JP2007161634A - 精製2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルの製造方法およびその中間体 - Google Patents
精製2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルの製造方法およびその中間体 Download PDFInfo
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- JP2007161634A JP2007161634A JP2005358631A JP2005358631A JP2007161634A JP 2007161634 A JP2007161634 A JP 2007161634A JP 2005358631 A JP2005358631 A JP 2005358631A JP 2005358631 A JP2005358631 A JP 2005358631A JP 2007161634 A JP2007161634 A JP 2007161634A
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- Prior art keywords
- dimethyl
- group
- formula
- substituted
- hydroxymethanesulfonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000004519 manufacturing process Methods 0.000 title claims description 11
- PTQGFDXPHNRDCV-UHFFFAOYSA-N 3-formyl-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C=O)C1C(O)=O PTQGFDXPHNRDCV-UHFFFAOYSA-N 0.000 title abstract description 7
- -1 alkali metal hydrogensulfite Chemical class 0.000 claims abstract description 101
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical class OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000002585 base Substances 0.000 claims abstract description 17
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- DETXZQGDWUJKMO-UHFFFAOYSA-M hydroxymethanesulfonate Chemical class OCS([O-])(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-M 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 18
- 239000012044 organic layer Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 229940079826 hydrogen sulfite Drugs 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000010410 layer Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000012535 impurity Substances 0.000 description 13
- 238000000746 purification Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- KVSRWNPBUMDYOQ-NTSWFWBYSA-N methyl (1s,3s)-3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound COC(=O)[C@H]1[C@H](C=O)C1(C)C KVSRWNPBUMDYOQ-NTSWFWBYSA-N 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- JVZYMEXLQMHFCI-PHDIDXHHSA-N dimethyl (1s,2s)-3,3-dimethylcyclopropane-1,2-dicarboxylate Chemical compound COC(=O)[C@H]1[C@H](C(=O)OC)C1(C)C JVZYMEXLQMHFCI-PHDIDXHHSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- CTLLMXVSHAUPFO-UHFFFAOYSA-N 6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one Chemical compound C1OC(=O)C2C(C)(C)C21 CTLLMXVSHAUPFO-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-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-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007248 oxidative elimination reaction Methods 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PQTDYOQEPYGGHF-UHFFFAOYSA-N 2,2-dimethylcyclopropane-1-carbaldehyde Chemical compound CC1(C)CC1C=O PQTDYOQEPYGGHF-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- GZVJRUASQZSDKH-UHFFFAOYSA-N 3-(hydroxymethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(CO)C1C(O)=O GZVJRUASQZSDKH-UHFFFAOYSA-N 0.000 description 1
- 125000004176 4-fluorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1F)C([H])([H])* 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- GWRPBZCVTGTVFK-UHFFFAOYSA-N CS(=O)(=O)O.OC1(C(C1C(=O)OCC1=CC(=CC=C1)OC1=CC=CC=C1)(C)C)[Na] Chemical compound CS(=O)(=O)O.OC1(C(C1C(=O)OCC1=CC(=CC=C1)OC1=CC=CC=C1)(C)C)[Na] GWRPBZCVTGTVFK-UHFFFAOYSA-N 0.000 description 1
- PIPCNZGRZSCRHQ-UHFFFAOYSA-N CS(=O)(=O)O.OC1(C(C1C(=O)OCCC)(C)C)[Na] Chemical compound CS(=O)(=O)O.OC1(C(C1C(=O)OCCC)(C)C)[Na] PIPCNZGRZSCRHQ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- CTPBGXQYXMEJIG-UHFFFAOYSA-N benzyl 3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)C(C=O)C1C(=O)OCC1=CC=CC=C1 CTPBGXQYXMEJIG-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CCRXWDGPHIGJEA-UHFFFAOYSA-N butyl 3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1C(C=O)C1(C)C CCRXWDGPHIGJEA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- WACQKHWOTAEEFS-UHFFFAOYSA-N cyclohexane;ethyl acetate Chemical compound CCOC(C)=O.C1CCCCC1 WACQKHWOTAEEFS-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- JMYVMOUINOAAPA-UHFFFAOYSA-N cyclopropanecarbaldehyde Chemical group O=CC1CC1 JMYVMOUINOAAPA-UHFFFAOYSA-N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- ZFZXRNVTYVRULM-UHFFFAOYSA-N ethyl 3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CCOC(=O)C1C(C=O)C1(C)C ZFZXRNVTYVRULM-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- KVSRWNPBUMDYOQ-UHFFFAOYSA-N methyl 3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound COC(=O)C1C(C=O)C1(C)C KVSRWNPBUMDYOQ-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 150000007522 mineralic acids 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000011137 process chromatography Methods 0.000 description 1
- DAXNHRYAZCESNW-UHFFFAOYSA-N propan-2-yl 3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC(C)OC(=O)C1C(C=O)C1(C)C DAXNHRYAZCESNW-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- VEMKTZHHVJILDY-UHFFFAOYSA-N resmethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- JCOOCDUHQWDERL-UHFFFAOYSA-N tert-butyl 3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC(C)(C)OC(=O)C1C(C=O)C1(C)C JCOOCDUHQWDERL-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
-
- 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
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/19—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
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- C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
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Abstract
Description
で示される2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルに、下記第1工程および第2工程を施すことによる精製2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルの製造方法を提供するものである。
<第1工程>
粗製の2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルとアルカリ金属亜硫酸水素塩とを反応させることにより、式(2)
で示される置換ヒドロキシメタンスルホン酸塩を得る工程
<第2工程>
第1工程で得た置換ヒドロキシメタンスルホン酸塩と、酸、塩基および水溶性アルデヒドからなる群から選ばれる少なくとも一つの化合物とを反応させることにより、精製2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルを得る工程
回収率(%)=精製後混合物中のホルミルシクロプロパン化合物(1)の重量÷精製前混合物中のホルミルシクロプロパン化合物(1)の重量×100
除去率(%)=100−(精製後混合物中の対象不純物の重量÷精製前混合物中の対象不純物の重量×100)
トランス−2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸メチルの27.9重量%トルエン溶液179.0g(不純物として、6,6−ジメチル−3−オキサ−2−オキソビシクロ[3.1.0]ヘキサンを3.5重量%含む。)に水55.7gを加えた後、25℃で35重量%亜硫酸水素ナトリウム水溶液115.0gを滴下し、同温度にて2時間攪拌した。有機層と水層とを分液し、回収した水層にトルエン75.1gを加え、50℃に昇温した後、23重量%水酸化ナトリウム溶液66.8gを滴下し、そのまま50℃にて0.5時間攪拌した。滴下終了後の水層のpHは9.9であった。有機層と水層とを分液した後、水層にトルエン26.0g、23重量%水酸化ナトリウム水溶液0.9gを加えて、pH10.0に調整し、50℃にて0.5時間攪拌した。有機層と水層とを分液し、先に得た有機層と合一することにより、トランス−2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸メチルのトルエン溶液148.7gを得た。
<GC−IS分析>
トランス−2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸メチルの含量は、33.0重量%であり、その回収率は98%であった。
6,6−ジメチル−3−オキサ−2−オキソビシクロ[3.1.0]ヘキサンの含量は、0.65重量%であり、その除去率は85%であった。
<GC面百>
トランス−2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸メチル:
(精製前)81.7% (精製後)93.6%
トランス−2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸メチルの24.7重量%トルエン溶液121.6g(不純物として、トランス−2,2−ジメチル−3−メトキシカルボニルシクロプロパンカルボン酸メチルを0.12重量%含む。)に35重量%亜硫酸水素ナトリウム水溶液69.2gを25℃で滴下し、同温度にて2時間攪拌した。有機層と水層とを分液し、回収した水層にトルエン46.0gを加え、50℃に昇温した後、37重量%ホルマリン水溶液28.6gを滴下した。滴下終了後、50℃にて2時間攪拌した。有機層と水層とを分液した後、水層にトルエン16.2gを加え、50℃にて1時間攪拌し、有機層と水層とを分液し、先に得た有機層と合一することにより、トランス−2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸メチルのトルエン溶液75.1gを得た。
<GC−IS分析>
トランス−2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸メチルの含量は、31.3重量%であり、その回収率は96%であった。
トランス−2,2−ジメチル−3−メトキシカルボニルシクロプロパンカルボン酸メチルの含量は0.04重量%以下であり、その除去率は80%以上であった。
<GC面百>
トランス−2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸メチル:
(精製前)98.5% (精製後)99.5%
98.0重量%トランス−2,2−ジメチル−3−メトキシカルボニルシクロプロパンカルボン酸メチル10.4gをトルエン12gに溶解し、35重量%亜硫酸水素ナトリウム水溶液9.9gを25℃で滴下した後、同温度にて2時間攪拌した。有機層と水層とを分液した後、回収した水層を減圧濃縮し、次いで、得られた固体をエタノールに溶解した後、再度、減圧下に濃縮乾燥させることにより、ヒドロキシ[3−(メトキシカルボニル)−2,2−ジメチルシクロプロピル]メタンスルホン酸ナトリウムの白色固体(融点:80〜88℃)8.6gを得た。
1H NMR(300Hz,DMSO−d6)δ1.09(s,1.2H),1.12(s,1.8H)、1.15(s,1.2H)、1.16(s,1.8H),1.44−1.71(m,2H)3.55(s、1.8H),3.57(s,1.2H),3.59−3.64(m,1H),5.42−5.44(m、1H)
13C NMR(75.4MHz,DMSO−d6)δ20.4,20.5,21.3,21.8,25.4,27.6,29.8,31.7,33.9,35.3,51.1,51.8,81.2、82.6、171.7、172.2
Claims (8)
- 粗製の式(1)
で示される2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルに、下記第1工程および第2工程を施すことによる精製2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルの製造方法。
<第1工程>
粗製の2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルとアルカリ金属亜硫酸水素塩とを反応させることにより、式(2)
で示される置換ヒドロキシメタンスルホン酸塩を得る工程
<第2工程>
第1工程で得た式(2)で示される置換ヒドロキシメタンスルホン酸塩と、酸、塩基および水溶性アルデヒドからなる群から選ばれる少なくとも一つの化合物とを反応させることにより、式(1)で示される2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルを得る工程 - 第1工程において、アルカリ金属亜硫酸水素塩の水溶液を用いて有機溶媒の存在下に反応を実施する請求項1に記載の製造方法。
- 第1工程において、反応混合物から有機層を分離することにより、水溶液として式(2)で示される置換ヒドロキシメタンスルホン酸塩を得る請求項2に記載の製造方法。
- 第2工程において、水溶性アルデヒドを用いて反応を実施する請求項1〜3のいずれかに記載の製造方法。
- 第2工程において、塩基としてアルカリ金属水酸化物またはアルカリ金属炭酸塩を用いて反応を実施する請求項1〜3のいずれかに記載の製造方法。
- 第2工程において、pH9〜11の範囲で反応を実施する請求項5に記載の製造方法。
- 式(2)で示される置換ヒドロキシメタンスルホン酸塩。
- 式(1)で示される2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルとアルカリ金属亜硫酸水素塩とを反応させる式(2)で示される置換ヒドロキシメタンスルホン酸塩の製造方法。
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JP2005358631A JP5076313B2 (ja) | 2005-12-13 | 2005-12-13 | 精製2,2−ジメチル−3−ホルミルシクロプロパンカルボン酸エステルの製造方法およびその中間体 |
US12/095,608 US8168816B2 (en) | 2005-12-13 | 2006-12-12 | Method for producing purified formylcyclopropane compound and intermediate of such formylcyclopropane compound |
PCT/JP2006/325141 WO2007069759A1 (ja) | 2005-12-13 | 2006-12-12 | 精製されたホルミルシクロプロパン化合物の製造方法およびその中間体 |
KR1020087016746A KR20080077276A (ko) | 2005-12-13 | 2006-12-12 | 정제된 포르밀시클로프로판 화합물의 제조 방법 및 그의중간체 |
CN2006800465002A CN101326158B (zh) | 2005-12-13 | 2006-12-12 | 用于制备纯化的甲酰基环丙烷化合物及其中间体的方法 |
EP06834868.9A EP1970369B1 (en) | 2005-12-13 | 2006-12-12 | Method for producing purified formylcyclopropane compound and intermediate of such formylcyclopropane compound |
IL191826A IL191826A (en) | 2005-12-13 | 2008-05-29 | Process and intermediate for the production of a purified compound of formylcyclopropane |
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CN111269121B (zh) * | 2020-03-10 | 2023-04-07 | 广州巨元生化有限公司 | 一种8-氧代-3,7-二甲基-2,6-辛二烯基羧酸酯化合物的纯化方法 |
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JPH0761948A (ja) * | 1993-06-14 | 1995-03-07 | Takeda Chem Ind Ltd | α,β−不飽和アルデヒドの製造法 |
JP2004099595A (ja) * | 2002-07-17 | 2004-04-02 | Sumitomo Chem Co Ltd | ホルミルシクロプロパンカルボン酸エステル類の製造方法 |
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US5471004A (en) * | 1993-06-14 | 1995-11-28 | Takeda Chemical Industries, Ltd. | Process for producing α,β-unsaturated aldehydes |
JP2002249457A (ja) | 2001-02-21 | 2002-09-06 | Daicel Chem Ind Ltd | アルデヒドの製造方法 |
JP2003267915A (ja) | 2002-01-10 | 2003-09-25 | Sumitomo Chem Co Ltd | 3,3−ジメチル−2−ホルミルシクロプロパンカルボン酸誘導体の製造方法 |
DE60225338T2 (de) | 2002-01-10 | 2009-02-26 | Sumitomo Chemical Co., Ltd. | Verfahren zur herstellung von derivaten von 3,3-dimethyl-2-formylcyclopropanekarbonsäure |
ATE555075T1 (de) * | 2002-07-17 | 2012-05-15 | Sumitomo Chemical Co | Verfahren zur herstellung von formylcyclopropancarbonsäureestern |
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JPH0225834A (ja) * | 1988-07-14 | 1990-01-29 | Canon Inc | 液晶装置の駆動法 |
JPH0761948A (ja) * | 1993-06-14 | 1995-03-07 | Takeda Chem Ind Ltd | α,β−不飽和アルデヒドの製造法 |
JP2004099595A (ja) * | 2002-07-17 | 2004-04-02 | Sumitomo Chem Co Ltd | ホルミルシクロプロパンカルボン酸エステル類の製造方法 |
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EP1970369A4 (en) | 2011-05-11 |
IL191826A0 (en) | 2008-12-29 |
CN101326158B (zh) | 2013-04-17 |
JP5076313B2 (ja) | 2012-11-21 |
KR20080077276A (ko) | 2008-08-21 |
IL191826A (en) | 2013-08-29 |
US8168816B2 (en) | 2012-05-01 |
US20100305353A1 (en) | 2010-12-02 |
EP1970369B1 (en) | 2013-09-25 |
EP1970369A1 (en) | 2008-09-17 |
WO2007069759A1 (ja) | 2007-06-21 |
CN101326158A (zh) | 2008-12-17 |
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