JPH0383974A - Production of lactones - Google Patents
Production of lactonesInfo
- Publication number
- JPH0383974A JPH0383974A JP1217236A JP21723689A JPH0383974A JP H0383974 A JPH0383974 A JP H0383974A JP 1217236 A JP1217236 A JP 1217236A JP 21723689 A JP21723689 A JP 21723689A JP H0383974 A JPH0383974 A JP H0383974A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- catalyst
- ruthenium
- diols
- lactones
- 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
Links
- 150000002596 lactones Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- 150000002009 diols Chemical class 0.000 claims abstract description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- -1 dicarboxylic acid ester Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 16
- 238000009835 boiling Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 13
- 238000004821 distillation Methods 0.000 description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000003304 ruthenium compounds Chemical class 0.000 description 3
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229960002903 benzyl benzoate Drugs 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 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 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- ZSSWXNPRLJLCDU-UHFFFAOYSA-N 1-diethylphosphorylethane Chemical compound CCP(=O)(CC)CC ZSSWXNPRLJLCDU-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- RTYCZCFQHXCMGC-UHFFFAOYSA-N 1-methoxy-2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethane Chemical compound COCCOCCOCCOCCOC.COCCOCCOCCOCCOC RTYCZCFQHXCMGC-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- CLRJSTYUENQJNT-UHFFFAOYSA-N C1(=CC=CC=C1)C(P(O)=O)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C(P(O)=O)C1=CC=CC=C1 CLRJSTYUENQJNT-UHFFFAOYSA-N 0.000 description 1
- AXKPBIUQVYVDHP-UHFFFAOYSA-N CCc1cccc(c1CC)P(O)=O Chemical compound CCc1cccc(c1CC)P(O)=O AXKPBIUQVYVDHP-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- YVASSEYOCLGNCH-UHFFFAOYSA-N OP(CC(C1=CC=CC=C1)C1=CC=CC=C1)=O Chemical compound OP(CC(C1=CC=CC=C1)C1=CC=CC=C1)=O YVASSEYOCLGNCH-UHFFFAOYSA-N 0.000 description 1
- HSNVNALJRSJDHT-UHFFFAOYSA-N P(=O)(=O)[Mo] Chemical compound P(=O)(=O)[Mo] HSNVNALJRSJDHT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910021603 Ruthenium iodide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- AKTGKEBIBGSCLD-UHFFFAOYSA-N [ethyl(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(CC)C1=CC=CC=C1 AKTGKEBIBGSCLD-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 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
- BPSLVNCMKDXZPC-UHFFFAOYSA-N benzyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC1=CC=CC=C1 BPSLVNCMKDXZPC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- IZEGUKURUPYBPY-UHFFFAOYSA-N chlorobenzene;nitromethane Chemical compound C[N+]([O-])=O.ClC1=CC=CC=C1 IZEGUKURUPYBPY-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- XYZMOVWWVXBHDP-UHFFFAOYSA-N cyclohexyl isocyanide Chemical compound [C-]#[N+]C1CCCCC1 XYZMOVWWVXBHDP-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- VMDTXBZDEOAFQF-UHFFFAOYSA-N formaldehyde;ruthenium Chemical compound [Ru].O=C VMDTXBZDEOAFQF-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons 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
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- IYIAWAACGTUPCC-UHFFFAOYSA-N n-(diethylsulfamoyl)-n-ethylethanamine Chemical compound CCN(CC)S(=O)(=O)N(CC)CC IYIAWAACGTUPCC-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- SWMBQMGPRYJSCI-UHFFFAOYSA-N octylphosphane Chemical compound CCCCCCCCP SWMBQMGPRYJSCI-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- JDNQPKBFOBQRBN-UHFFFAOYSA-N ruthenium monohydride Chemical compound [RuH] JDNQPKBFOBQRBN-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- LEMQFBIYMVUIIG-UHFFFAOYSA-N trifluoroborane;hydrofluoride Chemical compound F.FB(F)F LEMQFBIYMVUIIG-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はラクトン類の製造方法に間するものである。詳
しくは、ジカルボン酸、ジカルボン酸無水物及び／又は
ジカルボン酸エステルを液相で水素化することによりラ
クトン類を製造する方法の改良に間するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing lactones. Specifically, the present invention aims to improve a method for producing lactones by hydrogenating dicarboxylic acids, dicarboxylic anhydrides, and/or dicarboxylic esters in a liquid phase.
（従来の技術）
ジカルボン酸、ジカルボン酸無水物及び／又はジカルボ
ン酸エステルを水素化してラクトン類を製造する方法は
古くから検討されており、これまでに多数の提案がなさ
れている０例えば触媒として、ニッケル系触媒（特公昭
４３−６９４７号公報）、コバルト系触媒く特開昭５１
−９５０５７号公報）、銅−クロム系触媒（特公昭３８
−２０１１９号公報）、銅−亜鉛系触媒（特公昭４２−
１４４６３号公報）等を使用して、固定床又は懸濁液相
により水素化反応を行なう方法が知られている。(Prior Art) Methods for producing lactones by hydrogenating dicarboxylic acids, dicarboxylic acid anhydrides, and/or dicarboxylic acid esters have been studied for a long time, and many proposals have been made so far. , nickel-based catalyst (Japanese Patent Publication No. 43-6947), cobalt-based catalyst
-95057), copper-chromium catalyst (Japanese Patent Publication No. 38
-20119), copper-zinc catalyst (Japanese Patent Publication No. 1973-
14463), etc., to carry out the hydrogenation reaction in a fixed bed or in a suspension phase.
一方、均−系のルテニウム系触媒を使用して上記の水素
化反応を行なう方法も知られ、例えば米国特許３９５７
８２７号には、［ＲｕＸｎ（ＰＲ＋Ｒ２Ｒｓ）ｘＬｙ］
型のルテニウム系触媒を使用し４０〜４００ ｐｓｉの
加圧下で水素化してラクトン類を製造する方法が記載さ
れ、また米国特許４４８５２４６号には、同様の触媒に
よる水素化反応を有機アミンの存在下で行なうことが記
載されている。On the other hand, methods of carrying out the above hydrogenation reaction using homogeneous ruthenium-based catalysts are also known, for example, in US Pat.
No. 827 includes [RuXn(PR+R2Rs)xLy]
A method for producing lactones by hydrogenation under pressure of 40 to 400 psi using a type of ruthenium-based catalyst is described, and US Pat. No. 4,485,246 describes a hydrogenation reaction using a similar catalyst in the presence of an organic amine. It describes what to do.
（発明が解決しようとする課題）
しかしながら、上記のニッケル系触媒、コバルト系触媒
、銅−クロム系触媒、鋼−亜鉛系触媒等の固体触媒を使
用する従来の方法は、反・応条件が数十気圧以上の苛酷
な条件の採用は避けられないという問題点があった。一
方、上記均一系のルテニウム系触媒を使用する方法は、
比較的温和な条件下で水素化反応が進行するという特徴
がある半面、触媒活性がやや低水準であるうえ、触媒寿
命が短かく、またハロゲンを使用しているため反応装置
の腐蝕が生ずるという問題がある。(Problem to be solved by the invention) However, conventional methods using solid catalysts such as the above-mentioned nickel-based catalysts, cobalt-based catalysts, copper-chromium-based catalysts, and steel-zinc-based catalysts require several reaction conditions. The problem was that harsh conditions of ten atmospheres or more were unavoidable. On the other hand, the method using the homogeneous ruthenium catalyst mentioned above is
Although the hydrogenation reaction is characterized by proceeding under relatively mild conditions, the catalyst activity is rather low, the catalyst life is short, and the use of halogens causes corrosion of the reaction equipment. There's a problem.
そこで本出願人は、先に触媒としてルテニウム、有機ホ
スフィン及びｐＫａ値が２より小さい酸の共役塩基を含
有するルテニウム系触媒を使用し、液相で水素化する方
法を提案した（特開平１−２５７７１号公報）、この方
法では、高活性なルテニウム触媒を使用するので、温和
な条件下で良好に水素化反応を行うことができるが、ジ
カルボン酸、ジカルボン酸無水物及び／又はジカルボン
酸エステルを原料として水素化反応を継続すると、反応
帯域中で分解あるいは重縮合等による高沸点副生物が生
成しラクトン類の収率が低下する欠点があった。Therefore, the present applicant previously proposed a method of hydrogenation in a liquid phase using a ruthenium-based catalyst containing ruthenium, an organic phosphine, and a conjugated base of an acid with a pKa value of less than 2 (Japanese Patent Application Laid-Open No. 1999-1-1903-1). In this method, since a highly active ruthenium catalyst is used, the hydrogenation reaction can be carried out satisfactorily under mild conditions. If the hydrogenation reaction is continued as a raw material, high-boiling by-products are generated due to decomposition or polycondensation in the reaction zone, resulting in a decrease in the yield of lactones.
本発明は、ルテニウム触媒を使用する方法の上述の問題
点を解決し、ジカルボン酸、ジカルボン酸無水物及び／
又はジカルボン酸エステルから工業的有利にラクトン類
を製造することを目的とするものである。The present invention solves the above-mentioned problems of methods using ruthenium catalysts,
Alternatively, the purpose is to industrially advantageously produce lactones from dicarboxylic acid esters.
（課題を解決するための手段）
本発明者等は上記の目的を達成するために検討の結果、
ルテニウム触媒を使用してジカルボン酸、ジカルボン酸
無水物及び／又はジカルボン酸エステルを液相で水素化
することによりラクトン類を製造する際に、水素化の過
程で原料物質の水添により生成するジオール類の水素化
反応帯域中の濃度を５重量％以下に保持するときは、前
記高沸点副生物の生成量を低減することができることを
見出し本発明を達成した。即ち本発明の要旨は、ジカル
ボン酸、ジカルボン酸無水物及び／又はジカルボン酸エ
ステルをルテニウム触媒の存在下液相で水素化すること
によりラクトン類を製造する方法において、水素化反応
帯域中におけるジオール類の濃度を５重量％以下に保持
することを特徴とするラクトン類の製造方法に存する。(Means for Solving the Problem) As a result of studies to achieve the above object, the inventors have
When producing lactones by hydrogenating dicarboxylic acids, dicarboxylic acid anhydrides and/or dicarboxylic acid esters in the liquid phase using a ruthenium catalyst, diols produced by hydrogenation of raw materials during the hydrogenation process. The present invention was accomplished by discovering that the amount of high-boiling by-products produced can be reduced when the concentration in the hydrogenation reaction zone is maintained at 5% by weight or less. That is, the gist of the present invention is to provide a method for producing lactones by hydrogenating dicarboxylic acids, dicarboxylic acid anhydrides, and/or dicarboxylic acid esters in a liquid phase in the presence of a ruthenium catalyst, in which diols are produced in a hydrogenation reaction zone. A method for producing lactones, characterized in that the concentration of lactones is maintained at 5% by weight or less.
本発明の詳細な説明するに、本発明における原料物質と
しては、炭素数３〜７の飽和又は不飽和のジカルボン酸
、それ等の無水物、もしくはそれ等のジカルボン酸のエ
ステルが挙げられ、エステルとしては低級アルキルエス
テルが好ましい。具体的には例えば、マレイン酸、フマ
ール酸、コハク酸、無水マレイン酸、無水コハク酸、マ
レイン酸ジメチル、フマール酸ジエチル、コハク酸−ジ
−ｎ−ブチル等が使用される。To explain the present invention in detail, raw materials in the present invention include saturated or unsaturated dicarboxylic acids having 3 to 7 carbon atoms, anhydrides thereof, and esters of such dicarboxylic acids. As such, lower alkyl esters are preferred. Specifically, for example, maleic acid, fumaric acid, succinic acid, maleic anhydride, succinic anhydride, dimethyl maleate, diethyl fumarate, di-n-butyl succinate, etc. are used.
本発明に使用されるルテニウム触媒としては特に限定さ
れないが、例えば（イ）ルテニウム、（ロ）有機ホスフ
ィン及び（ハ）ｐＫａが２より小さい酸の共役塩基を含
有するルテニウム系触媒が挙げられ、場合によりこれに
更に（二〉中性配位子を含有させた触媒が好適に使用さ
れる。The ruthenium catalyst used in the present invention is not particularly limited, but includes, for example, a ruthenium-based catalyst containing (a) ruthenium, (b) an organic phosphine, and (c) a conjugated base of an acid with a pKa of less than 2. Therefore, a catalyst further containing a (di) neutral ligand is preferably used.
本発明は、上述のジカルボン酸、ジカルボン酸無水物及
び／又はジカルボン酸エステルを上記ルテニウム触媒の
存在下に液相で水素化してラクトン類を製造する際に、
水素化反応帯域中における、原料物質の水添によって生
成するジオール類の濃度を５重量％以下、好ましくは３
重量％以下に保持することを骨子とするものである。The present invention provides a method for producing lactones by hydrogenating the above-mentioned dicarboxylic acid, dicarboxylic acid anhydride, and/or dicarboxylic acid ester in the presence of the above-mentioned ruthenium catalyst in a liquid phase.
The concentration of diols produced by hydrogenation of the raw materials in the hydrogenation reaction zone is set to 5% by weight or less, preferably 3% by weight or less.
The main point is to maintain the content within % by weight.
水素化過程で生成するジオール類は反応性が高いために
、水素化反応条件下で容易に原料であるジカルボン酸、
ジカルボン酸無水物又はジカルボン酸エステルの加水分
解により生成するジカルボン酸等と重縮合反応してポリ
エステルなどを主成分とする高沸点副生物を生成するが
、水素化反応帯域中のジオール類の濃度を５重量％以下
、好ましくは３重量％以下に保持することにより、高沸
点副生物の生成量を著しく低減できるのである。Diols produced in the hydrogenation process are highly reactive, so they can easily be converted into dicarboxylic acids, raw materials, under hydrogenation reaction conditions.
A polycondensation reaction with dicarboxylic acids produced by hydrolysis of dicarboxylic acid anhydrides or dicarboxylic acid esters produces high-boiling byproducts mainly composed of polyesters, but the concentration of diols in the hydrogenation reaction zone is By keeping the content at 5% by weight or less, preferably 3% by weight or less, the amount of high-boiling by-products produced can be significantly reduced.
水素化反応帯域中のジオール類の濃度を５重量％以下に
保持する方法としては、例えば水素化反応帯域中に水素
ガスを大過剰に流通させて水素ガスのストリッピングに
よりジオール類を反応生成物たるラクトン類と共に反応
帯域外に抜き出す方法、原料物質と溶媒の比率をコント
ロールすることによりジオール類の濃度を調整する方法
、あるいは反応帯域から反応液の一部を抜き出し、蒸留
して触媒液とジオール類とを分離し、触媒液のみを反応
帯域に循環する方法等が採用される。As a method for maintaining the concentration of diols in the hydrogenation reaction zone at 5% by weight or less, for example, a large excess of hydrogen gas is passed through the hydrogenation reaction zone and the diols are converted into reaction products by stripping the hydrogen gas. One method is to extract the lactones out of the reaction zone along with the other lactones, one is to adjust the concentration of diols by controlling the ratio of the raw materials and the solvent, and the other is to extract a portion of the reaction solution from the reaction zone and distill it to separate the catalyst solution and diols. A method is adopted in which the catalyst liquid is separated from the catalyst liquid and only the catalyst liquid is circulated to the reaction zone.
このような方法により、ジオール類に基づく高沸点物言
の生成が抑制されてラクトン類の収率が向上する。By such a method, the production of high-boiling compounds based on diols is suppressed and the yield of lactones is improved.
以下に本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
本発明に使用される前売（イ）ルテニウム、（ロ）有機
ホスフィン及び（ハ）ｐＫａｆｄｌが２より小さい酸の
共役塩基を含有し更に場合により中性配位子を含有して
いてもよいルテニウム触媒の詳細は次の通りである。The ruthenium catalyst used in the present invention contains (a) ruthenium, (b) an organic phosphine, and (c) a conjugate base of an acid with pKafdl of less than 2, and optionally further contains a neutral ligand. The details are as follows.
（イ）ルテニウム：
ルテニウムとしては、金属ルテニウム及びルテニウム化
合物の何れも使用することができる。ルテニウム化合物
としては、ルテニウムの酸化物、ハロゲン化物、水酸化
物、無機酸塩、有機酸塩又は錯化合物が使用され、具体
的には例えば、二酸化ルテニウム、四酸化ルテニウム、
二本酸化ルテニウム、塩化ルテニウム、臭化ルテニウム
、ヨウ化ルテニウム、硝酸ルテニウム、酢酸ルテニウム
、トリス（アセチルアセトン）ルテニウム、ヘキサクロ
ロルテニウム酸ナトリウム、テトラカルボニルルテニウ
ム酸ジカリウム、ペンタカルボニルルテニウム、シクロ
ペンタジエニルジ力ルポニルルテニウム、ジブロモトリ
カルボニルルテニウム、クロロトリス（トリフェニルホ
スフィン）ヒドリドルテニウム、ビス（トリーｎ−ブチ
ルホスフィン）トリカルボニルルテニウム、ドデカカル
ボニルトリルテニウム、テトラヒドリドデカカルボニル
テトラルテニウム、オクタデカカルボニルへキサルテニ
ウム酸ジセシウム、ウンデカカルボニルヒドリドトリル
テニウム酸テトラフェニルホスホニウム等が挙げられる
。これ等の金属ルテニウム及びルテニウム化合物の使用
量は、反応溶液１リツトル中のルテニウムとして０．０
００１〜１００ミリモル、好ましくはｏ、ｏｏｔ〜１０
ミリモルである。(a) Ruthenium: As ruthenium, both metal ruthenium and ruthenium compounds can be used. As the ruthenium compound, ruthenium oxides, halides, hydroxides, inorganic acid salts, organic acid salts, or complex compounds are used, and specifically, for example, ruthenium dioxide, ruthenium tetroxide,
Ruthenium dioxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium acetate, tris(acetylacetone)ruthenium, sodium hexachlororuthenate, dipotassium tetracarbonylruthenate, pentacarbonylruthenium, cyclopentadienyldihydroporpe Nylruthenium, dibromotricarbonylruthenium, chlorotris(triphenylphosphine)hydridoruthenium, bis(tri-n-butylphosphine)tricarbonylruthenium, dodecacarbonyltriruthenium, tetrahydridodecacarbonyltetraruthenium, dicesium octadecacarbonylhexarthenate, Examples include undecacarbonylhydridotriruthenate tetraphenylphosphonium. The amount of these metal ruthenium and ruthenium compounds used is 0.0 as ruthenium per liter of reaction solution.
001 to 100 mmol, preferably o, oot to 10
Millimoles.
（ロ）有機ホスフィン：
有機ホスフィンは、主触媒である（イ）のルテニウムの
電子状態を制御したり、ルテニウムの活性状態を安定化
するのに寄与するものと考えられる。(b) Organic phosphine: The organic phosphine is thought to contribute to controlling the electronic state of ruthenium (a), which is the main catalyst, and to stabilizing the active state of ruthenium.
有機ホスフィンの具体例としては、トリー〇−オクチル
ホスフィン、トリーｎ−ブチルホスフィン、ジメチル−
ｎ−オクチルホスフィン等のトリアルキルホスフィン類
、トリシクロヘキシルホスフィンのようなトリシクロア
ルキルホスフィン類、トリフェニルホスフィンのような
トリアリールホスフィン類、ジメチルフェニルホスフィ
ンのようなアルキルアリールホスフィン類、１，２−ビ
ス（ジフェニルホスフィノ）エタンのような多官能性ホ
スフィン類が挙げられる。有機ホスフィンの使用量は通
常、ルテニウム１モルに対して、０．１〜１０００モル
程度、好ましくはｔ −ｔｏｏモルである。また、有機
ホスフィンは、それ自体単独で、あるいはルテニウム触
媒との複合体の形で、反応系に供給することができる。Specific examples of organic phosphine include tri-octylphosphine, tri-n-butylphosphine, dimethyl-
Trialkylphosphines such as n-octylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, triarylphosphines such as triphenylphosphine, alkylarylphosphine such as dimethylphenylphosphine, 1,2-bis Examples include polyfunctional phosphines such as (diphenylphosphino)ethane. The amount of organic phosphine used is usually about 0.1 to 1000 mol, preferably t -too mol, per 1 mol of ruthenium. Further, the organic phosphine can be supplied to the reaction system either alone or in the form of a complex with a ruthenium catalyst.
（ハ） ｐＫａ値が２より小さい酸の兵役塩基：ｐ Ｋ
ａ ｋＷが２より小さい酸の共役塩基は、ルテニウム
触媒の付加的促進剤として作用し、触媒：Ａｌ１中又は
反応系中において、ρにａｌｆｉが２より小さい酸の共
役塩基を生成するものであればよく、その供給形態とし
ては、ｐＫａ値が２より小さいブレンステッド酸又はそ
の各種の塩等が用いられる。具体的には例えば、硫酸、
亜硫酸、硝酸、亜硝酸、過塩素酸、燐酸、ホウフッ化水
素酸、ヘキサフルオロ燐酸、タングステン酸、燐モリブ
デン徴、燐タングステン酸、シリコンタングステン酸、
ポリケイ酸、フルオロスルホン酸等の無機酸類、トリク
ロロ酢酸、ジクロロ酢酸、トリフルオロ酢酸、メタンス
ルホン酸、トリフルオロメタンスルホン酸、ラウリルス
ルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン
酸等の有機酸、あるいはこれ等の酸のアンモニウム塩、
ホスホニウム塩が挙げられる。(c) Military base of acid with pKa value less than 2: pK
a The conjugate base of an acid with a kW smaller than 2 acts as an additional promoter of the ruthenium catalyst, and forms the conjugate base of an acid with an alfi smaller than 2 at ρ in the catalyst Al1 or in the reaction system. As its supply form, a Brønsted acid having a pKa value of less than 2 or various salts thereof may be used. Specifically, for example, sulfuric acid,
Sulfurous acid, nitric acid, nitrite, perchloric acid, phosphoric acid, hydrofluoroboric acid, hexafluorophosphoric acid, tungstic acid, phosphomolybdenum, phosphotungstic acid, silicon tungstic acid,
Inorganic acids such as polysilicic acid and fluorosulfonic acid; organic acids such as trichloroacetic acid, dichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, laurylsulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; or Ammonium salts of acids such as
Examples include phosphonium salts.
また、これ等の酸の共役塩基が反応系で生成すると考え
られる酸誘導体、例えば酸ハロゲン化物、酸無水物、エ
ステル、酸アミド等の形で添加しても同様の効果が得ら
れる。これ等の酸又はその塩の使用量は、ルテニウム１
モルに対して０．０１〜１０００モル、好ましくは０．
１〜１００モル、更に好ましくは０．５〜２０モルの範
囲である。Further, the same effect can be obtained even if the conjugate base of these acids is added in the form of an acid derivative thought to be produced in the reaction system, such as an acid halide, an acid anhydride, an ester, or an acid amide. The amount of these acids or their salts used is ruthenium 1
0.01 to 1000 mol, preferably 0.01 to 1000 mol.
The amount is in the range of 1 to 100 mol, more preferably 0.5 to 20 mol.
上記（イ）、（ロ）及び（ハ）の成分の外に、場合によ
り含有することができる（二）中性配位子としては、水
素、エチレン、プロピレン、ブテン、シクロペンテン、
シクロヘキセン、ブタジェン、シクロペンタジェン、シ
クロオクタジエン、ツルボナシエン等のオレフィン類、
−酸化炭素、ジエチルエーテル、アニソール、ジオキサ
ン、テトラヒドロフラン、アセトン、アセトフェノン、
ベンゾフェノン、シクロヘキサノン、プロピオン酸、カ
プロン酸、酪酸、安息香酸、酢酸エチル、酢酸アリル、
安息香酸ベンジル、ステアリン酸ベンジル等の含酸素化
合物、酸化窒素、アセトニトリル、プロピオニトリル、
ベンゾニトリル、シクロヘキシルイソニトリル、ブチル
アミン、アニリン、トルイジン、トリエチルアミン、ビ
ロール、ピリジン、Ｎ−メチルホルムアミド、アセトア
ミド、！、１，３．３−テトラメチル尿素、Ｎ−メチル
ピロリドン、カプロラクタム、ニトロメタン等の含窒素
化合物、二硫化炭素、ｎ−ブチルメルカプタン、チオフ
ェノール、ジメチルスルフィド、ジメチルジスルフィド
、チオフェン、ジメチルスルホキシド、ジフェニルスル
ホキシド等の含硫黄化合物、トリブチルホスフィンオキ
シト、エチルジフェニルホスフィンオキシト、トリフェ
ニルホスフィンオキシト、ジエチルフェニルホスフィネ
ート、ジフェニルメチルホスフィネート、ジフェニルエ
チルホスフィネート、０．０−ジメチルメチルホスホノ
チオレート、トリエチルホスファイト、トリフェニルホ
スファイト、トリエチルホスフェート、トリフェニルホ
スフェート、ヘキサメチルホスホリックトリアミド等の
有機ホスフィン以外の含燐化合物が挙げられる。In addition to the above components (a), (b) and (c), (2) neutral ligands that may optionally be contained include hydrogen, ethylene, propylene, butene, cyclopentene,
Olefins such as cyclohexene, butadiene, cyclopentadiene, cyclooctadiene, turbonasien,
-carbon oxide, diethyl ether, anisole, dioxane, tetrahydrofuran, acetone, acetophenone,
Benzophenone, cyclohexanone, propionic acid, caproic acid, butyric acid, benzoic acid, ethyl acetate, allyl acetate,
Oxygenated compounds such as benzyl benzoate and benzyl stearate, nitrogen oxide, acetonitrile, propionitrile,
Benzonitrile, cyclohexylisonitrile, butylamine, aniline, toluidine, triethylamine, virol, pyridine, N-methylformamide, acetamide,! , 1,3.3-tetramethylurea, N-methylpyrrolidone, caprolactam, nitrogen-containing compounds such as nitromethane, carbon disulfide, n-butylmercaptan, thiophenol, dimethylsulfide, dimethyldisulfide, thiophene, dimethylsulfoxide, diphenylsulfoxide Sulfur-containing compounds such as tributylphosphine oxide, ethyldiphenylphosphine oxide, triphenylphosphine oxide, diethylphenylphosphinate, diphenylmethylphosphinate, diphenylethylphosphinate, 0.0-dimethylmethylphosphonothiolate, triethylphosphine oxide, etc. Examples include phosphorus-containing compounds other than organic phosphines, such as phthalate, triphenyl phosphite, triethyl phosphate, triphenyl phosphate, and hexamethylphosphoric triamide.
本発明の方法は、特に溶媒を使用せず、原料物質自体を
溶媒として実施することができるが、原料物質以外に他
の溶媒を使用することもできる。The method of the present invention can be carried out without particularly using a solvent, using the raw material itself as a solvent, but other solvents can also be used in addition to the raw material.
このような溶媒としては、例えばジエチルエーテル、ア
ニソール、テトラヒドロフラン、エチレングリコールジ
エチルエーテル、トリエチレングリコールジメチルエー
テル、ジオキサン等のエーテル類；アセトン、メチルエ
チルケトン、アセトフェノン等のケトン類；メタノール
、エタノール、ｎ−ブタノール、ベンジルアルコール、
エチレングリコール、ジエチレングリコール等のアルコ
ール類；フェノール類；ギ酸、酢酸、プロピオン酸、ト
ルイル酸等のカルボン酸類；酢酸メチル、酢酸ｎ−ブチ
ル、安息香酸ベンジル等のエステル類；ベンゼン、トル
エン、エチルベンゼン、テトラリン等の芳香族炭化水素
；ｎ−ヘキサン、ｎ−オクタン、シクロヘキサン等の脂
肪族炭化水素；ジクロロメタン、トリクロロエタン、ク
ロロベンゼン等のハロゲン化炭化水素；ニトロメタン、
ニトロベンゼン等のニトロ化炭化水素； Ｎ、Ｎ−ジメ
チルホルムアミド、Ｎ、Ｎ−ジメチルアセトアミド、Ｎ
−メチルピロリドン等のカルボン酸アミド；ヘキサメチ
ルリン酸トリアミド、Ｎ、Ｎ、Ｎ’、Ｎ’−テトラエチ
ルスルファミド等のその他のアミド類； Ｎ、Ｎ’−ジ
メチルイミダゾリトン、Ｎ、Ｎ、Ｎ、Ｎ−テトラメチル
尿素等の尿素類；ジメチルスルホン、テトラメチレンス
ルホン等のスルホン類；ジメチルスルホキシド、ジフェ
ニルスルホキシド等のスルホキシド類；γ−ブチロラク
トン、ε−カプロラクトン等のラクトン類；トリプライ
ム（トリエチレングリコールジメチルエーテル）、テト
ラグライム（テトラエチレングリコールジメチルエーテ
ル）、１８−クラウン−６等のポリエーテル類、アセト
ニトリル、ベンゾニトリル等のニトリル類；ジメチルカ
ーボネート、エチレンカーボネート等の炭酸エステル類
が挙げられる。Examples of such solvents include ethers such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol diethyl ether, triethylene glycol dimethyl ether, and dioxane; ketones such as acetone, methyl ethyl ketone, and acetophenone; methanol, ethanol, n-butanol, and benzyl. alcohol,
Alcohols such as ethylene glycol and diethylene glycol; Phenols; Carboxylic acids such as formic acid, acetic acid, propionic acid, and toluic acid; Esters such as methyl acetate, n-butyl acetate, and benzyl benzoate; Benzene, toluene, ethylbenzene, tetralin, etc. Aromatic hydrocarbons; aliphatic hydrocarbons such as n-hexane, n-octane, and cyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, and chlorobenzene; nitromethane,
Nitrated hydrocarbons such as nitrobenzene; N,N-dimethylformamide, N,N-dimethylacetamide, N
-Carboxylic acid amides such as methylpyrrolidone; other amides such as hexamethylphosphoric acid triamide, N,N,N',N'-tetraethylsulfamide;N,N'-dimethylimidazolitone, N,N,N , N-tetramethylurea; sulfones such as dimethylsulfone and tetramethylene sulfone; sulfoxides such as dimethylsulfoxide and diphenylsulfoxide; lactones such as γ-butyrolactone and ε-caprolactone; Polyethers such as dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether), and 18-crown-6; nitriles such as acetonitrile and benzonitrile; and carbonic acid esters such as dimethyl carbonate and ethylene carbonate.
本発明の方法により水素化反応を行うには、反応容器に
、原料物質、前記の触媒成分及び所望により溶媒を導入
しこれに水素を導入する。水素は、窒素あるいは二酸化
炭素等の反応に不活性なガスで希釈されたものであって
もよい。反応温度は通常５０〜２５０℃、好ましくは１
００〜２００℃である。反応系内の水素分圧は特に限ら
れないが、工業的実施上は通常０．１−１００ ｋｇ／
ｃａ＋２、好ましくは１〜５０ｋｇ／ Ｃ１１２である
０反応は回分方式及び連続方式の何れでも実施すること
ができ、回分方式の場合の所要反応時間は通常１〜２０
時間である。In order to carry out the hydrogenation reaction according to the method of the present invention, a raw material, the above-mentioned catalyst component, and optionally a solvent are introduced into a reaction vessel, and hydrogen is introduced therein. Hydrogen may be diluted with a gas inert to the reaction, such as nitrogen or carbon dioxide. The reaction temperature is usually 50 to 250°C, preferably 1
00-200°C. The hydrogen partial pressure in the reaction system is not particularly limited, but in industrial practice it is usually 0.1-100 kg/
The 0 reaction with ca+2, preferably 1 to 50 kg/C112, can be carried out in either a batch system or a continuous system, and in the case of a batch system, the required reaction time is usually 1 to 20 kg/C112.
It's time.
反応生成液から蒸留、抽出等の通常の分離精製手段によ
り目的物であるラクトン類を採取することができる。ま
た蒸留残渣は触媒成分として反応系に循環される０本発
明においては、このようにして水素化反応を行う際に、
前記した種々の手段により水素化反応帯域中のジオール
類の濃度を５重量％以下に保持するものである。The target lactones can be collected from the reaction product liquid by conventional separation and purification means such as distillation and extraction. In addition, the distillation residue is recycled to the reaction system as a catalyst component.In the present invention, when carrying out the hydrogenation reaction in this way,
The concentration of diols in the hydrogenation reaction zone is maintained at 5% by weight or less by the various means described above.
（実施例）
以下本発明を実施例及び比較例について更に詳細に説明
するが、本発明はその要旨を超えない限りこれ等の実施
例に限定されるものではない。(Examples) The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.
実施例１
触媒液の調！１：
０．０５６重量％のルテニウムアセチルアセトナ−）
、０．５１重量％のトリオクチルホスフィン及び０．２
２重量％のｐ−）ルエンスルホン酸を２０００ ｍｌの
テトラエチレングリコールジメチルエーテル（テトラグ
ライム）に溶解し、２００℃で２時間加熱処理して触媒
液を１１１１Ｌ／た。Example 1 Preparation of catalyst liquid! 1: 0.056% by weight of ruthenium acetylacetonate)
, 0.51% by weight trioctylphosphine and 0.2
2% by weight of p-)luenesulfonic acid was dissolved in 2000 ml of tetraethylene glycol dimethyl ether (tetraglyme) and heated at 200°C for 2 hours to give a catalyst solution of 1111 L/glyme.
水素化反応：
第１図に示す流通型反応設備を使用して水素化反応を実
施した。第１図において、１は反応器、２は触媒容器、
３は圧縮機、４は原料容器、５は冷却器、６は気液分離
器、７は第一蒸留塔、８は第２蒸留塔である。Hydrogenation reaction: A hydrogenation reaction was carried out using the flow-type reaction equipment shown in FIG. In FIG. 1, 1 is a reactor, 2 is a catalyst container,
3 is a compressor, 4 is a raw material container, 5 is a cooler, 6 is a gas-liquid separator, 7 is a first distillation column, and 8 is a second distillation column.
触媒液を触媒容器２から５００ ｍｌ／ ｈｒの流量で
反応器ｌに供給し、一方水素ガスを圧縮機３より８００
Ｎｌ／ ｈｒの流量で反応器１ （５００ｍｌ加圧釜
）に供給し、反応器ｌの圧力を４０ ｋｇ／ｃｍ２ Ｇ
、温度を２００℃に加熱保持した。一方、無水コハク酸
８０１量％及びγ−ブチロラクトン２０重量％からなる
原料液を、原料容器４から１００３／ ｈｒの流量で連
続的に反応器ｌに供給して水素化反応を行った。The catalyst liquid was supplied from the catalyst container 2 to the reactor L at a flow rate of 500 ml/hr, while the hydrogen gas was supplied from the compressor 3 at a flow rate of 800 ml/hr.
It was supplied to reactor 1 (500 ml pressure cooker) at a flow rate of Nl/hr, and the pressure in reactor 1 was set to 40 kg/cm2 G.
, the temperature was heated and maintained at 200°C. On the other hand, a raw material liquid consisting of 801% by weight of succinic anhydride and 20% by weight of γ-butyrolactone was continuously supplied from raw material container 4 to reactor 1 at a flow rate of 1003/hr to carry out a hydrogenation reaction.
反応混合物は冷却Ｗ５で６０℃に冷却し、気液分離器６
で常圧下気液分離して廃ガスをパージした。The reaction mixture was cooled to 60°C by cooling W5, and passed through gas-liquid separator 6.
The waste gas was purged by gas-liquid separation under normal pressure.
反応生成液を第１蒸留塔７にフィードして塔頂から生成
ｒ−ブチロラクトン及び水を蒸留分離し、触媒液は塔底
から抜出してｗ９より触媒容１１２に循環すると共に、
その一部を管ｌＯより５０ ｍｌ／ｈｒの流量で第２蒸
留塔８にフィードし、塔頂から！、４−ブタンジオール
を蒸留分離し、缶出液は塔底から抜出して触媒容器２に
循環した。第１蒸留塔７の操作条件は２０段、塔頂真空
度３０ ｍ−水銀柱、還流比３であり、また第２蒸留塔
８の操作条件は３０段、塔頂真空度！０■■水銀柱、還
流比、３であった。The reaction product liquid is fed to the first distillation column 7 to distill and separate the produced r-butyrolactone and water from the top of the column, and the catalyst liquid is extracted from the bottom of the column and circulated through w9 to the catalyst volume 112.
A portion of it is fed into the second distillation column 8 at a flow rate of 50 ml/hr from the pipe IO, and from the top of the column! , 4-butanediol were separated by distillation, and the bottoms were extracted from the bottom of the column and circulated to the catalyst vessel 2. The operating conditions of the first distillation column 7 are 20 stages, the top vacuum level is 30 m-mercury column, and the reflux ratio is 3.The operating conditions of the second distillation column 8 are 30 stages and the top vacuum level! The mercury column was 0. The reflux ratio was 3.
このような方法により３日間連続して反応を行ったとこ
ろ２日以降安定した反応成績を示し、ガスクロマトグラ
フィーにより、反応器ｌ中及び生成物の分析を１日に２
回行ってジオール濃度及びγ−ブチロラクトンの収率を
求めた。またゲルパーミエイションクロマトグラフィー
（ＧＰＣ）により、触媒液の分析を行って高沸点副生物
の生成量を求めた。その結果を表１に示した。When the reaction was carried out continuously for 3 days using this method, stable reaction results were shown from the 2nd day onwards, and analysis of the inside of the reactor and the product was carried out twice a day by gas chromatography.
The diol concentration and the yield of γ-butyrolactone were determined by repeating the experiment several times. Further, the catalyst liquid was analyzed by gel permeation chromatography (GPC) to determine the amount of high-boiling byproducts produced. The results are shown in Table 1.
実施例２
実施例１における管１０より第２蒸留塔８への触媒液の
フィード量（５０ｍｌ／ ｈｒ）を１２ ｍｌ／ｈｒと
し、その他は実施例１と全く同様に反応を行った。その
結果を表１に示す。Example 2 The reaction was carried out in exactly the same manner as in Example 1, except that the feed amount (50 ml/hr) of the catalyst liquid from the tube 10 to the second distillation column 8 in Example 1 was changed to 12 ml/hr. The results are shown in Table 1.
実施例３
実施例１における水素ガスの反応器ｌへの流量（８００
Ｍｌ／ｈｒ）を８０００ Ｎｌ／ｈｒとし、その他は実
施例１と全く同様に反応を行っに、その結果を表１に示
す。Example 3 Flow rate of hydrogen gas to reactor l in Example 1 (800
The reaction was carried out in exactly the same manner as in Example 1, except that the reaction rate (Ml/hr) was set to 8000 Nl/hr, and the results are shown in Table 1.
比較例１
実施例１における管１０より第２蒸留塔８への触媒液の
フィード量（５０ｍｌ／ｈｒ）を５ｍｌ／ｈｒとし、そ
の他は実施例１と全く同様に反応を行った。その結果を
表１に示す。Comparative Example 1 The reaction was carried out in exactly the same manner as in Example 1, except that the feed amount (50 ml/hr) of the catalyst liquid from the tube 10 to the second distillation column 8 in Example 1 was changed to 5 ml/hr. The results are shown in Table 1.
比較例２
比較例１において、反応ｉｌｌの反応温度を２０８℃と
し、その他は比較例１と全く同様に反応を行った。その
結果を表１に示す。Comparative Example 2 In Comparative Example 1, the reaction temperature of the reaction ill was set to 208° C., and the reaction was carried out in exactly the same manner as in Comparative Example 1, except that the reaction temperature was 208° C. The results are shown in Table 1.
表
１
（注）
傘１：２月間４回の分析値の平均で、括弧内は分析値の
範囲を示す。Table 1 (Note) Umbrella 1: Average of 4 analysis values over 2 months. The range of analysis values is shown in parentheses.
＄２：高沸点副生物の生成量には１．４８Ｇを含めた。$2: 1.48G was included in the amount of high boiling point byproducts produced.
１．４８Ｇ：１，４−ブタンジオール
ＧＢＬ ：ｒ−ブチロラクトン
（発明の効果）
本発明方法によれば、ルテニウム触媒を使用してジカル
ボン酸、ジカルボン酸無水物及び／又はジカルボン酸エ
ステルを液相で水素化することによりラクトン類を製造
する場合に、水素化反応帯域における、原料物質の水添
により生成するジオール類の濃度を５重量％以下に保持
することにより、高沸点副生物の生成量を低減してラク
トン類の収率向上に寄与し工業的価値は大きい。1.48G: 1,4-butanediol GBL: r-butyrolactone (effects of the invention) According to the method of the present invention, dicarboxylic acid, dicarboxylic acid anhydride and/or dicarboxylic acid ester are produced in a liquid phase using a ruthenium catalyst. When producing lactones by hydrogenation, the amount of high-boiling byproducts produced can be reduced by maintaining the concentration of diols produced by hydrogenation of the raw material in the hydrogenation reaction zone at 5% by weight or less. This reduction contributes to improving the yield of lactones and is of great industrial value.
第１図は本発明の実施に使用される流通型反応設備の工
程図を示す。
図中１は反応器、２は触媒容器、３は圧縮機、４は原料
容器、５は冷却器、６は気液分離器、７は第１蒸留塔、
８は第２蒸留塔である。FIG. 1 shows a process diagram of a flow-through reaction facility used to carry out the present invention. In the figure, 1 is a reactor, 2 is a catalyst container, 3 is a compressor, 4 is a raw material container, 5 is a cooler, 6 is a gas-liquid separator, 7 is a first distillation column,
8 is a second distillation column.
Claims (1)
カルボン酸エステルをルテニウム触媒の存在下液相で水
素化することによりラクトン類を製造する方法において
、水素化反応帯域中におけるジオール類の濃度を５重量
％以下に保持することを特徴とするラクトン類の製造方
法。(1) In a method for producing lactones by hydrogenating dicarboxylic acid, dicarboxylic acid anhydride, and/or dicarboxylic acid ester in the liquid phase in the presence of a ruthenium catalyst, the concentration of diols in the hydrogenation reaction zone is A method for producing lactones, characterized in that the lactones are maintained at % by weight or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1217236A JP2785967B2 (en) | 1989-08-25 | 1989-08-25 | Method for producing lactones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1217236A JP2785967B2 (en) | 1989-08-25 | 1989-08-25 | Method for producing lactones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0383974A true JPH0383974A (en) | 1991-04-09 |
| JP2785967B2 JP2785967B2 (en) | 1998-08-13 |
Family
ID=16700986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1217236A Expired - Fee Related JP2785967B2 (en) | 1989-08-25 | 1989-08-25 | Method for producing lactones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2785967B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7427684B2 (en) | 2003-10-30 | 2008-09-23 | Davy Process Technology Limited | Process for the production of lactams |
| US7498450B2 (en) | 2003-10-31 | 2009-03-03 | Davy Process Technology Limited | Homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides thereof |
| US7709689B2 (en) | 2002-05-02 | 2010-05-04 | Davy Process Technololgy Limited | Homogenous process for the hydrogenation of carboxylic acids and derivatives thereof |
| CN105712961A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for preparing lactone by means of oxidizing dihydric alcohol |
-
1989
- 1989-08-25 JP JP1217236A patent/JP2785967B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7709689B2 (en) | 2002-05-02 | 2010-05-04 | Davy Process Technololgy Limited | Homogenous process for the hydrogenation of carboxylic acids and derivatives thereof |
| US9636671B2 (en) | 2002-05-02 | 2017-05-02 | Davy Process Technology Limited | Homogeneous process for the hydrogenation of carboxylic acids and derivatives thereof |
| US7427684B2 (en) | 2003-10-30 | 2008-09-23 | Davy Process Technology Limited | Process for the production of lactams |
| US7498450B2 (en) | 2003-10-31 | 2009-03-03 | Davy Process Technology Limited | Homogeneous process for the hydrogenation of dicarboxylic acids and/or anhydrides thereof |
| CN105712961A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for preparing lactone by means of oxidizing dihydric alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2785967B2 (en) | 1998-08-13 |
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