JPH03128346A - Production of aromatic carboxylic acids - Google Patents
Production of aromatic carboxylic acidsInfo
- Publication number
- JPH03128346A JPH03128346A JP2139692A JP13969290A JPH03128346A JP H03128346 A JPH03128346 A JP H03128346A JP 2139692 A JP2139692 A JP 2139692A JP 13969290 A JP13969290 A JP 13969290A JP H03128346 A JPH03128346 A JP H03128346A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- compounds
- aromatic
- thallium
- 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.)
- Pending
Links
- -1 aromatic carboxylic acids Chemical class 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 150000003476 thallium compounds Chemical class 0.000 claims abstract description 29
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000012546 transfer Methods 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 40
- 150000002739 metals Chemical class 0.000 claims description 23
- 239000001569 carbon dioxide Substances 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 20
- 235000010233 benzoic acid Nutrition 0.000 abstract description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 abstract description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000005711 Benzoic acid Substances 0.000 abstract description 2
- 239000004305 biphenyl Substances 0.000 abstract description 2
- 235000010290 biphenyl Nutrition 0.000 abstract description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000203 mixture Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- CMJCEVKJYRZMIA-UHFFFAOYSA-M thallium(i) iodide Chemical compound [Tl]I CMJCEVKJYRZMIA-UHFFFAOYSA-M 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 7
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- 150000001553 barium compounds Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 3
- 229940043430 calcium compound Drugs 0.000 description 3
- 150000001674 calcium compounds Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- GOMCKELMLXHYHH-UHFFFAOYSA-L dipotassium;phthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC=C1C([O-])=O GOMCKELMLXHYHH-UHFFFAOYSA-L 0.000 description 3
- 238000010813 internal standard method Methods 0.000 description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 3
- 150000003112 potassium compounds Chemical class 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 150000003298 rubidium compounds Chemical class 0.000 description 3
- 150000003326 scandium compounds Chemical class 0.000 description 3
- 150000003388 sodium compounds Chemical class 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 150000003438 strontium compounds Chemical class 0.000 description 3
- 150000003748 yttrium compounds Chemical class 0.000 description 3
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- IFVTZJHWGZSXFD-UHFFFAOYSA-N biphenylene Chemical group C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 150000002601 lanthanoid compounds Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-L naphthalene-2,6-dicarboxylate Chemical compound C1=C(C([O-])=O)C=CC2=CC(C(=O)[O-])=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-L 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 2
- ZYALGIIHWPHZBJ-UHFFFAOYSA-N phenanthrene-2,7-dicarboxylic acid Chemical compound OC(=O)C1=CC=C2C3=CC=C(C(=O)O)C=C3C=CC2=C1 ZYALGIIHWPHZBJ-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- JAAGVIUFBAHDMA-UHFFFAOYSA-M rubidium bromide Chemical compound [Br-].[Rb+] JAAGVIUFBAHDMA-UHFFFAOYSA-M 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 description 2
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- 229910003438 thallium oxide Inorganic materials 0.000 description 2
- IQVLXQGNLCPZCL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 2,6-bis[(2-methylpropan-2-yl)oxycarbonylamino]hexanoate Chemical compound CC(C)(C)OC(=O)NCCCCC(NC(=O)OC(C)(C)C)C(=O)ON1C(=O)CCC1=O IQVLXQGNLCPZCL-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- CCFAKBRKTKVJPO-UHFFFAOYSA-N 1-anthroic acid Chemical compound C1=CC=C2C=C3C(C(=O)O)=CC=CC3=CC2=C1 CCFAKBRKTKVJPO-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- KEDNSMBVYXSBFC-UHFFFAOYSA-N 6-bromo-2-chloroquinoline-4-carbonyl chloride Chemical compound C1=C(Br)C=C2C(C(=O)Cl)=CC(Cl)=NC2=C1 KEDNSMBVYXSBFC-UHFFFAOYSA-N 0.000 description 1
- RHYRCZZEWBVMTM-UHFFFAOYSA-H C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Sm+3].[Sm+3] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Sm+3].[Sm+3] RHYRCZZEWBVMTM-UHFFFAOYSA-H 0.000 description 1
- NHIXZCFNNJFZIQ-UHFFFAOYSA-H C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ce+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ce+3] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ce+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ce+3] NHIXZCFNNJFZIQ-UHFFFAOYSA-H 0.000 description 1
- IYPOOQFPPSJDOK-UHFFFAOYSA-H C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[La+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[La+3] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[La+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[La+3] IYPOOQFPPSJDOK-UHFFFAOYSA-H 0.000 description 1
- IJFCVSDHMYVPIF-UHFFFAOYSA-H C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Sc+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Sc+3] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Sc+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Sc+3] IJFCVSDHMYVPIF-UHFFFAOYSA-H 0.000 description 1
- IGQZMZOMDHKGFC-UHFFFAOYSA-H C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Y+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Y+3] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Y+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Y+3] IGQZMZOMDHKGFC-UHFFFAOYSA-H 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910016859 Lanthanum iodide Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- FCTMBHUXRGYAPT-UHFFFAOYSA-M [Cs+].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 Chemical compound [Cs+].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 FCTMBHUXRGYAPT-UHFFFAOYSA-M 0.000 description 1
- PUXXZWDHPRHNJK-UHFFFAOYSA-H [Yb+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Yb+3] Chemical compound [Yb+3].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Yb+3] PUXXZWDHPRHNJK-UHFFFAOYSA-H 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- CBXLQVFLPVYSJW-UHFFFAOYSA-L barium(2+);naphthalene-1-carboxylate Chemical compound [Ba+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 CBXLQVFLPVYSJW-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 1
- QNSOHXTZPUMONC-UHFFFAOYSA-N benzene pentacarboxylic acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O QNSOHXTZPUMONC-UHFFFAOYSA-N 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- PYSZASIZWHHPHJ-UHFFFAOYSA-L calcium;phthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O PYSZASIZWHHPHJ-UHFFFAOYSA-L 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- ZEDZJUDTPVFRNB-UHFFFAOYSA-K cerium(3+);triiodide Chemical compound I[Ce](I)I ZEDZJUDTPVFRNB-UHFFFAOYSA-K 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- CLDJTTWVDVIKKN-UHFFFAOYSA-N dibenzothiophene-1-carboxylic acid Chemical compound S1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O CLDJTTWVDVIKKN-UHFFFAOYSA-N 0.000 description 1
- UBRZUHOUIISJAZ-UHFFFAOYSA-L dicesium;phthalate Chemical compound [Cs+].[Cs+].[O-]C(=O)C1=CC=CC=C1C([O-])=O UBRZUHOUIISJAZ-UHFFFAOYSA-L 0.000 description 1
- VNSVQJIXVXZDJF-UHFFFAOYSA-L dilithium;phthalate Chemical compound [Li+].[Li+].[O-]C(=O)C1=CC=CC=C1C([O-])=O VNSVQJIXVXZDJF-UHFFFAOYSA-L 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- KGOKDPWKDBWITQ-UHFFFAOYSA-K gadolinium(3+);tribromide Chemical compound Br[Gd](Br)Br KGOKDPWKDBWITQ-UHFFFAOYSA-K 0.000 description 1
- IZZTUGMCLUGNPM-UHFFFAOYSA-K gadolinium(3+);triiodide Chemical compound I[Gd](I)I IZZTUGMCLUGNPM-UHFFFAOYSA-K 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- XAAKCCMYRKZRAK-UHFFFAOYSA-N isoquinoline-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=NC=CC2=C1 XAAKCCMYRKZRAK-UHFFFAOYSA-N 0.000 description 1
- KYKBXWMMXCGRBA-UHFFFAOYSA-K lanthanum(3+);triiodide Chemical compound I[La](I)I KYKBXWMMXCGRBA-UHFFFAOYSA-K 0.000 description 1
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- DAOCFLYDQCOXGE-UHFFFAOYSA-L magnesium;naphthalene-1-carboxylate Chemical compound [Mg+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 DAOCFLYDQCOXGE-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- WFEDZLQUUNHNKE-UHFFFAOYSA-M naphthalene-1-carboxylate rubidium(1+) Chemical compound C1=CC=C2C(=C1)C=CC=C2C(=O)[O-].[Rb+] WFEDZLQUUNHNKE-UHFFFAOYSA-M 0.000 description 1
- ZDLZKHLDCVDPSE-UHFFFAOYSA-K naphthalene-1-carboxylate;yttrium(3+) Chemical compound [Y+3].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 ZDLZKHLDCVDPSE-UHFFFAOYSA-K 0.000 description 1
- LNIQEBQSPWOLPH-UHFFFAOYSA-N naphthalene-1-carboxylic acid Chemical compound OC(=O)c1cccc2ccccc12.OC(=O)c1cccc2ccccc12 LNIQEBQSPWOLPH-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- LBWLQVSRPJHLEY-UHFFFAOYSA-K neodymium(3+);tribromide Chemical compound Br[Nd](Br)Br LBWLQVSRPJHLEY-UHFFFAOYSA-K 0.000 description 1
- DKSXWSAKLYQPQE-UHFFFAOYSA-K neodymium(3+);triiodide Chemical compound I[Nd](I)I DKSXWSAKLYQPQE-UHFFFAOYSA-K 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 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
- VKOQSSGPQRCFPD-UHFFFAOYSA-L phthalate;rubidium(1+) Chemical compound [Rb+].[Rb+].[O-]C(=O)C1=CC=CC=C1C([O-])=O VKOQSSGPQRCFPD-UHFFFAOYSA-L 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- ZVUVJTQITHFYHV-UHFFFAOYSA-M potassium;naphthalene-1-carboxylate Chemical compound [K+].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 ZVUVJTQITHFYHV-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- ICKYUJFKBKOPJT-UHFFFAOYSA-K samarium(3+);tribromide Chemical compound Br[Sm](Br)Br ICKYUJFKBKOPJT-UHFFFAOYSA-K 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- OJIKOZJGHCVMDC-UHFFFAOYSA-K samarium(iii) fluoride Chemical compound F[Sm](F)F OJIKOZJGHCVMDC-UHFFFAOYSA-K 0.000 description 1
- APPHYFNIXVIIJR-UHFFFAOYSA-K scandium bromide Chemical compound Br[Sc](Br)Br APPHYFNIXVIIJR-UHFFFAOYSA-K 0.000 description 1
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 1
- OEKDNFRQVZLFBZ-UHFFFAOYSA-K scandium fluoride Chemical compound F[Sc](F)F OEKDNFRQVZLFBZ-UHFFFAOYSA-K 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- NYMLCLICEBTBKR-UHFFFAOYSA-H scandium(3+);tricarbonate Chemical compound [Sc+3].[Sc+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NYMLCLICEBTBKR-UHFFFAOYSA-H 0.000 description 1
- HUIHCQPFSRNMNM-UHFFFAOYSA-K scandium(3+);triiodide Chemical compound [Sc+3].[I-].[I-].[I-] HUIHCQPFSRNMNM-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- WEGDVNIPLOLRJC-UHFFFAOYSA-M sodium;naphthalene-1-carboxylate Chemical compound [Na+].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 WEGDVNIPLOLRJC-UHFFFAOYSA-M 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229940074155 strontium bromide Drugs 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- KRIJWFBRWPCESA-UHFFFAOYSA-L strontium iodide Chemical compound [Sr+2].[I-].[I-] KRIJWFBRWPCESA-UHFFFAOYSA-L 0.000 description 1
- 229910001643 strontium iodide Inorganic materials 0.000 description 1
- OJXRUZAVBHFYRI-UHFFFAOYSA-L strontium naphthalene-1-carboxylate Chemical compound [Sr++].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12 OJXRUZAVBHFYRI-UHFFFAOYSA-L 0.000 description 1
- KGCOMQDJRDGWDD-UHFFFAOYSA-L strontium;phthalate Chemical compound [Sr+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O KGCOMQDJRDGWDD-UHFFFAOYSA-L 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- PGAPATLGJSQQBU-UHFFFAOYSA-M thallium(i) bromide Chemical compound [Tl]Br PGAPATLGJSQQBU-UHFFFAOYSA-M 0.000 description 1
- DASUJKKKKGHFBF-UHFFFAOYSA-L thallium(i) carbonate Chemical compound [Tl+].[Tl+].[O-]C([O-])=O DASUJKKKKGHFBF-UHFFFAOYSA-L 0.000 description 1
- CULOEOTWMUCRSJ-UHFFFAOYSA-M thallium(i) fluoride Chemical compound [Tl]F CULOEOTWMUCRSJ-UHFFFAOYSA-M 0.000 description 1
- TYIZUJNEZNBXRS-UHFFFAOYSA-K trifluorogadolinium Chemical compound F[Gd](F)F TYIZUJNEZNBXRS-UHFFFAOYSA-K 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- XRADHEAKQRNYQQ-UHFFFAOYSA-K trifluoroneodymium Chemical compound F[Nd](F)F XRADHEAKQRNYQQ-UHFFFAOYSA-K 0.000 description 1
- XQKBFQXWZCFNFF-UHFFFAOYSA-K triiodosamarium Chemical compound I[Sm](I)I XQKBFQXWZCFNFF-UHFFFAOYSA-K 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- LSSJSIMBIIVSTN-UHFFFAOYSA-K ytterbium(3+);triiodide Chemical compound I[Yb](I)I LSSJSIMBIIVSTN-UHFFFAOYSA-K 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 1
- QNLXXQBCQYDKHD-UHFFFAOYSA-K ytterbium(iii) bromide Chemical compound Br[Yb](Br)Br QNLXXQBCQYDKHD-UHFFFAOYSA-K 0.000 description 1
- XASAPYQVQBKMIN-UHFFFAOYSA-K ytterbium(iii) fluoride Chemical compound F[Yb](F)F XASAPYQVQBKMIN-UHFFFAOYSA-K 0.000 description 1
- 229940105965 yttrium bromide Drugs 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- 229940105970 yttrium iodide Drugs 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- LFWQXIMAKJCMJL-UHFFFAOYSA-K yttrium(3+);triiodide Chemical compound I[Y](I)I LFWQXIMAKJCMJL-UHFFFAOYSA-K 0.000 description 1
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 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
Landscapes
- Indole Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、芳香族カルボン酸又はその塩の製造方法及
びカルボキシル基の分子間移動方法並びにそれに使用す
る触媒に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an aromatic carboxylic acid or a salt thereof, a method for intermolecular transfer of a carboxyl group, and a catalyst used therefor.
芳香族カルボン酸塩は酸析により容易に相当するカルボ
ン酸に変換できる。芳香族カルボン酸の代表例であるナ
フタレン−２，６−ジカルボン酸は、ポリエステル原料
の酸部分として近年注目を集めており、工業的に価値の
ある化合物である。Aromatic carboxylic acid salts can be easily converted to the corresponding carboxylic acids by acid precipitation. Naphthalene-2,6-dicarboxylic acid, which is a typical example of aromatic carboxylic acids, has recently attracted attention as an acid moiety of polyester raw materials, and is an industrially valuable compound.
従来、芳香族カルボン酸又はその塩の製造については数
多くの方法が提唱されている。その代表例について、ナ
フタレン−２，６−ジカルボン酸又はその塩の製造方法
を例にとれば、以下の如くになる。Conventionally, many methods have been proposed for producing aromatic carboxylic acids or salts thereof. A representative example of the method for producing naphthalene-2,6-dicarboxylic acid or a salt thereof is as follows.
１つは、いわゆるヘンケル法である。すなわち、ナフタ
レンモノカルボン酸（ナフトエ酸）のアルカリ金属塩又
はナフタレンジカルボン酸のジアルカリ金属塩あるいは
これらの混合物を、触媒と共に炭酸ガス加圧下に、３５
０〜５ｏｏ０ｃに加熱する方法である。ナフトエ酸アル
カリ金属塩からは不均化反応によりナフタレン−２，６
−ジカルボン酸ジアルカリ金属塩とナフタレンとが生成
し、ナフタレンジカルボン酸ジアルカリ金属塩からは転
位反応によりナフタレン−２，６−ジカルボン酸ジアル
カリ金属塩が選択的に生成する（■Ｂ、 Ｒａｅｃｋｅ
。One is the so-called Henkel method. That is, an alkali metal salt of naphthalene monocarboxylic acid (naphthoic acid), a dialkali metal salt of naphthalene dicarboxylic acid, or a mixture thereof is heated with a catalyst under carbon dioxide gas pressure for 35 minutes.
This is a method of heating to 0 to 5oo0c. Naphthalene-2,6 is produced from naphthoic acid alkali metal salt through a disproportionation reaction.
- A dialkali metal salt of dicarboxylic acid and naphthalene are produced, and a dialkali metal salt of naphthalene-2,6-dicarboxylate is selectively produced from the dialkali metal salt of naphthalene dicarboxylate through a rearrangement reaction (■B, Raecke
.
Ａｎｇｅｗ、 Ｃｈｅｍ、、 ７０． １（１９５
８）；■Ｂ、Ｒａｅｃｋｅら、Ｏｒｇ、 Ｓｙｎ、 Ｃ
ａ１１．、５．８１３（１９７３）；■山下ら、有合化
、２０．５０１（１９６２）、■Ｅ、 ＭｃＮｅｌｉｓ
、 Ｊ、 Ｏｒｇ。Angew, Chem, 70. 1 (195
8);■B, Raecke et al., Org, Syn, C
a11. , 5.813 (1973); ■Yamashita et al., 20.501 (1962), ■E, McNelis
, J. Org.
Ｃｈｅｍ、、３０．１２０９（１９６５）；■米国特許
第２．８２３．２３１号明細書；■特公昭５１−１０．
２２４号公報；■ＥＰ ０２１７３２９ ＡＩ公報参照
）。Chem, 30.1209 (1965); ■U.S. Patent No. 2.823.231; ■Specification of Japanese Patent Publication No. 1983-10.
224 Publication; ■EP 0217329 AI Publication).
また、ヘンケル法の類似方法として、ピロメリット酸テ
トラカリウム塩とナフタレンとを原料とし、触媒として
アルミニウムカーバイドと塩化カドミウムの組合せを使
用し、二酸化炭素１，４５０気圧の加圧下に、４２５℃
で１５時間加熱する方法がある（ドイツ連邦共和国特許
第１．０５６．５９８号明細書）。In addition, as a method similar to the Henkel method, pyromellitic acid tetrapotassium salt and naphthalene are used as raw materials, a combination of aluminum carbide and cadmium chloride is used as a catalyst, and the temperature is heated at 425°C under a pressure of 1,450 atmospheres of carbon dioxide.
There is a method of heating for 15 hours (German Patent No. 1.056.598).
上記ナフタレン−２，６−ジカルボン酸ジアルカリ金属
塩を製造するための前者の方法においては、その原料と
してナフトエ酸のアルカリ金属塩又はナフタレンジカル
ボン酸のジアルカリ金属塩あるいはこれらの混合物が用
いられるが、これらの原料はその入手が困難でかつ高価
であるという問題がある。In the former method for producing the dialkali metal salt of naphthalene-2,6-dicarboxylic acid, an alkali metal salt of naphthoic acid, a dialkali metal salt of naphthalene dicarboxylic acid, or a mixture thereof is used as the raw material. The problem is that raw materials are difficult to obtain and expensive.
また、後者の方法においては、反応時に１． ４５０気
圧という非常に高い反応圧力を必要とするという大きな
問題がある。すなわち、工業的に大量生産を行う場合に
は、高圧反応用の設備に膨大なコストがかかり、しかも
、高圧反応による危険性が増大する。In the latter method, 1. A major problem is that a very high reaction pressure of 450 atmospheres is required. That is, when mass production is carried out industrially, a huge amount of cost is required for high-pressure reaction equipment, and moreover, the dangers due to high-pressure reactions increase.
本発明者らは、この様な従来法が有する課題、すなわち
原料が高価でしかも非常に高い反応圧力が必要であると
いう問題を解決すべく鋭意研究を行った結果、触媒とし
てタリウム化合物を存在させることにより、安価な原料
を使用し、かつ、低い反応圧力で芳香族カルボン酸を製
造し得ることを見出し、本発明を完成した。The present inventors conducted intensive research to solve the problems of conventional methods, namely that raw materials are expensive and require extremely high reaction pressures, and as a result, the present inventors discovered a method in which a thallium compound is present as a catalyst. The inventors have discovered that aromatic carboxylic acids can be produced using inexpensive raw materials and at low reaction pressures, and have completed the present invention.
すなわち、第一の発明は、カルボキシル基を有しない芳
香族化合物と芳香族カルボン酸塩とを、タリウム化合物
を存在させて炭酸ガス加圧下に加熱し、反応させて上記
芳香族化合物を母核とするカルボン酸又はその塩を製造
する方法である。That is, in the first invention, an aromatic compound having no carboxyl group and an aromatic carboxylate are heated under pressure of carbon dioxide gas in the presence of a thallium compound, and the aromatic compound is reacted with the aromatic compound as a mother nucleus. This is a method for producing a carboxylic acid or a salt thereof.
また、第二の発明は、１つ以上の置換可能な核結合水素
を有し、かつ、カルボキシル基を有しない芳香族化合物
と芳香族カルボン酸又はその塩とを、タリウム化合物を
存在させて炭酸ガス加圧下に加熱し、反応させるカルボ
キシル基の分子間移動方法である。Further, the second invention provides carbonation of an aromatic compound having one or more substitutable nuclear-bonded hydrogens and having no carboxyl group and an aromatic carboxylic acid or a salt thereof in the presence of a thallium compound. This is a method of intermolecular transfer of carboxyl groups by heating and reacting under gas pressure.
さらに、第三の発明は、タリウム化合物を含有する点に
特徴を有するカルボキシル基を芳香族化合物間で分子間
移動させるための触媒である。Furthermore, the third invention is a catalyst for intermolecularly transferring a carboxyl group between aromatic compounds, which is characterized in that it contains a thallium compound.
そして、第四の発明は、カルボキシル基を有しない芳香
族化合物と芳香族カルボン酸塩とを、（ａ）タリウム化
合物及び（ｂ） Ｉ ａ族金属、Ｕａａ族金属びＩＩＩ
ａ族金属の化合物からなる群から選ばれた１種又は２種
以上の化合物を存在させて炭酸ガス加圧下に加熱し、反
応させて上記芳香族化合物を母核とするカルボン酸又は
その塩を製造する方法である。And, the fourth invention combines an aromatic compound having no carboxyl group and an aromatic carboxylate with (a) a thallium compound and (b) a group Ia metal, a group Uaa metal, and a group III metal.
In the presence of one or more compounds selected from the group consisting of compounds of Group A metals, heated under pressure of carbon dioxide gas and reacted to produce a carboxylic acid or its salt having the aromatic compound as a core. This is a method of manufacturing.
また、第五の発明は、１つ以上の置換可能な核結合水素
を有し、かつ、カルボキシル基を有しない芳香族化合物
と芳香族カルボン酸又はその塩とを、（ａ）タリウム化
合物及び（ｂ） Ｉ ａ族金属、ＩＩａ族金属及びＩＩ
Ｉａ族金属の化合物からなる群から選ばれた１種又は２
種以上の化合物を存在させて炭酸ガス加圧下に加熱し、
反応させるカルボキシル基の分子間移動方法である。Further, the fifth invention provides an aromatic compound having one or more substitutable nuclear-bonded hydrogens and having no carboxyl group and an aromatic carboxylic acid or a salt thereof, (a) a thallium compound and ( b) Group Ia metals, Group IIa metals and II
One or two selected from the group consisting of Group Ia metal compounds
By heating under carbon dioxide gas pressure in the presence of more than one type of compound,
This is a method of intermolecular transfer of carboxyl groups to be reacted.
さらに、第六の発明は、（ａ）タリウム化合物及び（ｂ
） Ｉ ａ族金属、Ｉｌａ族金属及びＩｎａ族金属の化
合物からなる群から選ばれた１種又は２種以上の化合物
を含有する点に特徴を有するカルボキシル基を芳香族化
合物間で分子間移動させるための触媒である。Furthermore, the sixth invention provides (a) a thallium compound and (b) a thallium compound;
) Intermolecular transfer of a carboxyl group between aromatic compounds characterized by containing one or more compounds selected from the group consisting of compounds of Group Ia metals, Group Ila metals, and Group Ina metals. It is a catalyst for
本発明で使用する原料のカルボキシル基を有しない芳香
族化合物（以下、Ａｒという）としては、１つ以上の置
換可能な核結合水素を有する芳香族化合物であり、好ま
しくは多環縮合芳香族化合物である。その具体例として
は、ナフタレン、ビフェニル、フェナンスレン、アント
ラセン、インデン、ピレン、ターフェニル、ジフェニル
エーテル、インドール、キノリン、イソキノリン、カル
バゾール、アクリジン、チオナフテン、ジフェニレンオ
キサイド、ジベンゾチオフェン、フラン等を挙げること
ができる。The aromatic compound having no carboxyl group (hereinafter referred to as Ar) as a raw material used in the present invention is an aromatic compound having one or more substitutable nuclear-bonded hydrogen, preferably a polycyclic condensed aromatic compound. It is. Specific examples include naphthalene, biphenyl, phenanthrene, anthracene, indene, pyrene, terphenyl, diphenyl ether, indole, quinoline, isoquinoline, carbazole, acridine, thionaphthene, diphenylene oxide, dibenzothiophene, and furan.
本発明で使用するもう１つの原料の芳香族カルボン酸塩
（以下、Ｂ−Ｃという）としては、カルボキシル基を１
つ以上有するものであればよいが、経済性を考えると、
ベンゼンカルボン酸の塩が好ましい。その具体例として
は、安息香酸、フタル酸、イソフタル酸、テレフタル酸
、トリメリット酸、トリメシン酸、ヘミメリット酸、ピ
ロメリット酸、ブレニット酸、メロファン酸、ベンゼン
ペンタカルボン酸、メリット酸の如きベンゼンカルボン
酸類の塩あるいはこれらの混合物等を挙げることができ
る。これらベンゼンカルボン酸の塩の混合物は各々の塩
を混合することにより得られるが、さらに以下の方法に
よっても容易に入手できる。すなわち、石炭あるいはピ
ッチをアルカリ水溶液中で酸素ないしは酸素含有ガスで
酸化することにより、ベンゼンカルボン酸類の混合物が
アルカリ金属塩として得られる（例えば、神谷ら、有合
化、旦、 １０９（’１９５９） ）。Ｂ−Ｃはカルボ
ン酸の塩であるが、塩としては、各種の金属塩やアンモ
ニウム塩等が挙げられ、好ましくはアルカリ金属塩であ
り、より好ましくはカリウム塩及びナトリウム塩であり
、特にカリウム塩が最もよい結果を与える。Ｂ−Ｃの使
用量は、Ａｒに対して重量で０．０１〜２倍量、通常は
０．１−１倍量である。Another raw material aromatic carboxylate (hereinafter referred to as B-C) used in the present invention has a carboxyl group of 1
It is fine as long as it has more than one, but considering economic efficiency,
Salts of benzenecarboxylic acids are preferred. Specific examples include benzenecarboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, brennitic acid, merophanic acid, benzenepentacarboxylic acid, and mellitic acid. Examples include acid salts and mixtures thereof. A mixture of these benzenecarboxylic acid salts can be obtained by mixing the respective salts, but it can also be easily obtained by the following method. That is, by oxidizing coal or pitch with oxygen or an oxygen-containing gas in an alkaline aqueous solution, a mixture of benzenecarboxylic acids can be obtained as an alkali metal salt (for example, Kamiya et al., Yugoka, Dan, 109 ('1959)). ). B-C is a salt of a carboxylic acid, and examples of the salt include various metal salts and ammonium salts, preferably alkali metal salts, more preferably potassium salts and sodium salts, especially potassium salts. gives the best results. The amount of B-C used is 0.01 to 2 times the weight of Ar, usually 0.1-1 times the weight of Ar.
また、Ｂ−Ｃは、以下の方法によっても調製することが
できる。すなわち、芳香族カルボン酸無水物と金属塩と
を本発明の反応条件下で処理して目的のＢ−Ｃを得るこ
とができる。例えば、無水フタル酸と炭酸カリウムとの
モル比ｌ：１混合物を本発明の反応条件下に反応させる
と、フタル酸カリウム塩を得ることができる。この様に
して生成したＢ−Ｃを本発明に用いることは何ら差し支
えない。すなわち、芳香族カルボン酸無水物と金属塩を
本発明の一方の原料とすることも本発明の実施態様に含
まれる。なお、芳香族カルボン酸と水酸化アルカリ金属
塩とを本発明の反応条件下で処理すると、同様にＢ−Ｃ
を得ることができるが、同時に反応系内に水が生じてし
まい、反応が阻害されるので好ましくない。Moreover, BC can also be prepared by the following method. That is, the desired B-C can be obtained by treating an aromatic carboxylic acid anhydride and a metal salt under the reaction conditions of the present invention. For example, a 1:1 molar mixture of phthalic anhydride and potassium carbonate can be reacted under the reaction conditions of the invention to obtain a potassium phthalate salt. There is no problem in using BC produced in this manner in the present invention. That is, using an aromatic carboxylic acid anhydride and a metal salt as one of the raw materials of the present invention is also included in the embodiment of the present invention. Note that when an aromatic carboxylic acid and an alkali metal hydroxide salt are treated under the reaction conditions of the present invention, B-C
can be obtained, but at the same time water is generated in the reaction system, which is not preferable because the reaction is inhibited.
本発明の反応では、ＡｒとＢ−Ｃとを後記の触媒の存在
下に炭酸ガス加圧下で加熱して反応させることによりＢ
−Ｃのカルボキシル基が分子間移動し、Ａｒの核結合水
素がカルボキシル基に置換された化合物、すなわちＡｒ
を母核とするカルボン酸又はその塩（以下、Ａｒ−Ｃと
いう）が生成する。この様なＡｒ−Ｃの例としては、ナ
フタレン−２，６−ジカルボン酸又はその塩の如きナフ
タレンカルボン酸又はその塩や、４，４°−ジフェニル
ジカルボン酸又はその塩の如きジフェニルジカルボン酸
又はその塩や、ジフェニレンオキサイド−２、４，６，
８−テトラカルボン酸又はその塩の如きジフェニレンオ
キサイドカルボン酸又はその塩や、フェナンスレン−２
，７−ジカルボン酸又はその塩の如きフェナンスレンカ
ルボン酸又はその塩や、カルバゾール−１，３，６，８
−テトラカルボン酸又はその塩の如きカルバゾールカル
ボン酸又はその塩や、アントラセンカルボン酸又はその
塩や、ジベンゾチオフェンカルボン酸又はその塩や、キ
ノリンカルボン酸又はその塩や、イソキノリンカルボン
酸又はその塩等を挙げることができる。In the reaction of the present invention, Ar and B-C are reacted by heating under pressure of carbon dioxide gas in the presence of the catalyst described below.
A compound in which the carboxyl group of -C moves intermolecularly and the nuclear bonded hydrogen of Ar is replaced by the carboxyl group, that is, Ar
A carboxylic acid or a salt thereof (hereinafter referred to as Ar-C) having as a core is produced. Examples of such Ar-C include naphthalenecarboxylic acid or its salts such as naphthalene-2,6-dicarboxylic acid or its salts, and diphenyldicarboxylic acids or its salts such as 4,4°-diphenyldicarboxylic acid or its salts. Salt, diphenylene oxide-2, 4, 6,
Diphenylene oxide carboxylic acid or its salt such as 8-tetracarboxylic acid or its salt, phenanthrene-2
, 7-dicarboxylic acid or its salts, and carbazole-1,3,6,8
- Carbazolecarboxylic acid or its salts such as tetracarboxylic acid or its salts, anthracenecarboxylic acid or its salts, dibenzothiophenecarboxylic acid or its salts, quinolinecarboxylic acid or its salts, isoquinolinecarboxylic acid or its salts, etc. can be mentioned.
本発明では、反応触媒としてタリウム化合物を使用する
場合と、（ａ）タリウム化合物及び（ｂ） Ｉ ａ族金
属、ＩＩａ族金属及びＩＩＩａＩＩａ族金属物からなる
群から選ばれた１種又は２種以上の化合物を使用する場
合とがあり、後者の方が前者の場合に比べてその触媒作
用の点で優れている。In the present invention, when a thallium compound is used as a reaction catalyst, (a) a thallium compound and (b) one or more selected from the group consisting of group Ia metals, group IIa metals, and group IIIaIIa metals. There are cases where a compound is used, and the latter is superior to the former in terms of its catalytic action.
本発明で使用するタリウム化合物としては、フッ化タリ
ウム、塩化タリウム、臭化タリウム、ヨウ化タリウム、
酸化タリウム、炭酸タリウム等の無機タリウム化合物や
、フタル酸タリウム、ナフタル酸タリウム等の有機タリ
ウム化合物を挙げることができる。これらのタリウム化
合物の使用量は、Ｂ−Ｃに対して通常０．５〜５０モル
％、好ましくは４〜４０モル％の範囲である。５０モル
％を越える大量使用は炭化物の副生が促進されて好まし
くない。The thallium compounds used in the present invention include thallium fluoride, thallium chloride, thallium bromide, thallium iodide,
Examples include inorganic thallium compounds such as thallium oxide and thallium carbonate, and organic thallium compounds such as thallium phthalate and thallium naphthalate. The amount of these thallium compounds used is usually 0.5 to 50 mol%, preferably 4 to 40 mol%, based on B-C. If the amount exceeds 50 mol %, the by-product of carbides is promoted, which is not preferable.
本発明で触媒の一部として使用するＩａ族金属化合物と
しては、フッ化リチウム、塩化リチウム、臭化リチウム
、ヨウ化リチウム、酸化リチウム、炭酸リチウム等の如
き無機リチウム化合物やフタル酸リチウムやナフタル酸
リチウム等の如き有機リチウム化合物の様な各種リチウ
ム化合物、フッ化ナトリウム、塩化ナトリウム、臭化ナ
トリウム、ヨウ化ナトリウム、酸化ナトリウム、炭酸ナ
トリウム等の如き無機ナトリウム化合物やフタル酸ナト
リウムやナフタル酸ナトリウム等の如き有機ナトリウム
化合物の様な各種ナトリウム化合物、フッ化カリウム、
塩化カリウム、臭化カリウム、ヨウ化カリウム、酸化カ
リウム、炭酸カリウム等の如き無機カリウム化合物やフ
タル酸カリウムやナフタル酸カリウム等の如き有機カリ
ウム化合物の様な各種カリウム化合物、フッ化ルビジウ
ム、塩化ルビジウム、臭化ルビジウム、ヨウ化ルビジウ
ム、酸化ルビジウム、炭酸ルビジウム等の如き無機ルビ
ジウム化合物やフタル酸ルビジウムやナフタル酸ルビジ
ウム等の如き有機ルビジウム化合物の様な各種ルビジウ
ム化合物、フッ化セシウム、塩化セシウム、臭化セシウ
ム、ヨウ化セシウム、酸化セシウム、炭酸セシウム等の
如き無機セシウム化合物やフタル酸セシウムやナフタル
酸セシウム等の如き有機セシウム化合物の様な各種セシ
ウム化合物、あるいはこれらの混合物を挙げることがで
きる。Group Ia metal compounds used as part of the catalyst in the present invention include inorganic lithium compounds such as lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium oxide, lithium carbonate, and lithium phthalate and naphthalate. Various lithium compounds such as organic lithium compounds such as lithium, inorganic sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium oxide, sodium carbonate, etc., sodium phthalate, sodium naphthalate, etc. various sodium compounds such as organic sodium compounds, potassium fluoride,
Various potassium compounds such as inorganic potassium compounds such as potassium chloride, potassium bromide, potassium iodide, potassium oxide, potassium carbonate, etc. and organic potassium compounds such as potassium phthalate, potassium naphthalate, etc., rubidium fluoride, rubidium chloride, Various rubidium compounds such as inorganic rubidium compounds such as rubidium bromide, rubidium iodide, rubidium oxide, rubidium carbonate, organic rubidium compounds such as rubidium phthalate, rubidium naphthalate, cesium fluoride, cesium chloride, cesium bromide, etc. , various cesium compounds such as inorganic cesium compounds such as cesium iodide, cesium oxide, cesium carbonate, and organic cesium compounds such as cesium phthalate and cesium naphthalate, or mixtures thereof.
また、本発明で触媒の一部として使用するＩＩａＩａ族
金属化合物ては、フッ化マグネシウム、塩化マグネシウ
ム、臭化マグネシウム、ヨウ化マグネシウム、酸化マグ
ネシウム、炭酸マグネシウム等の如き無機マグネシウム
化合物やフタル酸マグネシウムやナフタル酸マグネシウ
ム等の如き有機マグネシウム化合物の様な各種マグネシ
ウム化合物、フッ化カルシウム、塩化カルシウム、臭化
カルシウム、ヨウ化カルシウム、酸化カルシウム、炭酸
カルシウム等の如き無機カルシウム化合物やフタル酸カ
ルシウムやナックル酸カルシウム等の如き有機カルシウ
ム化合物の様な各種カルシウム化合物、フッ化ストロン
チウム、塩化ストロンチウム、臭化ストロンチウム、ヨ
ウ化ストロンチウム、酸化ストロンチウム、炭酸ストロ
ンチウム等の如き無機ストロンチウム化合物やフタル酸
ストロンチウムやナフタル酸ストロンチウム等の如き有
機ストロンチウム化合物の様な各種ストロンチウム化合
物、フッ化バリウム、塩化バリウム、臭化バリウム、ヨ
ウ化バリウム、酸化バリウム、炭酸バリウム等の如き無
機バリウム化合物やフタル酸バリウムやナフタル酸バリ
ウム等の如き有機バリウム化合物の様な各種バリウム化
合物、あるいはこれらの混合物を挙げることができる。In addition, the IIaIa group metal compounds used as part of the catalyst in the present invention include inorganic magnesium compounds such as magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium oxide, magnesium carbonate, and magnesium phthalate. Various magnesium compounds such as organic magnesium compounds such as magnesium naphthalate, inorganic calcium compounds such as calcium fluoride, calcium chloride, calcium bromide, calcium iodide, calcium oxide, calcium carbonate, etc., calcium phthalate and calcium knuckle. Various calcium compounds such as organic calcium compounds such as strontium fluoride, strontium chloride, strontium bromide, strontium iodide, strontium oxide, strontium carbonate, etc., and inorganic strontium compounds such as strontium phthalate, strontium naphthalate, etc. Various strontium compounds such as organic strontium compounds, inorganic barium compounds such as barium fluoride, barium chloride, barium bromide, barium iodide, barium oxide, barium carbonate, etc., and organic barium compounds such as barium phthalate, barium naphthalate, etc. Examples include various barium compounds such as, or mixtures thereof.
さらに、本発明で触媒の一部として使用する■ａ族金属
化合物としては、フッ化スカンジウム、塩化スカンジウ
ム、臭化スカンジウム、ヨウ化スカンジウム、酸化スカ
ンジウム、炭酸スカンジウム等の如き無機スカンジウム
化合物やフタル酸スカンジウムやナフタル酸スカンジウ
ム等の如き有機スカンジウム化合物の様な各種スカンジ
ウム化合物、フッ化イツトリウム、塩化イツトリウム、
臭化イツトリウム、ヨウ化イツトリウム、酸化イツトリ
ウム、炭酸イツトリウム等の如き無機イツトリウム化合
物やフタル酸イツトリウムやナフタル酸イツトリウム等
の如き有機イツトリウム化合物の様な各種イツトリウム
化合物、フッ化ランタン、塩化ランタン、臭化ランタン
、ヨウ化ランタン、フッ化セリウム、塩化セリウム、臭
化セリウム、ヨウ化セリウム、フッ化ネオジウム、塩
化ネオジウム、臭化ネオジウム、ヨウ化ネオジウム、フ
ッ化ガドリニウム、塩化ガドリニウム、臭化ガドリニウ
ム、ヨウ化ガドリニウム、フッ化サマリウム、塩化サマ
リウム、臭化サマリウム、ヨウ化サマリウム、フッ化イ
ッテルビウム、塩化イッテルビウム、臭化イッテルビウ
ム、ヨウ化イッテルビウム等の無機ランタノイド化合物
や、フタル酸ランタン、フタル酸セリウム、フタル酸プ
ラセオジウム、フタル酸ネオジウム、フタル酸ガドリニ
ウム、フタル酸サマリウム、フタル酸イッテルビウム等
の有機ランタノイド化合物、あるいはこれらの混合物を
挙げることができる。Further, as the Group A metal compound used as a part of the catalyst in the present invention, inorganic scandium compounds such as scandium fluoride, scandium chloride, scandium bromide, scandium iodide, scandium oxide, scandium carbonate, etc., and scandium phthalate. various scandium compounds such as organic scandium compounds such as scandium naphthalate, yttrium fluoride, yttrium chloride,
Various yttrium compounds such as inorganic yttrium compounds such as yttrium bromide, yttrium iodide, yttrium oxide, yttrium carbonate, etc., and organic yttrium compounds such as yttrium phthalate, yttrium naphthalate, etc., lanthanum fluoride, lanthanum chloride, and lanthanum bromide. , lanthanum iodide, cerium fluoride, cerium chloride, cerium bromide, cerium iodide, neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, gadolinium fluoride, gadolinium chloride, gadolinium bromide, gadolinium iodide, Inorganic lanthanoid compounds such as samarium fluoride, samarium chloride, samarium bromide, samarium iodide, ytterbium fluoride, ytterbium chloride, ytterbium bromide, ytterbium iodide, lanthanum phthalate, cerium phthalate, praseodymium phthalate, phthalic acid Examples include organic lanthanide compounds such as neodymium, gadolinium phthalate, samarium phthalate, and ytterbium phthalate, or mixtures thereof.
これらＩａ族金属、ＩＩａ族金属及びＩＩＩａ族金属の
化合物のいずれか１種又は２種以上を使用する場合にお
けるその使用量は、Ｂ−Ｃに対して通常０．５〜２００
モル％、好ましくは５〜１００モル％の範囲である。０
．５モル％以下の少量使用ではその触媒作用が不十分で
あり、反対に２００モル％を超える大量使用は経済性を
考慮すると好ましくない。また、（ａ）タリウム化合物
とこれら（ｂ）Ｉａ族金属、ＩＩａ族金属及びＩＩａ族
金属の化合物からなる群から選ばれた１種又は２種以上
の化合物とのモル比（（ａ） ／ （ｂ） ）は、０．
１〜５の範囲が好ましい。When using one or more of these group Ia metal, group IIa metal, and group IIIa metal compounds, the amount used is usually 0.5 to 200% relative to B-C.
mol %, preferably in the range of 5 to 100 mol %. 0
．． If it is used in a small amount of 5 mol% or less, its catalytic action will be insufficient, and on the other hand, if it is used in a large amount exceeding 200 mol%, it is not preferable from an economic point of view. In addition, the molar ratio of (a) the thallium compound and (b) one or more compounds selected from the group consisting of group Ia metals, group IIa metals, and compounds of group IIa metals ((a) / ( b) ) is 0.
A range of 1 to 5 is preferred.
また、本発明の反応を行うに際しては、反応に先駆けて
上記Ｂ−Ｃとタリウム化合物、又はＢ−Ｃと（ａ）タリ
ウム化合物及び（ｂ） Ｉ ａ族金属、ＩＩａ族金属及
びＩＩＩａ族金属の化合物からなる群から選ばれた１種
又は２種以上の化合物とを予め良く混合しておくのがよ
い。このための方法として、例えば、原料の水溶液に触
媒を加えてよく混合し、しかる後に水を加熱留去して原
料と触媒との混合物を得る方法や、原料と触媒とをボー
ルミルでよく粉砕混合する方法等を挙げることができ、
これらの方法はそのいずれの方法であっても本発明の実
施には差し支えない。In addition, when carrying out the reaction of the present invention, prior to the reaction, the above B-C and a thallium compound, or B-C and (a) a thallium compound and (b) a group Ia metal, a group IIa metal, and a group IIIa metal are combined. It is preferable to thoroughly mix one or more compounds selected from the group consisting of compounds in advance. Methods for this purpose include, for example, adding the catalyst to an aqueous solution of the raw material and mixing well, and then heating and distilling off the water to obtain a mixture of the raw material and catalyst, or thoroughly pulverizing and mixing the raw material and catalyst with a ball mill. There are ways to do this,
Any of these methods may be used to implement the present invention.
本発明において、反応の際の炭酸ガスの圧力は、その反
応温度において１０〜２００ｋｇ／ｃｒｌ−６１好まし
くは２０〜１５０ｋｇ／ｃｒｌ−Ｇの範囲である。In the present invention, the pressure of carbon dioxide during the reaction is in the range of 10 to 200 kg/crl-61, preferably 20 to 150 kg/crl-G at the reaction temperature.
また、反応温度は、原料並びに触媒により若干具なるが
、通常３００〜５００℃の範囲であり、反応を速やかに
生起させ、かつ、炭化物生成等の副反応を制御する観点
から３５０〜４５０℃の範囲が好ましい。反応時間は、
反応温度により異なるが、通常ｌ〜５０時間の範囲であ
る。The reaction temperature varies depending on the raw materials and catalyst, but is usually in the range of 300 to 500°C, and from the viewpoint of causing the reaction to occur quickly and controlling side reactions such as carbide formation, the reaction temperature is 350 to 450°C. A range is preferred. The reaction time is
Although it varies depending on the reaction temperature, it is usually in the range of 1 to 50 hours.
反応終了後、反応混合物に水を加えてこの反応混合物中
に含有する芳香族カルボン酸塩類を水に溶解させ、また
、トルエンやキシレンの如き有機溶剤をさらに加えて未
反応物及び反応時に副生ずる芳香族化合物を溶解させ、
水層と有機溶剤層とを分離し、水層から目的物を分離す
る。触媒中のタリウム化合物は、水及び有機溶剤のいず
れにも不溶なタリウムの酸化物又は炭酸塩となり、同様
に水及び有機溶剤のいずれにも不溶な副生炭化物と共に
濾過等の手段で容易に分離できる。After the reaction is completed, water is added to the reaction mixture to dissolve the aromatic carboxylic acid salts contained in the reaction mixture, and an organic solvent such as toluene or xylene is further added to remove unreacted substances and by-products during the reaction. dissolve aromatic compounds,
The aqueous layer and organic solvent layer are separated, and the target product is separated from the aqueous layer. The thallium compound in the catalyst becomes a thallium oxide or carbonate that is insoluble in both water and organic solvents, and can be easily separated by means such as filtration along with by-product carbides that are also insoluble in both water and organic solvents. can.
以下、実施例及び比較例に基づいて、本発明方法を具体
的に説明する。The method of the present invention will be specifically explained below based on Examples and Comparative Examples.
実施例１
フタル酸ジカリウム塩（以下、ＰＴＫという）にヨウ化
タリウムをこのＰＴＫに対して１６モル％添加し、ボー
ルミルで粉砕混合した。Example 1 Thallium iodide was added to dipotassium phthalate (hereinafter referred to as PTK) in an amount of 16 mol % based on the PTK, and the mixture was ground and mixed in a ball mill.
この様にして得られたＰＴＫ−ヨウ化タリウム混合物１
０．０ｇとナフタレン３０．０ｇとをオートクレーブに
仕込み、１００℃に加熱した。オートクレーブ内を炭酸
ガスで置換した後、炭酸ガスを４０ｋｇ／ｃｒｌ−Ｇの
圧力まで導入した。PTK-thallium iodide mixture 1 obtained in this way
0.0 g and 30.0 g of naphthalene were placed in an autoclave and heated to 100°C. After replacing the inside of the autoclave with carbon dioxide gas, carbon dioxide gas was introduced to a pressure of 40 kg/crl-G.
次に、オートクレーブ内の混合物を攪拌しながら、５°
Ｃ／ｍｉｎ、の速度で４３０℃まで昇温させ、その温度
で１８時間攪拌を継続した。Next, while stirring the mixture in the autoclave,
The temperature was raised to 430° C. at a rate of C/min, and stirring was continued at that temperature for 18 hours.
反応終了後、反応混合物にトルエン２００−及び水２０
０−を加えてよく攪拌し、水層並びにトルエン層のいず
れにも不溶な固体を濾別した後、水層を分離した。After the reaction is complete, add 20% of toluene and 20% of water to the reaction mixture.
After adding 0- and stirring well, solids insoluble in both the aqueous layer and the toluene layer were filtered off, and the aqueous layer was separated.
得られた水層の一部を採取し、高速液体クロマトグラフ
ィを用いて内部標準法で生成したナフタレン−２，６−
ジカルボン酸塩を定量した結果、ＰＴＫ （−に造型を
基準とする収率が５モル％であった。A part of the obtained aqueous layer was collected and naphthalene-2,6- produced using an internal standard method using high performance liquid chromatography.
As a result of quantifying the dicarboxylate salt, the yield was 5 mol % based on the PTK (-) molding.
比較例Ｉ
ＰＴＫＩＯ，Ｏｇとナフタレン３０．０ｇとをオートク
レーブに仕込み、Ｌ００℃に加熱した。Comparative Example I PTKIO, Og and 30.0 g of naphthalene were placed in an autoclave and heated to L00°C.
オートクレーブ内を炭酸ガスで置換した後、炭酸ガスを
４０ｋｇ／ｃｎｌ’−Ｇの圧力まで導入した。After replacing the inside of the autoclave with carbon dioxide gas, carbon dioxide gas was introduced to a pressure of 40 kg/cnl'-G.
次に、オートクレーブ内の混合物を攪拌しながら、５°
Ｃ／ｍｉｎ、の速度で４３０°Ｃまで昇温させ、その温
度で１８時間攪拌を継続した。Next, while stirring the mixture in the autoclave,
The temperature was raised to 430° C. at a rate of 100° C./min, and stirring was continued at that temperature for 18 hours.
反応終了後、反応混合物にトルエン２００ｍｌ及び水２
００−を加えてよく攪拌し、水層並びにトルエン層のい
ずれにも不溶な固体を濾別した後、水層を分離した。After the reaction is complete, add 200 ml of toluene and 2 ml of water to the reaction mixture.
After adding 00- and stirring well, solids that were insoluble in both the aqueous layer and the toluene layer were filtered off, the aqueous layer was separated.
得られた水層の一部を採取し、高速液体クロマトグラフ
ィを用いて分析した結果、ナフタレン２．６−ジカルボ
ン酸塩は全く生成していなかった。A portion of the obtained aqueous layer was collected and analyzed using high performance liquid chromatography, and as a result, no naphthalene 2,6-dicarboxylate was produced.
実施例２
ＰＴＫにヨウ化タリウム及びヨウ化セシウムをこのＰＴ
Ｋに対して１６モル％添加し、ボールミルで粉砕混合し
た。Example 2 Adding thallium iodide and cesium iodide to PTK
It was added in an amount of 16 mol % based on K, and mixed by pulverization using a ball mill.
この様にして得られたＰＴＫ−ヨウ化タリウム・ヨウ化
セシウム混合物１０．０ｇとナフタレン３０゜Ｏｇとを
オートクレーブに仕込み、１００°Ｃに加熱した。オー
トクレーブ内を炭酸ガスで置換した後、炭酸ガスを４０
ｋｇ／ｃＩＩｒ−Ｇの圧力まで導入した。10.0 g of the PTK-thallium iodide/cesium iodide mixture thus obtained and 30° Og of naphthalene were placed in an autoclave and heated to 100°C. After replacing the inside of the autoclave with carbon dioxide gas,
A pressure of kg/cIIr-G was introduced.
次に、オートクレーブ内の混合物を攪拌しながら、５°
Ｃ／ｍｉｎ、の速度で４００００まで昇温させ、その温
度で１８時間攪拌を継続した。Next, while stirring the mixture in the autoclave,
The temperature was raised to 40,000 C/min at a rate of C/min, and stirring was continued at that temperature for 18 hours.
反応終了後、反応混合物にトルエン２００７ｎｌ及び水
２００−を加えてよく攪拌し、水層並びにトルエン層の
いずれにも不溶な固体を濾別した後、水層を分離した。After the reaction was completed, 2007 nl of toluene and 200 g of water were added to the reaction mixture and stirred thoroughly. After filtering off solids that were insoluble in both the aqueous layer and the toluene layer, the aqueous layer was separated.
得られた水層の一部を採取し、高速液体クロマトグラフ
ィを用いて内部標準法で生成したナフタレン−２，６−
ジカルボン酸塩を定量した結果、ＰＴＫ仕込量を基準と
する収率が８モル％であった。A part of the obtained aqueous layer was collected and naphthalene-2,6- produced using an internal standard method using high performance liquid chromatography.
As a result of quantifying the dicarboxylate salt, the yield was 8 mol% based on the amount of PTK charged.
実施例３
反応温度を４３０℃とした以外は、上記実施例２と同様
にして反応を行い、同様に生成物の分析を行った結果、
目的物のナフタレン−２，６−ジカルボン酸塩の収率は
ＰＴＫ仕込量基準で１６モル％であった。Example 3 The reaction was carried out in the same manner as in Example 2 above, except that the reaction temperature was 430°C, and the product was analyzed in the same manner.
The yield of the target product, naphthalene-2,6-dicarboxylic acid salt, was 16 mol% based on the amount of PTK charged.
実施例４
ＰＴＫにヨウ化タリウム及び塩化バリウムをこのＰＴＫ
に対して１６モル％添加し、ボールミルで粉砕混合した
。Example 4 Adding thallium iodide and barium chloride to PTK
16 mol% was added to the total amount of the powder, and the mixture was ground and mixed using a ball mill.
この様にして得られたＰＴＫ−ヨウ化タリウム・塩化バ
リウム混合物１０．０ｇとナフタレン３０゜０ｇとをオ
ートクレーブに仕込み、以下実施例２と同様に反応を行
い、同様に生成物の分析を行った結果、目的物のナフタ
レン−２，６−ジカルボン酸塩の収率はＰＴＫ仕込量基
準で１０モル％であった。10.0 g of the PTK-thallium iodide/barium chloride mixture thus obtained and 30.0 g of naphthalene were charged into an autoclave, and the reaction was carried out in the same manner as in Example 2, and the product was analyzed in the same manner. As a result, the yield of the target naphthalene-2,6-dicarboxylic acid salt was 10 mol % based on the amount of PTK charged.
実施例５
ＰＴＫにヨウ化タリウム及び塩化ランタンをこのＰＴＫ
に対して１６モル％添加し、ボールミルで粉砕混合した
。Example 5 Adding thallium iodide and lanthanum chloride to PTK
16 mol% was added to the total amount of the powder, and the mixture was ground and mixed using a ball mill.
この様にして得られたＰＴＫ−ヨウ化タリウム・塩化ラ
ンタン混合物１０．０ｇとナフタレン３０゜０ｇとをオ
ートクレーブに仕込み、以下実施例２と同様に反応を行
い、同様に生成物の分析を行った結果、目的物のナフタ
レン−２，６−ジカルボン酸塩の収率はＰＴＫ仕込量基
準で１１モル％であった。10.0 g of the PTK-thallium iodide/lanthanum chloride mixture thus obtained and 30.0 g of naphthalene were charged into an autoclave, and the reaction was carried out in the same manner as in Example 2, and the product was analyzed in the same manner. As a result, the yield of the target product, naphthalene-2,6-dicarboxylic acid salt, was 11 mol% based on the amount of PTK charged.
実施例６
ＰＴＫにヨウ化タリウムをこのＰＴＫに対して１６モル
％添加し、ボールミルで粉砕混合した。Example 6 Thallium iodide was added to PTK in an amount of 16 mol % based on the PTK, and the mixture was ground and mixed in a ball mill.
この様にして得られたＰＴＫ−ヨウ化タリウム混合物１
０．０ｇとジフェニレンオキサイド３０．０ｇとをオー
トクレーブに仕込み、１００℃に加熱した。オートクレ
ーブ内を炭酸ガスで置換した後、炭酸ガスを４０ ｋｇ
／ ｃｒｔ−Ｇの圧力まで導入した。PTK-thallium iodide mixture 1 obtained in this way
0.0 g and 30.0 g of diphenylene oxide were placed in an autoclave and heated to 100°C. After replacing the inside of the autoclave with carbon dioxide gas, 40 kg of carbon dioxide gas was added.
/ crt-G pressure was introduced.
次に、オートクレーブ内の混合物を攪拌しながら、５°
（：：／ｍｉｎ、の速度で４３０°Ｃまで昇温させ、そ
の温度で１８時間攪拌を継続した。Next, while stirring the mixture in the autoclave,
The temperature was raised to 430°C at a rate of (::/min), and stirring was continued at that temperature for 18 hours.
反応終了後、反応混合物にトルエン２００ｄ及び水２０
０ｄを加えてよく攪拌し、水層並びにトルエン層のいず
れにも不溶な固体を濾別した後、水層を分離した。After the reaction is complete, add 200 d of toluene and 20 d of water to the reaction mixture.
After adding 0d and stirring thoroughly, solids insoluble in both the aqueous layer and the toluene layer were filtered off, and the aqueous layer was separated.
得られた水層を塩酸で酸析し、得られた酸析物のジフェ
ニレンオキサイドカルボン酸類とベンゼンカルボン酸類
との混合物をカラムクロマトグラフィー（充填剤：５ｅ
ｐｈａｄｅｘ ＬＨ−２０）で分離精製し、０．４９ｇ
のジフェニレンオキサイド−２，４，６，８−テトラカ
ルボン酸を得た。The resulting aqueous layer was precipitated with hydrochloric acid, and the resulting acid precipitate, a mixture of diphenylene oxide carboxylic acids and benzene carboxylic acids, was subjected to column chromatography (filling material: 5e).
phadex LH-20) and 0.49g
Diphenylene oxide-2,4,6,8-tetracarboxylic acid was obtained.
実施例７
Ａｒとしてジフェニレンオキサイドに代えてフェナンス
レンを使用した以外は、上記実施例６と同様にして反応
を行い、また、後処理を行って０゜１７ｇのフェナンス
レン−２，７−ジカルボン酸を得た。Example 7 The reaction was carried out in the same manner as in Example 6 above, except that phenanthrene was used instead of diphenylene oxide as Ar, and post-treatment was performed to produce 0.17 g of phenanthrene-2,7-dicarboxylic acid. Obtained.
実施例８
Ａｒとしてジフェニレンオキサイドに代えてカルバゾー
ルを使用した以外は、上記実施例６と同様にして反応を
行い、また、後処理を行って１゜４４ｇのカルバゾール
−１，３，６，８−ジカルボン酸を得た。Example 8 The reaction was carried out in the same manner as in Example 6 above, except that carbazole was used instead of diphenylene oxide as Ar, and 1°44 g of carbazole-1,3,6,8 was post-treated. -Dicarboxylic acid was obtained.
実施例９
ピロメリット酸テトラカリウム塩にヨウ化タリウムをこ
のテトラカリウム塩に対して１６モル％及びヨウ化タリ
ウムをこのテトラカリウム塩に対して１００モル％添加
し、ボールミルで粉砕混合した。Example 9 To a tetrapotassium pyromellitic acid salt, 16 mol % of thallium iodide and 100 mol % of thallium iodide, based on the tetrapotassium salt, were added, and the mixture was ground and mixed using a ball mill.
この様にして得られた混合物１０．０ｇとナフタレン３
０．０ｇとをオートクレーブに仕込み、１００°Ｃに加
熱した。オートクレーブ内を炭酸ガスで置換した後、炭
酸ガスを４０に、ｇ／Ｃｒｌ・Ｇの圧力まで導入した。10.0 g of the mixture thus obtained and 3 naphthalene
0.0g was placed in an autoclave and heated to 100°C. After replacing the inside of the autoclave with carbon dioxide gas, carbon dioxide gas was introduced to a pressure of 40 g/Crl.G.
次に、オートクレーブ内の混合物を攪拌しながら、５°
Ｃ／ｍｉｎ、の速度で４５０°Ｃまで昇温させ、その温
度で１時間攪拌を継続した。Next, while stirring the mixture in the autoclave,
The temperature was raised to 450° C. at a rate of C/min, and stirring was continued at that temperature for 1 hour.
反応終了後、反応混合物にトルエン２００Ｔｔｌ及び水
２００！ｎｌを加えてよく攪拌し、水層並びにトルエン
層のいずれにも不溶な固体を濾別した後、水層を分離し
た。After the reaction is completed, 200 Ttl of toluene and 200 Ttl of water are added to the reaction mixture. After adding nl and stirring well, solids that were insoluble in both the aqueous layer and the toluene layer were filtered off, the aqueous layer was separated.
得られた水層の一部を採取し、高速液体クロマトグラフ
ィを用いて内部標準法で生成したナフタレン−２，３，
６，７−テトラカルボン酸塩を定量した結果、ピロメリ
ット酸テトラカリウム塩仕込量を基準とする収率が８モ
ル％であった。A part of the obtained aqueous layer was collected, and naphthalene-2,3, which was generated using an internal standard method using high-performance liquid chromatography, was
As a result of quantifying the 6,7-tetracarboxylic acid salt, the yield was 8 mol% based on the amount of pyromellitic acid tetrapotassium salt charged.
本発明では、触媒としてタリウム化合物を使用すること
により、比較的穏やかな反応条件で芳香族カルボン酸又
はその塩を収率良く製造することができ、その結果、芳
香族カルボン酸類を低圧で安全かつ安価に製造すること
ができる。さらに、触媒として（ａ）タリウム化合物と
（ｂｌ Ｉ ａ族金属、■ａａ族金属びＩｆＩａ族金属
の化合物からなる群から選ばれた１種又は２種以上の化
合物とを併用使用することにより、触媒作用がより一層
向上し、比較的穏やかな反応条件で芳香族カルボン酸又
は−１−の塩を収率良く製造することができる。また、
本発明の触媒を使用することにより、カルボキシル基を
芳香族化合物間で分子間移動させることができる。In the present invention, by using a thallium compound as a catalyst, aromatic carboxylic acids or salts thereof can be produced in high yield under relatively mild reaction conditions, and as a result, aromatic carboxylic acids can be produced safely and at low pressure. It can be manufactured at low cost. Furthermore, by using (a) a thallium compound as a catalyst in combination with one or more compounds selected from the group consisting of compounds of group Ia metals, group II aa metals, and group IfIa metals, The catalytic action is further improved, and the aromatic carboxylic acid or -1- salt can be produced in good yield under relatively mild reaction conditions.
By using the catalyst of the present invention, carboxyl groups can be transferred intermolecularly between aromatic compounds.
Claims (6)
カルボン酸塩とを、タリウム化合物を存在させて炭酸ガ
ス加圧下に加熱し、反応させることを特徴とする上記芳
香族化合物を母核とするカルボン酸又はその塩の製造方
法。(1) An aromatic compound having no carboxyl group and an aromatic carboxylate salt are heated under pressure of carbon dioxide in the presence of a thallium compound to cause the aromatic compound to react with the above-mentioned aromatic compound as a core. Method for producing carboxylic acid or its salt.
カルボキシル基を有しない芳香族化合物と芳香族カルボ
ン酸又はその塩とを、タリウム化合物を存在させて炭酸
ガス加圧下に加熱し、反応させることを特徴とするカル
ボキシル基の分子間移動方法。(2) has one or more substitutable nuclear-bonded hydrogens, and
A method for intermolecular transfer of a carboxyl group, which comprises heating an aromatic compound having no carboxyl group and an aromatic carboxylic acid or a salt thereof under pressure of carbon dioxide in the presence of a thallium compound to react.
ボキシル基を芳香族化合物間で分子間移動させるための
触媒。(3) A catalyst for intermolecular transfer of carboxyl groups between aromatic compounds, which is characterized by containing a thallium compound.
カルボン酸塩とを、（ａ）タリウム化合物及び（ｂ）
I ａ族金属、IIａ族金属及びIIIａ族金属の化合物から
なる群から選ばれた１種又は２種以上の化合物を存在さ
せて炭酸ガス加圧下に加熱し、反応させることを特徴と
する上記芳香族化合物を母核とするカルボン酸又はその
塩の製造方法。(4) An aromatic compound having no carboxyl group and an aromatic carboxylate are combined into (a) a thallium compound and (b)
The above-mentioned aromatic aroma, which is characterized in that one or more compounds selected from the group consisting of compounds of Group Ia metals, Group IIa metals, and Group IIIa metals are present, heated under pressure of carbon dioxide gas, and reacted. A method for producing a carboxylic acid or a salt thereof using a group compound as a core.
カルボキシル基を有しない芳香族化合物と芳香族カルボ
ン酸又はその塩とを、（ａ）タリウム化合物及び（ｂ）
I ａ族金属、IIａ族金属及びIIIａ族金属の化合物から
なる群から選ばれた１種又は２種以上の化合物を存在さ
せて炭酸ガス加圧下に加熱し、反応させることを特徴と
するカルボキシル基の分子間移動方法。(5) has one or more substitutable nuclear-bonded hydrogen, and
An aromatic compound having no carboxyl group and an aromatic carboxylic acid or its salt are combined into (a) a thallium compound and (b)
A carboxyl group characterized by reacting by heating under pressure of carbon dioxide gas in the presence of one or more compounds selected from the group consisting of compounds of Group Ia metals, Group IIa metals, and Group IIIa metals. Intermolecular transfer method.
IIａ族金属及びIIIａ族金属の化合物からなる群から選
ばれた１種又は２種以上の化合物を含有することを特徴
とするカルボキシル基を芳香族化合物間で分子間移動さ
せるための触媒。(6) (a) thallium compound and (b) Group Ia metal,
A catalyst for intermolecular transfer of carboxyl groups between aromatic compounds, characterized by containing one or more compounds selected from the group consisting of compounds of group IIa metals and group IIIa metals.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US361,180 | 1982-03-24 | ||
| US07/361,180 US5081252A (en) | 1988-06-06 | 1989-06-05 | Process for the preparation of aromatic carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03128346A true JPH03128346A (en) | 1991-05-31 |
Family
ID=23420978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2139692A Pending JPH03128346A (en) | 1989-06-05 | 1990-05-31 | Production of aromatic carboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03128346A (en) |
-
1990
- 1990-05-31 JP JP2139692A patent/JPH03128346A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3390169B2 (en) | Method for producing 2,6-naphthalenedicarboxylic acid | |
| JPH03128346A (en) | Production of aromatic carboxylic acids | |
| JP2002097168A (en) | Method for producing aromatic tetracarboxylic acid | |
| DE68904599T2 (en) | AROMATIC CARBONIC ACIDS. | |
| JPH03130247A (en) | Production of aromatic carboxylic acid | |
| CA2551446A1 (en) | Carboxylation of aromatic hydrocarbons to produce aromatic carboxylic acids | |
| JP2002097185A (en) | Method for producing aromatic tetracarboxylic dianhydride | |
| JPH0334979B2 (en) | ||
| JP2003508367A (en) | Process for producing aromatic dibasic acid in one step using a single catalyst system | |
| JPH023777B2 (en) | ||
| JP2003525215A (en) | Alkylcarboxylates as solvents for Henkel-related processes | |
| JP2003521480A (en) | Carboxylation of hydrocarbons to terephthalic acid or naphthalenedicarboxylic acid | |
| JPH03255049A (en) | Preparation of biphenylcarboxylic acid | |
| JP3264733B2 (en) | Method for producing 4-biphenylcarboxylic acid | |
| EP1210311B1 (en) | A process for carboxylation of naphthoic acid to naphthalene dicarboxylic acid | |
| JPH02149573A (en) | Diphenylene oxide-2,4,6,8-tetracarboxylic acid | |
| JP2004321889A (en) | Method for recovering catalyst from slurry and method for producing aromatic carboxylic acid | |
| US6479699B2 (en) | Process for carboxylation of naphthoic acid to naphthalene dicarboxylic acid | |
| US6441224B1 (en) | Process for carboxylation of naphthoic acid to naphthalene dicarboxylic acid | |
| JPH05286967A (en) | Dibenzothiophenetetracarboxylic acid and its production | |
| JPH03284648A (en) | Method for industrially producing naphthalene-2,6-dicarboxylic acid | |
| JPS62106035A (en) | Production of terephthalic acid and phenol | |
| JP2003508365A (en) | Production of diacids by carboxylation of phenolic compounds | |
| JPH06271501A (en) | Production of naphthalenepolycarboxylic acid | |
| JP2003342227A (en) | Method for producing biphenyltetracarboxylic acid |