JP2549046B2 - Method for producing mixed acid anhydride - Google Patents
Method for producing mixed acid anhydrideInfo
- Publication number
- JP2549046B2 JP2549046B2 JP4244185A JP24418592A JP2549046B2 JP 2549046 B2 JP2549046 B2 JP 2549046B2 JP 4244185 A JP4244185 A JP 4244185A JP 24418592 A JP24418592 A JP 24418592A JP 2549046 B2 JP2549046 B2 JP 2549046B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- chloride
- organic acid
- butylammonium
- tetra
- 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.)
- Expired - Fee Related
Links
- 150000008065 acid anhydrides Chemical class 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000003983 crown ethers Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 4
- 150000004714 phosphonium salts Chemical class 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 claims description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 7
- -1 alkali metal salt Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229960002446 octanoic acid Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 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
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- KHAVLLBUVKBTBG-UHFFFAOYSA-N dec-9-enoic acid Chemical compound OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- DLGVYULRVSVFQI-UHFFFAOYSA-N octanoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCCCC(O)=O DLGVYULRVSVFQI-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZONJATNKKGGVSU-UHFFFAOYSA-N 14-methylpentadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCC(O)=O ZONJATNKKGGVSU-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- VUAXHMVRKOTJKP-UHFFFAOYSA-N 2,2-dimethylbutyric acid Chemical compound CCC(C)(C)C(O)=O VUAXHMVRKOTJKP-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GDKSGUPCUITVJN-UHFFFAOYSA-M benzyl(diethyl)sulfanium;chloride Chemical compound [Cl-].CC[S+](CC)CC1=CC=CC=C1 GDKSGUPCUITVJN-UHFFFAOYSA-M 0.000 description 1
- WCHPXAFAEZGCMB-UHFFFAOYSA-M benzyl(tributyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 WCHPXAFAEZGCMB-UHFFFAOYSA-M 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- BQAQHFMZRLEURF-UHFFFAOYSA-N bromo(butyl)phosphane Chemical compound CCCCPBr BQAQHFMZRLEURF-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical class CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 1
- RAFYDKXYXRZODZ-UHFFFAOYSA-N octanoyl octanoate Chemical compound CCCCCCCC(=O)OC(=O)CCCCCCC RAFYDKXYXRZODZ-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- UIUWNILCHFBLEQ-NSCUHMNNSA-N trans-pent-3-enoic acid Chemical compound C\C=C\CC(O)=O UIUWNILCHFBLEQ-NSCUHMNNSA-N 0.000 description 1
- LWBLDXRXGCRDDS-UHFFFAOYSA-M tributylsulfanium;bromide Chemical compound [Br-].CCCC[S+](CCCC)CCCC LWBLDXRXGCRDDS-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene Substances 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、混合酸無水物、より詳
述すれば、異種混合有機酸無水物の高純度品の製造方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mixed acid anhydride, and more particularly to a method for producing a highly pure product of a heterogeneous mixed organic acid anhydride.
【０００２】[0002]
【従来の技術】従来の有機酸無水物の合成は、有機酸中
に脱水剤、例えば硫酸を入れて反応せしめる方法、有機
酸と無水酢酸とを加熱する方法、有機酸のアルカリ金属
塩又は有機アミン塩と有機酸クロライドを反応せしめる
方法などが公知である。2. Description of the Related Art Conventional organic acid anhydrides are synthesized by adding a dehydrating agent such as sulfuric acid to an organic acid for reaction, heating an organic acid and acetic anhydride, an alkali metal salt of an organic acid or an organic acid. A method of reacting an amine salt with an organic acid chloride is known.
【０００３】しかしながら、脱水剤又は無水酢酸を用い
た反応では、異種脂肪酸からなる混合酸無水物が高純度
で合成できない。また、有機酸のアルカリ金属塩と有機
酸クロライドとの反応では、適当な溶媒が必須であり、
この溶媒は溶解度パラメーターが大である必要があり、
一般にはジメチルスルホキサイド又は水などが用いられ
る。前者の如き溶媒では、８０℃以上の反応温度が必要
で、加熱により混合酸無水物の変換反応、例えば目的物
をＲ1 ＣＯＯＣＯＲ2 （Ｒ1 及びＲ2 は異なるアルキル
基）とすると、Ｒ1 ＣＯＯＣＯＲ1 とＲ2 ＣＯＯＣＯＲ
2 に変換する反応がおこり、純度を下げる現象がおこ
る。However, in the reaction using a dehydrating agent or acetic anhydride, a mixed acid anhydride composed of different fatty acids cannot be synthesized with high purity. Further, in the reaction of the alkali metal salt of an organic acid with an organic acid chloride, a suitable solvent is essential,
This solvent must have a large solubility parameter,
Generally, dimethyl sulfoxide or water is used. A solvent such as the former requires a reaction temperature of 80 ° C. or higher, and a reaction for converting a mixed acid anhydride by heating, for example, R 1 COOCOR 2 (where R 1 and R 2 are different alkyl groups) is used, R 1 COOCOR 1 and R 2 COOCOR
The reaction of converting into 2 occurs, and the phenomenon of decreasing the purity occurs.
【０００４】後者の溶媒、即ち水を用いた場合には、有
機酸クロライドが水に不溶であり、一方の原料である有
機酸のアルカリ金属塩が水可溶であるため、不均一系の
反応となる。その為に反応速度が遅く、主反応がおこる
前に、有機酸クロライドの加水分解がおこり、収率の低
下及び、加水分解した有機酸と有機酸クロライドの無水
物の反応がおこり、純度低下をおこし、好ましくない。When the latter solvent, that is, water is used, the organic acid chloride is insoluble in water, and the alkali metal salt of the organic acid, which is one of the starting materials, is water-soluble. Becomes Therefore, the reaction rate is slow, the hydrolysis of the organic acid chloride occurs before the main reaction occurs, the yield decreases, and the reaction between the hydrolyzed organic acid and the anhydride of the organic acid chloride occurs, resulting in a decrease in purity. It is not preferable.
【０００５】上述の反応として、最も好ましい反応形態
は、有機酸の有機アミン塩と有機酸クロライドとを適当
な有機溶媒中にて反応せしめる方法である。しかしなが
ら、本反応形態では、有機アミンの塩酸塩が塩として析
出し、反応終期にはスラリー状となる。従って大過剰の
有機溶媒を使用しなければ撹拌ができず、工業的には不
利な反応といえる。As the above-mentioned reaction, the most preferable reaction mode is a method in which an organic amine salt of an organic acid and an organic acid chloride are reacted in a suitable organic solvent. However, in this reaction mode, the hydrochloride salt of the organic amine is precipitated as a salt and becomes a slurry at the end of the reaction. Therefore, unless a large excess of organic solvent is used, stirring cannot be performed, which is an industrially disadvantageous reaction.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記問題点
を解決すべき異種の混合酸無水物を工業的に高純度で製
造し得る、新規な製造方法を提供することを課題とす
る。SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel production method capable of industrially producing a mixed acid anhydride of a different type which should solve the above problems with high purity.
【０００７】[0007]
【課題を解決するための手段】本発明の要旨は、一般式
Ｒ１ＣＯＯＨ（式中、Ｒ１は炭素数３〜２４の飽和又は
不飽和アルキル基、又は置換されていてもよいフェニル
基であり、かつ後述するＲ２と異なる基である。）で表
わされる有機酸（以下、有機酸と略す。）と、一般式Ｒ
２ＣＯＣｌ（式中、Ｒ２は炭素数３〜２４の飽和又は不
飽和アルキル基、又は置換されていてもよいフェニル基
であり、かつ前述するＲ１と異なる基である。）で表わ
される有機酸クロライド（以下、有機酸クライドと略
す。）を反応せしめて一般式Ｒ１ＣＯＯＣＯＲ２（式
中、Ｒ１及びＲ２は前述と同意義である。）で表わされ
る混合酸無水物（以下、混合酸無水物と略す。）を製造
するに際し、アルカリ金属水酸化物水溶液中で、特定の
相関移動触媒（以下、相関移動触媒と略す。）の存在下
に反応せしめることを特徴とする混合酸無水物の製造方
法である。The gist of the present invention is to provide a compound represented by the general formula R 1 COOH (wherein R 1 is a saturated or unsaturated alkyl group having 3 to 24 carbon atoms, or an optionally substituted phenyl group). And an organic acid (hereinafter abbreviated as “organic acid”) represented by a group different from R 2 described below.
2 COCl (wherein R 2 is a saturated or unsaturated alkyl group having 3 to 24 carbon atoms or an optionally substituted phenyl group, and is a group different from R 1 described above). A mixed acid anhydride represented by the general formula R 1 COOCOR 2 (wherein R 1 and R 2 have the same meanings as described above) by reacting an acid chloride (hereinafter, abbreviated as organic acid clide) (hereinafter, A mixed acid, which is characterized by reacting in the presence of a specific phase transfer catalyst (hereinafter abbreviated as phase transfer catalyst) in an aqueous solution of an alkali metal hydroxide when producing a mixed acid anhydride. It is a method for producing an anhydride.
【０００８】本発明で使用される有機酸としては、プロ
ピオン酸、ブタン酸、ペンタン酸、ヘキサン酸、オクタ
ン酸、ペラルゴン酸、カプリル酸、ウンデカン酸、ラウ
リン酸、トリデシル酸、ミリスチン酸、パルミチン酸、
ステアリン酸、ベヘン酸、リグノセリン酸等の直鎖脂肪
族酸、アクリル酸、クロトン酸、メタクリル酸、３−ペ
ンテン酸、カプロレイン酸、オレイン酸等の不飽和脂肪
族酸、イソブタン酸、イソペンタン酸、ネオペンタン
酸、イソオクタン酸、２−エチルヘキサン酸、ネオヘキ
サン酸、イソノナン酸、ネオデカン酸、イソパルミチン
酸、イソステアリン酸等の分岐脂肪族酸、安息香酸、ｐ
−ニトロ安息香酸、ｐ−ブロモ安息香酸等の芳香族酸が
挙げられる。Examples of the organic acid used in the present invention include propionic acid, butanoic acid, pentanoic acid, hexanoic acid, octanoic acid, pelargonic acid, caprylic acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid,
Straight-chain aliphatic acids such as stearic acid, behenic acid, lignoceric acid, acrylic acid, crotonic acid, methacrylic acid, 3-pentenoic acid, caproleic acid, unsaturated aliphatic acids such as oleic acid, isobutanoic acid, isopentanoic acid, neopentane Acids, isooctanoic acid, 2-ethylhexanoic acid, neohexanoic acid, isononanoic acid, neodecanoic acid, isopalmitic acid, branched aliphatic acids such as isostearic acid, benzoic acid, p
Examples thereof include aromatic acids such as -nitrobenzoic acid and p-bromobenzoic acid.
【０００９】本発明で使用される有機酸クロライドとし
ては、前述した有機酸の酸クロライドが挙げられる。具
体的には前述の有機酸と三塩化燐、あるいは塩化チオニ
ルを反応せしめることにより得られる。Examples of the organic acid chloride used in the present invention include the acid chlorides of the above-mentioned organic acids. Specifically, it can be obtained by reacting the above-mentioned organic acid with phosphorus trichloride or thionyl chloride.
【００１０】次に有機酸と有機酸クロライドから混合酸
無水物を製造する際の反応条件としては、本反応で使用
される有機酸１モルに対して、有機酸クロライドは０．
８〜２．０モル、好ましくは１〜１．５モルである。Next, the reaction conditions for producing a mixed acid anhydride from an organic acid and an organic acid chloride are as follows.
It is 8-2.0 mol, preferably 1-1.5 mol.
【００１１】本発明で使用されるアルカリ金属水酸化物
水溶液中のアルカリ金属水酸化物としては、例えば水酸
化ナトリウム、水酸化カリウム、水酸化リチウム等が挙
げられる。またアルカリ金属水酸化物の使用量として
は、有機酸クロライド１モルに対して、１．０〜２．０
モルの範囲から選ぶことができ、好ましくは、１．０〜
１．５モルであり、水溶液濃度は特に限定するものでは
ないが、アルカリ金属水酸化物が実質的に水に溶解して
いることが操作上好ましい。Examples of the alkali metal hydroxide in the alkali metal hydroxide aqueous solution used in the present invention include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. The amount of alkali metal hydroxide used is 1.0 to 2.0 with respect to 1 mol of the organic acid chloride.
It can be selected from the range of moles, preferably 1.0 to
It is 1.5 mol, and the concentration of the aqueous solution is not particularly limited, but it is preferable from the viewpoint of operation that the alkali metal hydroxide is substantially dissolved in water.
【００１２】本発明において使用される相関移動触媒
は、特定の第四級アンモニウム塩、ホスホニウム塩、ス
ルホニウム塩、クラウンエーテル、ポリエチレングリコ
ールであり、特定の第四級アンモニウム塩、ホスホニウ
ム塩、スルホニウム塩、クラウンエーテル等について
は、低級分子としても、又は高分子に組み込まれた形態
としても有効である。The phase transfer catalyst used in the present invention is a specific quaternary ammonium salt, phosphonium salt, sulfonium salt, crown ether or polyethylene glycol, and a specific quaternary ammonium salt, phosphonium salt, sulfonium salt, The crown ether and the like are effective both as a lower molecule and as a form incorporated in a polymer.
【００１３】相関移動触媒の具体例としては、テトラメ
チルアンモニウムクロライド、ベンジルトリメチルアン
モニウムクロライド、ベンジルトリエチルアンモニウム
クロライド、ベンジルトリ−ｎ−ブチルアンモニウムク
ロライド、テトラ−ｎ−ブチルアンモニウムクロライ
ド、テトラ−ｎ−ブチルアンモニウムブロマイド及びテ
トラ−ｎ−ブチルアンモニウムハイドロジエンサルフェ
ートから選ばれた第四級アンモニウム塩類、ベンジル−
トリ−ｎ−ブチルホスホニウムクロライド、テトラ−ｎ
−ブチルホスホニウムブロマイド等のホスホニウム塩
類、トリ−ｎ−ブチルスルホニウムブロマイド、ベンジ
ルジエチルスルホニウムクロライド等のスルホニウム塩
類、１８−クラウン６−エーテル、ジベンゾ−１８−ク
ラウン６−エーテル等のクラウンエーテル類、ポリエチ
レングリコール４００、１０００、４０００等のポリエ
チレングリコール類を挙げることができる。これらのう
ちでも、効果等を考慮し、かつ工業的には第四級アンモ
ニウム塩類の使用が好ましい。Specific examples of the phase transfer catalyst include tetramethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltri-n-butylammonium chloride, tetra-n-butylammonium chloride and tetra-n-butylammonium bromide. And quaternary ammonium salts selected from tetra-n-butylammonium hydrogensulfate, benzyl-
Tri-n-butylphosphonium chloride, tetra-n
-Phosphonium salts such as butylphosphonium bromide, sulfonium salts such as tri-n-butylsulfonium bromide and benzyldiethylsulfonium chloride, crown ethers such as 18-crown 6-ether and dibenzo-18-crown 6-ether, polyethylene glycol 400 , 1000, 4000 and the like polyethylene glycols. Among these, it is preferable to use quaternary ammonium salts in consideration of effects and the like and industrially.
【００１４】相関移動触媒の使用量については有機酸ク
ロライド及び有機酸の総量に対して０．０１〜１０％の
範囲から選ぶことができ、好ましくは０．１〜５％であ
る。The amount of the phase transfer catalyst used can be selected from the range of 0.01 to 10%, preferably 0.1 to 5%, based on the total amount of the organic acid chloride and the organic acid.
【００１５】本反応においては、有機溶媒の使用は不可
欠ではないが、有機溶媒の使用は好ましい結果をもたら
す。特に使用される有機溶媒としては、反応条件下で安
定であり、水と実質的に溶け合わないものが好ましい。
具体的には、例えばペンタン、ヘキサン、ヘプタン、オ
クタン等の脂肪族炭化水素類、ベンゼン、トルエン、キ
シレン等の芳香族炭化水素類、四塩化炭素、クロロホル
ム、ジクロルメタン等のハロゲン化合物等を挙げること
ができる。なお、有機溶媒は単独あるいは２種以上混合
して使用してもよい。In this reaction, the use of an organic solvent is not essential, but the use of an organic solvent gives favorable results. As the organic solvent used in particular, those which are stable under the reaction conditions and which are substantially insoluble in water are preferable.
Specific examples include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, halogen compounds such as carbon tetrachloride, chloroform and dichloromethane. it can. The organic solvents may be used alone or in combination of two or more.
【００１６】反応温度は−５〜６０℃、好ましくは０〜
２０℃が望ましい。６０℃より高い温度では、加水分解
及びエステル交換反応がおこり、好ましくない。ここで
いうエステル交換反応とは、Ｒ1 ＣＯＯＣＯＲ2 がＲ1
ＣＯＯＣＯＲ1 とＲ2 ＣＯＯＣＯＲ2 になる反応を指
す。The reaction temperature is -5 to 60 ° C, preferably 0 to
20 ° C is desirable. At a temperature higher than 60 ° C., hydrolysis and transesterification occur, which is not preferable. As used herein, the transesterification reaction means that R 1 COOCOR 2 is R 1
Refers to the reaction that produces COOCOR 1 and R 2 COOCOR 2 .
【００１７】[0017]
【作用】本発明の製造方法は、相関移動触媒が存在する
ため、アルカリ金属水酸化物の水溶液を用いても、反応
速度は早く、従って有機酸クロライドの加水分解が抑制
され、高収率、高純度の混合有機酸無水物が得れるもの
と考えられる。In the production method of the present invention, since a phase transfer catalyst is present, the reaction rate is fast even when an aqueous solution of an alkali metal hydroxide is used. Therefore, hydrolysis of organic acid chloride is suppressed, and high yield, It is considered that a highly pure mixed organic acid anhydride can be obtained.
【００１８】[0018]
【実施例】以下に、実施例にて本発明をさらに具体的に
説明するが、本発明はこれら実施例に限定されるもので
はない。 実施例１；撹拌機、温度計および滴下ロートを取り付け
た１Ｌのフラスコにアクリル酸７２ｇ（１モル）、水酸
化ナトリウム４４ｇ（１．１モル）を水１７６ｇに溶か
した溶液、トルエン３００ｇ、テトラｎ−ブチルアンモ
ニウムクロライド２．０ｇを仕込み、０〜６℃で撹拌し
ながらオクタン酸クロライド１７８．８ｇ（１．１モ
ル）を２時間で滴下した。滴下終了後、更に２時間、０
〜６℃で撹拌した。反応終了後、分液し、トルエン層を
水洗し、無水硫酸ナトリウムで乾燥した。次いで、ロ−
タリ−エバポレ−タ−にて、高真空下に液温２０℃以下
にてトルエンを留去した。The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Example 1; A 1 L flask equipped with a stirrer, a thermometer, and a dropping funnel was equipped with a solution of 72 g (1 mol) of acrylic acid and 44 g (1.1 mol) of sodium hydroxide in 176 g of water, 300 g of toluene, and tetra-n. 2.0 g of -butylammonium chloride was charged, and 178.8 g (1.1 mol) of octanoic acid chloride was added dropwise over 2 hours while stirring at 0 to 6 ° C. 2 hours after the dropping is completed,
Stir at ~ 6 ° C. After completion of the reaction, liquid separation was carried out, the toluene layer was washed with water and dried over anhydrous sodium sulfate. Then,
Toluene was distilled off under a high vacuum at a liquid temperature of 20 ° C. or lower with a tally evaporator.
【００１９】このようにして得た液を、キャピラリーガ
スクロマトグラフにて分析したところ、アクリル酸無水
物の含量は０．４％、オクタン酸無水物の含量は０．６
％であり、アクリル酸−オクタン酸の混合酸無水物は９
８．７％、オクタン酸含量は０．２％であった。なお、
これらの成分はＧＣ−ＭＳによって確認した。液の収量
は１９５ｇであり、アクリル酸−オクタン酸混合酸無水
物として純度換算すると１９２．４ｇ（０．９７モル）
であった。When the liquid thus obtained was analyzed by a capillary gas chromatograph, the content of acrylic acid anhydride was 0.4% and the content of octanoic acid anhydride was 0.6%.
%, And the mixed acid anhydride of acrylic acid-octanoic acid is 9%.
The content was 8.7% and the octanoic acid content was 0.2%. In addition,
These components were confirmed by GC-MS. The yield of the liquid was 195 g, which was 192.4 g (0.97 mol) in terms of purity as an acrylic acid-octanoic acid mixed acid anhydride.
Met.
【００２０】実施例２〜８および比較例１〜４；実施例
１と同様に各種有機酸および有機酸クロライドとの反応
によって、異種の混合酸無水物を合成した。結果を表
１，表２に示した。Examples 2 to 8 and Comparative Examples 1 to 4; Similar to Example 1, different kinds of mixed acid anhydrides were synthesized by reaction with various organic acids and organic acid chlorides. The results are shown in Tables 1 and 2.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【発明の効果】本発明製造方法に従えば、相関移動触媒
が存在するためアルカリ金属水酸化物水溶液を用いて
も、反応速度は早く、有機酸クロライドの加水分解も抑
制され、高収率、高純度の混合有機酸無水物を得ること
ができる。さらに、アルカリ金属水酸化物の水溶液とい
う安価な原料を用い、発生する塩酸の処理もアルカリ金
属の塩化物として除去が容易であり、工業的に有利な方
法である。According to the production method of the present invention, since a phase transfer catalyst is present, the reaction rate is fast even when an aqueous alkali metal hydroxide solution is used, hydrolysis of organic acid chloride is suppressed, and high yield, A highly pure mixed organic acid anhydride can be obtained. Furthermore, the treatment of the generated hydrochloric acid using an inexpensive raw material such as an aqueous solution of an alkali metal hydroxide is easy to remove as a chloride of the alkali metal, which is an industrially advantageous method.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 57/00 Ｃ０７Ｃ 57/00 63/06 63/06 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07C 57/00 C07C 57/00 63/06 63/06 // C07B 61/00 300 C07B 61/00 300
Claims (1)
数３〜２４の飽和又は不飽和アルキル基、又は置換され
ていてもよいフェニル基であり、かつ後述するＲ２と異
なる基である）で表わされる有機酸と、一般式Ｒ２ＣＯ
Ｃｌ（式中、Ｒ２は炭素数３〜２４の飽和又は不飽和ア
ルキル基、又は置換されていてもよいフェニル基であ
り、かつ前述するＲ１と異なる基である）で表わされる
有機酸クロライドを反応せしめて一般式Ｒ１ＣＯＯＣＯ
Ｒ２（式中、Ｒ１及びＲ２は前述と同意義である）で表
わされる混合酸無水物を製造するに際し、アルカリ金属
水酸化物水溶液中で、下記の相関移動触媒の存在下に反
応せしめることを特徴とする混合酸無水物の製造方法。
相関移動触媒は、テトラメチルアンモニウムクロライ
ド、ベンジルトリメチルアンモニウムクロライド、ベン
ジルトリエチルアンモニウムクロライド、ベンジルトリ
−ｎ−ブチルアンモニウムクロライド、テトラ−ｎ−ブ
チルアンモニウムクロライド、テトラ−ｎ−ブチルアン
モニウムブロマイド及びテトラ−ｎ−ブチルアンモニウ
ムハイドロジエンサルフェートからなる第四級アンモニ
ウム塩、ホスホニウム塩、スルホニウム塩、クラウンエ
ーテル並びにポリエチレングリコールからなる群より選
ばれた少なくとも１種以上の化合物である。1. A general formula R 1 COOH (wherein R 1 is a saturated or unsaturated alkyl group having 3 to 24 carbon atoms or an optionally substituted phenyl group, and is different from R 2 described later). And an organic acid represented by the general formula R 2 CO
An organic acid chloride represented by Cl (in the formula, R 2 is a saturated or unsaturated alkyl group having 3 to 24 carbon atoms or an optionally substituted phenyl group, and is a group different from R 1 described above). To react with the general formula R 1 COOCO
When a mixed acid anhydride represented by R 2 (wherein R 1 and R 2 have the same meanings as described above) is produced, the reaction is carried out in an aqueous alkali metal hydroxide solution in the presence of the following phase transfer catalyst. A method for producing a mixed acid anhydride, characterized by comprising:
Phase transfer catalysts include tetramethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltri-n-butylammonium chloride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide and tetra-n-butylammonium. It is at least one compound selected from the group consisting of quaternary ammonium salts consisting of hydrogen sulfate, phosphonium salts, sulfonium salts, crown ethers and polyethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4244185A JP2549046B2 (en) | 1992-08-19 | 1992-08-19 | Method for producing mixed acid anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4244185A JP2549046B2 (en) | 1992-08-19 | 1992-08-19 | Method for producing mixed acid anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0665138A JPH0665138A (en) | 1994-03-08 |
| JP2549046B2 true JP2549046B2 (en) | 1996-10-30 |
Family
ID=17115037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4244185A Expired - Fee Related JP2549046B2 (en) | 1992-08-19 | 1992-08-19 | Method for producing mixed acid anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2549046B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3144791A1 (en) * | 1981-11-11 | 1983-05-19 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF CARBONIC ACID ANHYDRIDES |
-
1992
- 1992-08-19 JP JP4244185A patent/JP2549046B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0665138A (en) | 1994-03-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |