JP5921500B2 - ケトマロン酸化合物の製造方法 - Google Patents
ケトマロン酸化合物の製造方法 Download PDFInfo
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- JP5921500B2 JP5921500B2 JP2013150046A JP2013150046A JP5921500B2 JP 5921500 B2 JP5921500 B2 JP 5921500B2 JP 2013150046 A JP2013150046 A JP 2013150046A JP 2013150046 A JP2013150046 A JP 2013150046A JP 5921500 B2 JP5921500 B2 JP 5921500B2
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- Prior art keywords
- acid compound
- chlorine dioxide
- hydrate
- producing
- reaction
- Prior art date
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- -1 ketomalonic acid compound Chemical class 0.000 title claims description 222
- 238000004519 manufacturing process Methods 0.000 title claims description 98
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 266
- 239000004155 Chlorine dioxide Substances 0.000 claims description 133
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 133
- 238000006243 chemical reaction Methods 0.000 claims description 90
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 87
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 239000003002 pH adjusting agent Substances 0.000 claims description 43
- 125000001424 substituent group Chemical group 0.000 claims description 32
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 10
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000000034 method Methods 0.000 description 102
- 239000007789 gas Substances 0.000 description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000002904 solvent Substances 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 21
- DBKKFIIYQGGHJO-UHFFFAOYSA-N diethyl 2-oxopropanedioate Chemical compound CCOC(=O)C(=O)C(=O)OCC DBKKFIIYQGGHJO-UHFFFAOYSA-N 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 8
- 229960002218 sodium chlorite Drugs 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000007664 blowing Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 235000011054 acetic acid Nutrition 0.000 description 6
- 229910001919 chlorite Inorganic materials 0.000 description 6
- 229910052619 chlorite group Inorganic materials 0.000 description 6
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 5
- ISAKWFYKUTYAQE-UHFFFAOYSA-N dipropan-2-yl 2-oxopropanedioate Chemical compound CC(C)OC(=O)C(=O)C(=O)OC(C)C ISAKWFYKUTYAQE-UHFFFAOYSA-N 0.000 description 5
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 description 5
- IZLVEXGQQKYSSI-UHFFFAOYSA-N dipropyl 2-oxopropanedioate Chemical compound CCCOC(=O)C(=O)C(=O)OCCC IZLVEXGQQKYSSI-UHFFFAOYSA-N 0.000 description 5
- LWIWFCDNJNZEKB-UHFFFAOYSA-N dipropyl propanedioate Chemical compound CCCOC(=O)CC(=O)OCCC LWIWFCDNJNZEKB-UHFFFAOYSA-N 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical class OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- BQQVEASFNMRTBA-UHFFFAOYSA-N 2-[4-(3-aminopropyl)piperazin-1-yl]ethanol Chemical compound NCCCN1CCN(CCO)CC1 BQQVEASFNMRTBA-UHFFFAOYSA-N 0.000 description 4
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- RRKNRHIOERXTHD-UHFFFAOYSA-N dibutyl 2-oxopropanedioate Chemical compound CCCCOC(=O)C(=O)C(=O)OCCCC RRKNRHIOERXTHD-UHFFFAOYSA-N 0.000 description 4
- NFKGQHYUYGYHIS-UHFFFAOYSA-N dibutyl propanedioate Chemical compound CCCCOC(=O)CC(=O)OCCCC NFKGQHYUYGYHIS-UHFFFAOYSA-N 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- VVOCYQDSDXLBEA-UHFFFAOYSA-N dimethyl 2-oxopropanedioate Chemical compound COC(=O)C(=O)C(=O)OC VVOCYQDSDXLBEA-UHFFFAOYSA-N 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 3
- OCOBFMZGRJOSOU-UHFFFAOYSA-N 3-o-tert-butyl 1-o-ethyl propanedioate Chemical compound CCOC(=O)CC(=O)OC(C)(C)C OCOBFMZGRJOSOU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- KTQZIUYTZLTGJE-UHFFFAOYSA-N bis(2-methylpropyl) 2-oxopropanedioate Chemical compound CC(C)COC(=O)C(=O)C(=O)OCC(C)C KTQZIUYTZLTGJE-UHFFFAOYSA-N 0.000 description 3
- SWBJZPDGKVYSLT-UHFFFAOYSA-N bis(2-methylpropyl) propanedioate Chemical compound CC(C)COC(=O)CC(=O)OCC(C)C SWBJZPDGKVYSLT-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- QVRUXRSUYSWFJN-UHFFFAOYSA-N diethyl 2,2-dichloropropanedioate Chemical compound CCOC(=O)C(Cl)(Cl)C(=O)OCC QVRUXRSUYSWFJN-UHFFFAOYSA-N 0.000 description 3
- CLPHAYNBNTVRDI-UHFFFAOYSA-N ditert-butyl propanedioate Chemical compound CC(C)(C)OC(=O)CC(=O)OC(C)(C)C CLPHAYNBNTVRDI-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- NHCREQREVZBOCH-UHFFFAOYSA-N 1-methyl-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene Chemical compound C1CCCC2C(C)CCCC21 NHCREQREVZBOCH-UHFFFAOYSA-N 0.000 description 2
- OLGXVKQPZBFKBA-UHFFFAOYSA-N 1-o-ethyl 3-o-propyl propanedioate Chemical compound CCCOC(=O)CC(=O)OCC OLGXVKQPZBFKBA-UHFFFAOYSA-N 0.000 description 2
- LGIUQPZVYULVIG-UHFFFAOYSA-N 1-o-methyl 3-o-propyl propanedioate Chemical compound CCCOC(=O)CC(=O)OC LGIUQPZVYULVIG-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- BANXPJUEBPWEOT-UHFFFAOYSA-N 2-methyl-Pentadecane Chemical compound CCCCCCCCCCCCCC(C)C BANXPJUEBPWEOT-UHFFFAOYSA-N 0.000 description 2
- FJZRUSFQHBBTCC-UHFFFAOYSA-N 2-oxo-1h-pyrazine-3-carboxylic acid Chemical compound OC(=O)C1=NC=CNC1=O FJZRUSFQHBBTCC-UHFFFAOYSA-N 0.000 description 2
- CVIAKQVBBHBHJK-UHFFFAOYSA-N 3-(2-methylbutan-2-yloxy)-2,3-dioxopropanoic acid Chemical compound CCC(C)(C)OC(=O)C(=O)C(O)=O CVIAKQVBBHBHJK-UHFFFAOYSA-N 0.000 description 2
- DFPRVJYBFLBYOZ-UHFFFAOYSA-N 3-(2-methylbutan-2-yloxy)-3-oxopropanoic acid Chemical compound CCC(C)(C)OC(=O)CC(O)=O DFPRVJYBFLBYOZ-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- VACYGZSWHGKBFF-UHFFFAOYSA-N 3-methoxy-2,3-dioxopropanoic acid Chemical compound COC(=O)C(=O)C(O)=O VACYGZSWHGKBFF-UHFFFAOYSA-N 0.000 description 2
- LIRDIZPKBSSVBK-UHFFFAOYSA-N 3-o-ethyl 1-o-methyl propanedioate Chemical compound CCOC(=O)CC(=O)OC LIRDIZPKBSSVBK-UHFFFAOYSA-N 0.000 description 2
- XPSYZCWYRWHVCC-UHFFFAOYSA-N 3-o-tert-butyl 1-o-methyl propanedioate Chemical compound COC(=O)CC(=O)OC(C)(C)C XPSYZCWYRWHVCC-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- QQXQNPKZBSJJTA-UHFFFAOYSA-N dibutan-2-yl propanedioate Chemical compound CCC(C)OC(=O)CC(=O)OC(C)CC QQXQNPKZBSJJTA-UHFFFAOYSA-N 0.000 description 2
- MQXAJNXSULJYCY-UHFFFAOYSA-N dihexyl propanedioate Chemical compound CCCCCCOC(=O)CC(=O)OCCCCCC MQXAJNXSULJYCY-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 2
- MOJJCFBDUWMVJK-UHFFFAOYSA-N dipentyl propanedioate Chemical compound CCCCCOC(=O)CC(=O)OCCCCC MOJJCFBDUWMVJK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- BVEXQQTWYCTFSF-UHFFFAOYSA-N ditert-butyl 2-oxopropanedioate Chemical compound CC(C)(C)OC(=O)C(=O)C(=O)OC(C)(C)C BVEXQQTWYCTFSF-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
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- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 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
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 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
- 159000000000 sodium salts Chemical group 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 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
- C07C67/31—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 functional groups containing oxygen only in singly bound form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
即ち、本発明は、次の一般式(1)
で表されるマロン酸化合物を二酸化塩素と反応させることによる、次の一般式(2)
で表されるケトマロン酸化合物又はその抱水体の製造方法に関する。特に、マロン酸化合物と二酸化塩素との反応がpH4〜pH11、好ましくはpH5〜pH10の範囲で行われることを特徴とする一般式(2)で表されるケトマロン酸化合物又はその抱水体の製造方法に関する。
本発明は、一般式(1)で表されるマロン酸化合物(原料化合物)を酸化剤としての二酸化塩素と反応させること特徴とする。本発明者らは、二酸化塩素がマロン酸ジエステル等のマロン酸化合物のメチレン部分を特異的に酸化する能力を有していることを、初めて見出したのである。
以上のように、本発明の方法は工業的な製造方法として極めて有用である。
〔1〕一般式(1)
で表されるマロン酸化合物を二酸化塩素と反応させることによる、一般式(2)
で表されるケトマロン酸化合物又はその抱水体の製造方法。
(a)置換基を有していてもよいC1〜C6アルキル基;
(b)置換基を有していてもよいC3〜C6シクロアルキル基;
(c)置換基を有していてもよい炭素原子数6〜12個の芳香族炭化水素基;
(d)置換基を有していてもよい窒素原子、酸素原子及び硫黄原子から選ばれる1〜4個のヘテロ原子を有する5〜10員環の芳香族複素環基;又は、
(e)2つのRは互いに結合して隣接する酸素原子と共に環を形成してもよい;
のいずれかから選ばれる基である、〔1〕から〔26〕のいずれか1項に記載のケトマロン酸化合物又はその抱水体の製造方法。
(a)亜塩素酸塩水溶液と無機強酸から発生させる方法;
(b)塩素酸塩水溶液、無機強酸及び過酸化水素から発生させる方法;又は、
(c)塩素酸塩水溶液と無機強酸から発生させる方法;
で発生させた二酸化塩素ガスを希釈したものである、〔38〕から〔51〕のいずれか1項に記載のケトマロン酸化合物又はその抱水体の製造方法。
次に、本発明の方法の原料として用いる、上記した一般式(1)で表されるマロン酸化合物(以下、「原料化合物」と記載することがある。)について説明する。
次に、本発明の方法により製造される目的物である一般式(2)で表されるケトマロン酸化合物について説明する。
次に、本発明の方法により製造される目的物である一般式(2)で表されるケトマロン酸化合物の抱水体について説明する。
次に、本発明の方法に用いる二酸化塩素について説明する。
本発明の方法に用いる二酸化塩素の使用量は、反応が充分に進行する範囲であればよいが、例えば、一般式(1)で表される原料化合物1モルに対して、通常1モル〜10モル、好ましくは1モル〜3モル、より好ましくは1モル〜2モルの範囲である。
次に、本発明の方法におけるpHについて説明する。
次に、本発明の方法に用いるpH調整剤について説明する。
本発明の方法に用いるpH調整剤の使用量としては、反応が充分に進行する範囲であればよいが、例えば、使用される二酸化塩素1モルに対して、通常1当量以上、好ましくは1当量〜5当量、より好ましくは1当量〜2当量、さらに好ましくは1.2当量〜1.5当量の範囲が挙げられる。
次に、本発明の方法における溶媒について説明する。
本発明の方法における溶媒量は、反応系の撹拌が充分にできる量であればよいが、例えば、一般式(1)で表される原料化合物1モルに対して、通常0〜20L(リットル)、好ましくは0.01L〜10L、より好ましくは0.05L〜5L、さらに好ましくは0.1L〜3L、特に好ましくは0.2L〜2Lの範囲であるが、これらに限定されるものではない。
次に、本発明の方法における反応温度について説明する。
本発明の方法における反応圧力としては、減圧、加圧、常圧のいずれでもよいが、常圧で行うのが好ましい。
次に、本発明の方法における反応時間について説明する。
次に、実施例を挙げて本発明を具体的に説明するが、本発明はこれら実施例によって何ら限定されるものではない。
(ケトマロン酸ジエチルの製造)
(pH5〜8における反応)
(1) マロン酸ジエチル30g(0.187mol)を水100gに懸濁させ、数滴の5%水酸化ナトリウム水溶液でpHを10に調整し、液温を10℃にした。
1H NMR(300MHz,CDCl3) δ ppm:
4.39 (q, J = 6.0 Hz, 2H), 1.36 (t, J = 6.0 Hz, 3H).
13C NMR(300MHz,CDCl3) δ ppm:
178.2, 160.2, 63.5, 13.9.
GC−MS(EI)m/z:
174 [M]+.
(ケトマロン酸ジエチルの製造)
(pH10付近における反応)
マロン酸ジエチル30g(0.187mol)を水100gに懸濁させ、数滴の5%水酸化ナトリウム水溶液でpHを10に調整し、液温を10℃にした後に、実施例1と同様にして、8vol%の二酸化塩素ガスの吹き込みを開始し、5%水酸化ナトリウム水溶液を適宜滴下することによりpHを10付近に維持しながら、13℃〜18℃で5時間かけて二酸化塩素ガスを吹き込んだ。使用した5%水酸化ナトリウム水溶液は180gであった。
1H NMR(300MHz,CDCl3)δ ppm:
4.39 (q, J = 6.0 Hz, 2H), 1.36 (t, J = 6.0 Hz, 3H).
13C NMR(300MHz,CDCl3)δ ppm:
178.2, 160.2, 63.5, 13.9.
1H NMR(300MHz,CDCl3)δ ppm:
4.36 (q, J = 6.0 Hz, 2H), 1.33 (t, J = 6.0 Hz, 3H).
13C NMR(300MHz,CDCl3)δ ppm:
163.0, 100.5, 64.5, 13.6.
(ケトマロン酸ジエチルの製造の検討)
(pHをコントロールしない方法)
マロン酸ジエチル30g(0.187mol)を水100gに懸濁させ、液温を10℃にした後に、実施例1と同様にして、8vol%の二酸化塩素ガスの吹き込みを開始し、13℃〜18℃で5時間かけて二酸化塩素ガスを吹き込んだ。
1H核磁気共鳴スペクトル分析(1H−NMR)は、機種:JNM−LA300 FT NMR SYSTEM(日本電子株式会社製)、内部基準物質:テトラメチルシラン又はクロロホルムを用いて実施された。
GC分析は、機種:6890N Network GC System(Agilent Technologies製)を用いて実施された。GC分析方法に関しては、必要に応じて、以下の文献を参照することができる。
(a):(社)日本化学会編、「新実験化学講座9 分析化学 II」、第60〜86頁(1977年)、発行者 飯泉新吾、丸善株式会社(例えば、カラムに使用可能な固定相液体に関しては、第66頁を参照できる。)
(b):(社)日本化学会編、「実験化学講座20−1 分析化学」第5版、第121〜129頁(2007年)、発行者 村田誠四郎、丸善株式会社(例えば、中空キャピラリー分離カラムの具体的な使用方法に関しては、第124〜125頁を参照できる。)
GC−MS分析は、分析装置に機種:6890N Network GC System(Agilent Technologies製)、質量検出器に機種:5973N MSD(Agilent Technologies製)を用いて実施された。
pHはガラス電極式水素イオン濃度指示計により測定した。ガラス電極式水素イオン濃度指示計としては、具体的には、例えば、形式:パーソナルpH/ORPメータPH72(横川電気株式会社製)又は形式:HM−20P(東亜ディーケーケー株式会社製)などが使用できる。
二酸化塩素ガスのガス濃度及びガス純度に関して、二酸化塩素ガスの定量分析は、当業者に知られたヨウ素滴定により行われた。例えば、二酸化塩素ガスのヨウ素滴定は、次のような手順で行うことができる;リン酸緩衝液でpH7又はpH8に調整した5〜10%ヨウ化カリウム水溶液に、二酸化塩素ガスを吸収させる。澱粉を指示薬として、遊離したヨウ素を10規定チオ硫酸ナトリウム水溶液で滴定する。その後、滴定後の溶液を2規定硫酸などで酸性にする。遊離したヨウ素を、同様にして滴定する。
Claims (13)
- マロン酸化合物と二酸化塩素との反応がpH5〜pH10の範囲で行われる、請求項1に記載のケトマロン酸化合物又はその抱水体の製造方法。
- マロン酸化合物と二酸化塩素との反応がpH5〜pH8の範囲で行われる、請求項1又は2に記載のケトマロン酸化合物又はその抱水体の製造方法。
- マロン酸化合物と二酸化塩素との反応がpH6〜pH8の範囲で行われる、請求項1から3のいずれか1項に記載のケトマロン酸化合物又はその抱水体の製造方法。
- pH調整剤を用いてpHをコントロールする、請求項1から4のいずれか1項に記載のケトマロン酸化合物又はその抱水体の製造方法。
- pH調整剤として無機塩基を用いる、請求項5に記載のケトマロン酸化合物又はその抱水体の製造方法。
- pH調整剤としてアルカリ金属水酸化物を用いる、請求項5に記載のケトマロン酸化合物又はその抱水体の製造方法。
- pH調整剤として水酸化ナトリウムを用いる、請求項5に記載のケトマロン酸化合物又はその抱水体の製造方法。
- pH調整剤として水酸化ナトリウムを用いてpHをコントロールし、マロン酸化合物と二酸化塩素との反応がpH5〜pH10の範囲で行われる、請求項1に記載のケトマロン酸化合物又はその抱水体の製造方法。
- pH調整剤として水酸化ナトリウムを用いてpHをコントロールし、マロン酸化合物と二酸化塩素との反応がpH5〜pH8の範囲で行われる、請求項1に記載のケトマロン酸化合物又はその抱水体の製造方法。
- pH調整剤として水酸化ナトリウムを用いてpHをコントロールし、マロン酸化合物と二酸化塩素との反応がpH6〜pH8の範囲で行われる、請求項1に記載のケトマロン酸化合物又はその抱水体の製造方法。
- 一般式(1)のRがC1〜C4アルキル基である、請求項1から11のいずれか1項に記載のケトマロン酸化合物又はその抱水体の製造方法。
- 一般式(1)のRがメチル又はエチルである、請求項1から11のいずれか1項に記載のケトマロン酸化合物又はその抱水体の製造方法。
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TW103122807A TWI639581B (zh) | 2013-07-19 | 2014-07-02 | 酮基丙二酸化合物的製造方法 |
EP14825779.3A EP3023411B1 (en) | 2013-07-19 | 2014-07-03 | Production method of ketomalonic acid compound |
CN201480039814.4A CN105377803B (zh) | 2013-07-19 | 2014-07-03 | 酮基丙二酸化合物的制造方法 |
US14/905,645 US9499469B2 (en) | 2013-07-19 | 2014-07-03 | Production method of ketomalonic acid compound |
PCT/JP2014/067728 WO2015008629A1 (ja) | 2013-07-19 | 2014-07-03 | ケトマロン酸化合物の製造方法 |
KR1020167001745A KR102034610B1 (ko) | 2013-07-19 | 2014-07-03 | 케토말론산 화합물의 제조방법 |
AU2014291365A AU2014291365B2 (en) | 2013-07-19 | 2014-07-03 | Production method of ketomalonic acid compound |
ES14825779T ES2713376T3 (es) | 2013-07-19 | 2014-07-03 | Procedimiento de producción de compuesto de ácido cetomalónico |
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CN105377803A (zh) | 2016-03-02 |
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