JP5858998B2 - シクロペンタノン化合物の製造方法、および中間体化合物 - Google Patents
シクロペンタノン化合物の製造方法、および中間体化合物 Download PDFInfo
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- JP5858998B2 JP5858998B2 JP2013519486A JP2013519486A JP5858998B2 JP 5858998 B2 JP5858998 B2 JP 5858998B2 JP 2013519486 A JP2013519486 A JP 2013519486A JP 2013519486 A JP2013519486 A JP 2013519486A JP 5858998 B2 JP5858998 B2 JP 5858998B2
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- 150000001875 compounds Chemical class 0.000 title claims description 242
- -1 cyclopentanone compound Chemical class 0.000 title claims description 92
- 238000004519 manufacturing process Methods 0.000 title claims description 75
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclo-pentanone Natural products O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 title claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 105
- 125000005843 halogen group Chemical group 0.000 claims description 53
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 45
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 230000002140 halogenating effect Effects 0.000 claims description 30
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 17
- 125000001188 haloalkyl group Chemical group 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 16
- 229910052727 yttrium Inorganic materials 0.000 claims description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 9
- 231100000622 toxicogenomics Toxicity 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 54
- 229910052739 hydrogen Inorganic materials 0.000 description 52
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 49
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000000203 mixture Substances 0.000 description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 15
- 239000012044 organic layer Substances 0.000 description 15
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 15
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 11
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 10
- 239000012312 sodium hydride Substances 0.000 description 10
- 229910000104 sodium hydride Inorganic materials 0.000 description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 description 9
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- 150000002170 ethers Chemical class 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 6
- 229940102396 methyl bromide Drugs 0.000 description 6
- 239000005868 Metconazole Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- WGBOKZNIAWFOPN-UHFFFAOYSA-N [3-[(4-chlorophenyl)methyl]-1-(methylsulfonyloxymethyl)-2-oxocyclopentyl]methyl methanesulfonate Chemical compound O=C1C(COS(=O)(=O)C)(COS(C)(=O)=O)CCC1CC1=CC=C(Cl)C=C1 WGBOKZNIAWFOPN-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- XWPZUHJBOLQNMN-UHFFFAOYSA-N metconazole Chemical compound C1=NC=NN1CC1(O)C(C)(C)CCC1CC1=CC=C(Cl)C=C1 XWPZUHJBOLQNMN-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 235000009518 sodium iodide Nutrition 0.000 description 5
- DLPBZANLIRTMKU-UHFFFAOYSA-N 5-[(4-chlorophenyl)methyl]-2,2-dimethylcyclopentan-1-one Chemical compound O=C1C(C)(C)CCC1CC1=CC=C(Cl)C=C1 DLPBZANLIRTMKU-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- DEBIZNDUYYZCBO-UHFFFAOYSA-N COC(=O)C1(Cc2ccc(Cl)cc2)CCC(COS(=O)(=O)c2ccc(C)cc2)(COS(=O)(=O)c2ccc(C)cc2)C1=O Chemical compound COC(=O)C1(Cc2ccc(Cl)cc2)CCC(COS(=O)(=O)c2ccc(C)cc2)(COS(=O)(=O)c2ccc(C)cc2)C1=O DEBIZNDUYYZCBO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- VLDMZKWZJOABBR-UHFFFAOYSA-N [3-[(4-chlorophenyl)methyl]-1-[(4-methylphenyl)sulfonyloxymethyl]-2-oxocyclopentyl]methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1(COS(=O)(=O)C=2C=CC(C)=CC=2)C(=O)C(CC=2C=CC(Cl)=CC=2)CC1 VLDMZKWZJOABBR-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000000855 fungicidal effect Effects 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 0 C*CC(C*)(CCC1)C1=O Chemical compound C*CC(C*)(CCC1)C1=O 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000003983 crown ethers Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- TXQPWONTBLGDEC-UHFFFAOYSA-N methyl 1-(methylsulfonyloxymethyl)-2-oxocyclopentane-1-carboxylate Chemical compound COC(=O)C1(C(CCC1)=O)COS(=O)(=O)C TXQPWONTBLGDEC-UHFFFAOYSA-N 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- LEYKBQSHZTVKRV-UHFFFAOYSA-N 2,2-bis(bromomethyl)-5-[(4-chlorophenyl)methyl]cyclopentan-1-one Chemical compound C1=CC(Cl)=CC=C1CC1C(=O)C(CBr)(CBr)CC1 LEYKBQSHZTVKRV-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 101100132433 Arabidopsis thaliana VIII-1 gene Proteins 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000005948 methanesulfonyloxy group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- XEFHZYULZFZBFU-UHFFFAOYSA-N methyl 1-[(4-chlorophenyl)methyl]-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OC)CCCC1=O XEFHZYULZFZBFU-UHFFFAOYSA-N 0.000 description 2
- DCLNQHDBQDTZAT-UHFFFAOYSA-N methyl 1-[(4-chlorophenyl)methyl]-3-methyl-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OC)CCC(C)C1=O DCLNQHDBQDTZAT-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 description 1
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- JTQYDLRRSJEPEW-UHFFFAOYSA-N 2,2-bis(chloromethyl)-5-[(4-chlorophenyl)methyl]cyclopentan-1-one Chemical compound O=C1C(CCl)(CCl)CCC1CC1=CC=C(Cl)C=C1 JTQYDLRRSJEPEW-UHFFFAOYSA-N 0.000 description 1
- YKNHSSJVHPLBCO-UHFFFAOYSA-N 2-(chloromethyl)-5-[(4-chlorophenyl)methyl]-2-methylcyclopentan-1-one Chemical compound O=C1C(C)(CCl)CCC1CC1=CC=C(Cl)C=C1 YKNHSSJVHPLBCO-UHFFFAOYSA-N 0.000 description 1
- WPHUUIODWRNJLO-UHFFFAOYSA-N 2-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=CC=C1S(Cl)(=O)=O WPHUUIODWRNJLO-UHFFFAOYSA-N 0.000 description 1
- AEQAVKREMWDWAE-UHFFFAOYSA-N 3,3-dimethyl-2-oxocyclopentane-1-carbonitrile Chemical compound CC1(C)CCC(C#N)C1=O AEQAVKREMWDWAE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 description 1
- XAZWLWOIAFPOTF-UHFFFAOYSA-N C(C1=CC=CC=C1)C1C(C(CC1)=O)(C)C Chemical compound C(C1=CC=CC=C1)C1C(C(CC1)=O)(C)C XAZWLWOIAFPOTF-UHFFFAOYSA-N 0.000 description 1
- YYLYWZBXTVFUMG-UHFFFAOYSA-N CC(Cc1ccccc1)(CCC1(CN)CN)C1=O Chemical compound CC(Cc1ccccc1)(CCC1(CN)CN)C1=O YYLYWZBXTVFUMG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- QLSYIEGOUWSMMQ-UHFFFAOYSA-N acetonitrile;ethyl acetate Chemical compound CC#N.CC#N.CCOC(C)=O QLSYIEGOUWSMMQ-UHFFFAOYSA-N 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- 238000005574 benzylation reaction Methods 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000005949 ethanesulfonyloxy group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- VCCWPCPYZBSBOR-UHFFFAOYSA-N methyl 1-[(4-chlorophenyl)methyl]-3,3-bis(hydroxymethyl)-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OC)CCC(CO)(CO)C1=O VCCWPCPYZBSBOR-UHFFFAOYSA-N 0.000 description 1
- QGUHMUXBDNKLNM-UHFFFAOYSA-N methyl 1-[(4-chlorophenyl)methyl]-3,3-dimethyl-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OC)CCC(C)(C)C1=O QGUHMUXBDNKLNM-UHFFFAOYSA-N 0.000 description 1
- WRXULUDQOYWPEL-UHFFFAOYSA-N methyl 1-[(4-chlorophenyl)methyl]-3-(hydroxymethyl)-3-methyl-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OC)CCC(C)(CO)C1=O WRXULUDQOYWPEL-UHFFFAOYSA-N 0.000 description 1
- QGKLLBZTOIHLBV-UHFFFAOYSA-N methyl 1-[(4-chlorophenyl)methyl]-3-methyl-3-(methylsulfonyloxymethyl)-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OC)CCC(C)(COS(C)(=O)=O)C1=O QGKLLBZTOIHLBV-UHFFFAOYSA-N 0.000 description 1
- PZBBESSUKAHBHD-UHFFFAOYSA-N methyl 2-oxocyclopentane-1-carboxylate Chemical compound COC(=O)C1CCCC1=O PZBBESSUKAHBHD-UHFFFAOYSA-N 0.000 description 1
- CNBXWQWCQRDZOS-UHFFFAOYSA-N methyl 3,3-bis(chloromethyl)-1-[(4-chlorophenyl)methyl]-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OC)CCC(CCl)(CCl)C1=O CNBXWQWCQRDZOS-UHFFFAOYSA-N 0.000 description 1
- DXFDPSGNXNPLRF-UHFFFAOYSA-N methyl 3-(chloromethyl)-1-[(4-chlorophenyl)methyl]-3-methyl-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OC)CCC(C)(CCl)C1=O DXFDPSGNXNPLRF-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- KPBSJEBFALFJTO-UHFFFAOYSA-N propane-1-sulfonyl chloride Chemical compound CCCS(Cl)(=O)=O KPBSJEBFALFJTO-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 1
- RKIDPTUGNXTOMU-UHFFFAOYSA-N thionyl iodide Chemical compound IS(I)=O RKIDPTUGNXTOMU-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000003652 trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 1
- GRGCWBWNLSTIEN-UHFFFAOYSA-N trifluoromethanesulfonyl chloride Chemical compound FC(F)(F)S(Cl)(=O)=O GRGCWBWNLSTIEN-UHFFFAOYSA-N 0.000 description 1
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 description 1
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 1
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- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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- C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/73—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
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- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
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Description
で示されるシクロペンタノン化合物の製造方法であって、式(III)
で示される化合物もしくは当該化合物から得られる中間体化合物を触媒もしくはハロゲン化剤と反応させて、Yで示す基を水素原子に置換する工程Aと、上記式(III)で示される化合物もしくは当該化合物から得られる中間体化合物を還元することにより、Z1および水素原子ではない場合のZ2で示す基または原子を水素原子に置換する工程Bとを含む、シクロペンタノン化合物の製造方法である。
で示される中間体化合物である。
で示される中間体化合物である。
本発明に係るシクロペンタノン化合物の製造方法は、式(I)
で示される5−(置換または無置換)ベンジル−2,2−ジメチルシクロペンタノンを製造する方法であって、式(III)
で示される化合物を指す。式(IV)で示される化合物は、下記工程Bにおいて、式(III)で示される化合物を還元することにより得られる化合物である。
で示される化合物を指す。式(II)で示される化合物は、上記工程Aにおいて、式(III)で示される化合物を触媒またはハロゲン化剤と反応させることにより得られる化合物である。
本発明に係るシクロペンタノン化合物の製造方法の一態様では、上記式(III)におけるZ2が置換スルホニルオキシ基またはハロゲン原子である。
工程D:式(V)で示される化合物を、スルホニルクロライドまたはハロゲン化剤と反応させることにより、式(IIIa)を得る工程。
本発明に係るシクロペンタノン化合物の製造方法の一態様では、上記式(III)におけるZ2が水素原子である。
で示される化合物は、下記反応スキーム(反応スキーム4)に示すように、工程Eおよび工程Fにより得ることができる。
工程F:式(VII)で示される化合物を、スルホニルクロライドまたはハロゲン化剤と反応させることにより、式(IIIb)(式中、Z1は、上記式(III)におけるZ1と同義である。)を得る工程。
同様に、式(II)で示される化合物中のZ1が置換スルホニルオキシ基であり、Z2が置換スルホニルオキシ基または水素原子である、式(IIc)で示される化合物を、溶媒中、ハロゲン化塩等で置換する方法により、式(II)で示される化合物中のZ1がハロゲン原子であり、Z2がハロゲン原子または水素原子である、化合物式(IId)で示される化合物を製造することも可能である(下記反応スキーム6参照)。
反応は通常、式(IIIc)または式(IIc)で示される化合物とフッ化カリウム、フッ化セシウム、塩化リチウム、塩化カリウム、臭化リチウム、臭化マグネシウムおよびヨウ化ナトリウム等のハロゲン化塩とを溶媒中で混合することにより行なわれる。
上記式(II)で示される中間体化合物(図1中、式(IIa)で示される中間体化合物および式(IIb)で示される中間体化合物)、上記式(III)で示される中間体化合物(上記式(IIIa)で示される中間体化合物および上記式(IIIb)で示される中間体化合物)、および上記式(V)で示される中間体化合物はいずれも、上述のシクロペンタノン化合物の製造方法に好適に利用される化合物である。すなわち、これらの中間体化合物もまた本願発明の範疇に含まれる。
〔製造例1:1−(4−クロロベンジル)−3−ヒドロキシメチル−3−メチル−2−オキソシクロペンタンカルボン酸メチルエステル(化合物VII−1)の合成〕
異性体VII−1a
収率:18%
異性体VII−1b
収率:76%
〔製造例2:1−(4−クロロベンジル)−3−クロロメチル−3−メチル−2−オキソシクロペンタンカルボン酸メチルエステル(化合物III−1)の合成〕
収率:84%
異性体III−1a
1H-NMR(400MHz,CDCl3)δ:
0.78 (3 H, s), 1.51 - 1.61 (1 H, m), 1.75 - 1.90 (1 H, m), 2.15 - 2.27 (1 H, m),2.36 - 2.48 (1 H, m), 3.15 (2 H, s), 3.42 (1 H, d, J=11.0 Hz), 3.61 (1 H, d, J=11.0 Hz), 3.72 (3 H, s), 7.00 - 7.06 (2 H, m), 7.20 - 7.26 (2 H, m).
異性体III−1b
1H-NMR(400MHz,CDCl3)δ:
1.18 (3 H, s), 1.75 - 1.90 (1 H, m), 1.90 - 2.01 (1 H, m), 2.01 - 2.10 (1H, m), 2.36 - 2.48 (1 H, m), 2.97 (1 H, d, J=14.0Hz), 3.23 (1 H, d, J=14.0 Hz),3.29 (1 H, d, J=11.0 Hz), 3.33 (1 H, d, J=11.0Hz), 3.73 (3 H, s), 7.06 - 7.11 (2 H, m), 7.20 - 7.26 (2 H, m).
〔製造例3:5−(4−クロロベンジル)−2,2−ジメチルシクロペンタノン(化合物I−1)の合成1〕
収率:52%
上記で得られた化合物I−1の性状および1H−NMRスペクトルデータは上記特許文献1に記載のデータと一致した。
〔製造例4:5−(4−クロロベンジル)−2−クロロメチル−2−メチルシクロペンタノン(化合物II−1)の合成〕
収率:90%
1H-NMR(400MHz,CDCl3)δ:
0.93(1.8 H, s), 1.14 (1.2 H, s) 1.42 - 1.75 (2 H, m), 1.90 - 2.34 (2 H, m), 2.35- 2.48 (0.6 H, m), 2.50 - 2.70 (1.4 H, m), 2.90 - 3.10 (0.4 H, m), 3.10 (0.6 H, dd, J= 14.0 Hz), 3.33 (0.4 H, d, J= 10.9 Hz), 3.41 (0.6 H, d, J= 10.8 Hz), 3.47 (0.4 H, d, J= 10.9 Hz), 3.67 (0.6 H, d, J= 10.8 Hz), 7.00 - 7.13 (2 H, m), 7.22- 7.30 (2 H, m).
〔製造例5:5−(4−クロロベンジル)−2,2−ジメチルシクロペンタノン(化合物I−1)の合成2〕
収率:48%
(実施例3)
〔製造例6:1−(4−クロロベンジル)−3,3−ビス(ヒドロキシメチル)−2−オキソシクロペンタンカルボン酸メチルエステル(化合物V−1)の合成〕
収率:94%
1H-NMR(400MHz,CDCl3)δ:
1.72 - 1.80 (1 H, m), 1.91 - 2.01 (3 H, m), 2.15 - 2.19 (1 H, m), 2.40 - 2.45 (1H, m), 3.10 (1 H, d, J=13.8 Hz), 3.17 (1 H, d, J=13.8 Hz), 3.36 (1 H, dd , J=11.0, 7.3 Hz), 3.43 (1 H, dd, J=11.0, 4.2 Hz), 3.69 - 3.75 (2 H, m), 3.73 (3 H, s), 7.05 (2 H, d, J=8.4 Hz), 7.24 (2 H, d, J=8.4Hz).
〔製造例7:1−(4−クロロベンジル)−3,3−ビス(クロロメチル)−2−オキソシクロペンタンカルボン酸メチルエステル(化合物III−2)の合成〕
収率:54%
1H-NMR(400MHz,CDCl3)δ:
1.82 - 2.07 (2 H, m), 2.14 - 2.28 (1 H, m), 2.37 - 2.53 (1 H, m), 3.08 (1 H, d, J= 13.9 Hz), 3.21 (1 H, d, J= 13.9 Hz), 3.34 (1 H, d, J= 11.4 Hz), 3.38 (1 H, d, J= 11.4 Hz),3.61 (1 H, d, J= 11.4 Hz), 3.64 (1 H, d, J= 11.4 Hz), 7.20 - 7.10 (2H, m), 7.22 - 7.28 (2 H, m).
〔製造例8:5−(4−クロロベンジル)−2,2−ビス(クロロメチル)シクロペンタノン(化合物II−2)の合成〕
収率:80%
1H-NMR(400MHz,CDCl3)δ:
1.50 - 1.68 (1 H, m), 2.02 - 2.22 (3 H, m), 2.48 - 2.60 (1 H, m), 2.64 (1 H, dd, J= 13.8, 8.6 Hz), 3.08 (1 H, dd, J= 13.8, 4.3 Hz), 3.41(2 H, s), 3.61(1 H, d, J= 11.0 Hz), 3.66(1 H, d, J= 11.0 Hz), 7.05 - 7.13 (2 H, m), 7.22 - 7.30 (2 H, m).
〔製造例9:5−(4−クロロベンジル)−2,2−ジメチルシクロペンタノン(化合物I−1)の合成3〕
収率:49%
(実施例4)
〔製造例10:1−(4−クロロベンジル)−3−メタンスルホニルオキシメチル−3−メチル−2−オキソシクロペンタンカルボン酸メチルエステル(化合物III−5)の合成〕
収率:91%
異性体III−5a
1H-NMR(CDCl3)δ=
0.72(3H,s),1.55-1.65(1H,m),1.82-1.90(1H,m),2.17-2.26(1H,m),2.38-2.45(1H,m),2.95(3H,s),3.15(2H,s),3.73(3H,s),4.01(1H,d,9.7Hz),4.18(1H,d,J=9.7Hz),7.03(2H,d,J=8.5Hz),7.23(2H,d,J=8.5Hz).
異性体III−5b
1H-NMR(CDCl3)δ=
1.13(3H,s),1.80-1.91(1H,m),1.93-2.09(2H,m),2.38-2.48(1H,m),2.91(1H,d,J=13.9Hz),2.92(3H,s),3.24(1H,d,J=13.9Hz),3.74(3H,s),3.98(2H,s),7.09(2H,d,J=8.5Hz),7.23(2H,d,J=8.5Hz).
〔製造例11:1−(4−クロロベンジル)−3,3−ジメチル−2−オキソシクロペンタンカルボン酸メチルエステル(化合物IV−1)の合成〕
化合物IV−1
収率:51%
化合物I−1
収率:17%
本製造例で得られた化合物IV−1および化合物I−1の性状および1H−NMRスペクトルデータは上記特許文献1に記載のデータと一致した。
〔製造例12:5−(4−クロロベンジル)−2,2−ジメチルシクロペンタノン(化合物I−1)の合成4〕
収率:86%
本製造例で得られた化合物I−1の性状および1H−NMRスペクトルデータは特許文献1に記載のデータと一致した。
(1)中間体、1−(4−クロロベンジル)−3,3−ビス(メタンスルホニルオキシメチル)−2−オキソシクロペンタンカルボン酸メチルエステル(化合物III−3)の合成
収率:94%
1H-NMR(400MHz,CDCl3)δ:
1.98 - 2.00 (2 H, m), 2.07-2.16 (1 H, m), 2.46 - 2.50 (1 H, m), 2.95 (3 H, s), 3.00 (3 H, s),3.06 (1 H, d, J=14.0 Hz), 3.22 (1 H, d, J=14.0 Hz), 3.75 (3 H, s), 3.86 (1 H, d, J=10.0 Hz), 3.98 (1 H, d, J=10.0 Hz), 4.21(2 H, s), 7.00 - 7.10 (2 H, m), 7.20 - 7.30 (2 H, m).
(2)5−(4−クロロベンジル)−2,2−ビス(メタンスルホニルオキシメチル)シクロペンタノン(化合物II−3)の合成
収率:41%
1H-NMR(400MHz,CDCl3)δ:
1.62 - 1.70 (1 H, m), 2.01 - 2.18 (3 H, m), 2.55 - 2.59 (1 H, m), 2.62 (1 H, dd, J= 13.2, 8.4 Hz), 2.99 (3 H, s), 3.02 (3 H, s), 3.08 (1 H, dd, J= 13.2, 3.8 Hz), 4.07 (2 H, s), 4.21 (1 H, d, J= 10.0 Hz), 4.21 (1 H, d, J= 10.0 Hz), 7.05 - 7.12 (2 H, m), 7.23 - 7.31 (2 H, m).
〔参考製造例2〕:5−(4−クロロベンジル)−2,2−ビス(p−トルエンスルホニルオキシメチル)シクロペンタノン(化合物II−4)の合成
(1)中間体、1−(4−クロロベンジル)−3,3−ビス(p−トルエンスルホニルオキシメチル)−2−オキソシクロペンタンカルボン酸メチルエステル(化合物III−4)の合成
粗収率:77%
(2)5−(4−クロロベンジル)−2,2−ビス(p−トルエンスルホニルオキシメチル)シクロペンタノン(化合物II−4)の合成
収率:68%
1H-NMR(400MHz,CDCl3)δ:
1.40 - 1.57 (1 H, m), 1.85 - 2.10 (3 H, m), 2.40 - 2.52 (2 H, m), 2.45 (3 H, s), 2.46 (3H, s), 2.92 - 3.00 (1 H, m), 3.65 - 3.77 (2 H, m), 3.80 - 3.97 (2 H, m), 6.97 - 7.04 (2 H, m), 7.17 - 7.24 (2 H, m), 7.30 - 7.39 (2 H, m), 7.60 - 7.74 (2 H, m).
〔参考製造例3〕:2,2−ビス(ブロモメチル)−5−(4−クロロベンジル)シクロペンタノン(化合物II−5)の合成
収率:51%
1H-NMR(400MHz,CDCl3)δ:
1.50 - 1.70 (1 H, m), 2.02 - 2.20 (3 H, m), 2.50 - 2.62 (1 H, m), 2.65 (1 H, dd, J= 13.8, 8.5 Hz), 3.08 (1 H, dd, J= 13.8, 4.3 Hz), 3.27 (1 H, d, J= 10.8 Hz), 3.30 (1 H, d, J= 10.8 Hz), 3.49(1 H, d, J= 10.3 Hz), 3.53(1 H, d, J= 10.3 Hz), 7.05 - 7.13 (2 H, m), 7.22 - 7.30 (2 H, m).
また、上記の実施例及び参考製造例に準じた方法で、式(II)で示される化合物であって、表1に示した化合物を合成することができる。表1中および後述の表2中、「(X)n」のカラムにおける「4−Cl」は、シクロペンタン環に結合している置換または無置換のベンジル基が、4−クロロベンジル基であることを表している。
Claims (12)
- 式(I)
で示されるシクロペンタノン化合物の製造方法であって、
式(III)
で示される化合物もしくは当該化合物から得られる中間体化合物を触媒もしくはハロゲン化剤と反応させて、Yで示す基を水素原子に置換する工程Aと、
上記式(III)で示される化合物もしくは当該化合物から得られる中間体化合物を還元することにより、Z1および水素原子ではない場合のZ2で示す基または原子を水素原子に置換する工程Bと、を含み、
上記工程Aにおける上記中間体化合物は、上記工程Bにおいて上記式(III)で示される化合物を還元することにより得られる、式(IV)
で示される化合物であり、
上記工程Bにおける上記中間体化合物は、上記工程Aにおいて上記式(III)で示される化合物を触媒もしくはハロゲン化剤と反応させて得られる、式(II)
で示される化合物である、シクロペンタノン化合物の製造方法。 - 上記工程Aは、上記式(III)で示される化合物を酸触媒と反応させることにより、上記式(II)で示される中間体化合物を得る工程であり、
上記工程Bは、上記式(II)で示される中間体化合物を還元することにより、上記式(I)で示される化合物を得る工程である、請求項1に記載のシクロペンタノン化合物の製造方法。 - 上記式(III)中、Yはアルコキシカルボニル基であり、
上記工程Aは、Yがアルコキシコアルボニル基である上記式(III)で示される化合物をハロゲン化剤と反応させることにより、上記式(II)で示される中間体化合物を得る工程であり、
上記工程Bは、上記式(II)で示される中間体化合物を還元することにより、上記式(I)で示される化合物を得る工程である、請求項1に記載のシクロペンタノン化合物の製造方法。 - 上記工程Bは、上記式(III)で示される化合物を還元することにより、上記式(IV)で示される中間体化合物を得る工程であり、
上記工程Aは、上記式(IV)で示される中間体化合物を触媒またはハロゲン化剤と反応させることにより、上記式(I)で示される化合物を得る工程である、請求項1に記載のシクロペンタノン化合物の製造方法。 - 上記Z2が置換スルホニルオキシ基またはハロゲン原子であることを特徴とする請求項1〜4の何れか1項に記載のシクロペンタノン化合物の製造方法。
- 上記Z2が水素原子であることを特徴とする請求項1〜4の何れか1項に記載のシクロペンタノン化合物の製造方法。
- 式(VI)
で示される化合物を、ホルムアルデヒドまたはホルムアルデヒド誘導体と反応させることにより、式(V)
上記式(V)で示される化合物を、スルホニルクロライドまたはハロゲン化剤と反応させることにより、上記Z2が置換スルホニルオキシ基またはハロゲン原子である上記式(III)で示される化合物を得る工程とをさらに含む、請求項5に記載のシクロペンタノン化合物の製造方法。 - 式(VIII)
で示される化合物を、ホルムアルデヒドまたはホルムアルデヒド誘導体と反応させることにより、式(VII)
で示される化合物を得る工程と、
上記式(VII)で示される化合物を、スルホニルクロライドまたはハロゲン化剤と反応させることにより、上記Z2が水素原子である上記式(III)で示される化合物を得る工程とをさらに含む、請求項6に記載のシクロペンタノン化合物の製造方法。 - 上記工程Aにおいて上記触媒として用いられる酸触媒および上記工程Bにおける還元に用いられる還元剤の両方が反応系に同時に存在するよう、該酸触媒および該還元剤を反応系に添加する、請求項1に記載のシクロペンタノン化合物の製造方法。
- 上記工程Aにおいて用いられる上記ハロゲン化剤および上記工程Bにおける還元に用いられる還元剤の両方が反応系に同時に存在するよう、該ハロゲン化剤および該還元剤を反応系に添加する、請求項1に記載のシクロペンタノン化合物の製造方法。
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