により9−ジクロロメチレン−1,2,3,4−テトラヒドロ−1,4−メタノ−ナフタレン−5−イルアミンを調製することが知られている。
a)ラジカル開始剤の存在下、シクロペンタジエンをCXCl3(ここでXはクロロ又はブロモである)と反応させて式II
とするステップか、
aa)金属触媒の存在下、シクロペンタジエンをCXCl3(ここでXはクロロである)と反応させて式II
b)適切な溶媒の存在下、式IIの化合物を塩基と反応させて、式III
c)1,2−デヒドロ−6−ニトロベンゼンの存在下、式IIIの化合物を、式IV
d)金属触媒の存在下、式IVの化合物を水素源と共に水素化するステップ、を含んでなる製造方法が提供される。
a)ラジカル開始剤の存在下、シクロペンタジエンをCXCl3(ここでXはクロロ又はブロモである)と反応させて式II
式IIの化合物は、以下:
反応ステップb)の好ましい塩基は、アルカリ金属アルコラート、例えば、ナトリウムtert−ブトキシド及びカリウムtert−ブトキシド又はNaNH2又はリチウムジイソプロピルアミドなどの金属アミドである。
当該方法は、
a)ラジカル開始剤の存在下、シクロペンタジエンをCXCl3(ここでXはクロロ又はブロモである)と反応させて式II
b)適切な溶媒の存在下で、式IIの化合物を塩基と反応させるステップ、
を含んでなる。
1,2−デヒドロ−6−ニトロベンゼンは、インサイチュで作られる
[例えば、L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977) and H. Seidel, Chemische Berichte, 34, 4351 (1901)に記載されるように、式(A)
水素化反応のための好ましい金属触媒は、ラネー(Raney)ニッケル、プラチナ、好ましくは炭素などの担体上のプラチナ、好ましくは、炭素などの担体上のパラジウムからなる群から選択されるが、当該群に限定されない。特に好ましい触媒は、ラネーニッケルである。好適な水素源は、水素又はヒドラジンであり、好ましくは水素である。
aa)金属触媒の金属成分が、ルテニウム、銅、鉄、パラジウム及びラジウムから選択される金属触媒の存在下、シクロペンタジエンをCXCl3(ここでXはクロロである)と反応させて式II
b)適切な溶媒の存在下、式IIの化合物を、アルカリ金属アルコラートから選択される塩基と反応させ、式III
c)1,2−デヒドロ−6−ニトロベンゼンの存在下、式IIIの化合物を、式IV
d)金属触媒の存在下、式IVの化合物を水素源と共に水素化するステップ、を含んでなる。
実施例P1:式IIaの化合物の調製
オートクレーブに、THF(130mL)、湿ラニーニッケル(2g)及び式IVの化合物(20g)を充填した。オートクレーブを閉め、含有物を掻き混ぜ、窒素を3回パージして酸素を除去し、その後、水素を3回パージした。水素取り込み終了後、典型的には3〜4時間後、反応塊(mass)を40℃でさらに30分保持した。この後、圧力を解放し含有物を環境温度まで冷却した。真空下で溶媒を除去し、得られたオイルを静置して結晶化させ、黄色がかった色から茶色の式Iの化合物を収量18gで得た(96%、純度94%の生成物)。
塩化銅(I)(0.99g)、テトラメチレルエチレンジアミン(TMEDA、2.32g)及びアセトニトリル(100mL)の混合物を、窒素雰囲気下75℃で25分加熱し、その後室温まで冷却した。
新たに調製したシクロペンタジエン(66.0g)を、四塩化炭素(307g)中に溶解させた。
窒素雰囲気下、アセトニトリル(80g)及び40%の触媒溶液を、窒素下でガラスリアクターに入れた。混合物を温度75℃まで加熱した。その後、40%のシクロペンタジエン溶液を一度にリアクターに入れ、温度を60℃〜70℃に維持しながら、触媒溶液の残り及びシクロペンタジエン溶液を同時に添加した。シクロペンタジエン溶液を1時間で、そして触媒溶液を1.5時間で添加した。反応混合物を70℃でさらに1時間攪拌し、環境温度まで冷却し、濾過した。溶媒をロータリーエバポレーターで除去し、残存物を真空蒸留により分画した(40〜45℃、0.1mbar)。収量は170g(75%、純度97〜98%)であり3つの位置異性体の混合物であった。
Claims (7)
- 式I
a)ラジカル開始剤の存在下、シクロペンタジエンをCXCl3(ここでXはクロロ又はブロモである)と反応させて式II
とするステップか、
aa)金属触媒の存在下、シクロペンタジエンをCXCl3(ここでXはクロロである)と反応させて式II
b)適切な溶媒の存在下、式IIの化合物を塩基と反応させて、式III
c)1,2−デヒドロ−6−ニトロベンゼンの存在下、式IIIの化合物を、式IV
d)金属触媒の存在下、式IVの化合物を水素源と共に水素化するステップ、を含んでなる製造方法。 - Xがブロモである、請求項4に記載の製造方法。
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JP2000143560A (ja) * | 1998-11-04 | 2000-05-23 | Asahi Chem Ind Co Ltd | シクロアルケンの塩素化法 |
WO2007048556A1 (en) * | 2005-10-25 | 2007-05-03 | Syngenta Participations Ag | Heterocyclic amide derivatives useful as microbiocides |
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