JP2546992B2 - Method for producing cyclic dihydroxydicarboxylic acid - Google Patents
Method for producing cyclic dihydroxydicarboxylic acidInfo
- Publication number
- JP2546992B2 JP2546992B2 JP61235281A JP23528186A JP2546992B2 JP 2546992 B2 JP2546992 B2 JP 2546992B2 JP 61235281 A JP61235281 A JP 61235281A JP 23528186 A JP23528186 A JP 23528186A JP 2546992 B2 JP2546992 B2 JP 2546992B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- cyclic
- dihydroxydicarboxylic
- producing
- reaction
- 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 - Lifetime
Links
- 239000002253 acid Substances 0.000 title claims description 32
- 125000004122 cyclic group Chemical group 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003054 catalyst Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- 150000008378 aryl ethers Chemical class 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims 1
- 229960001826 dimethylphthalate Drugs 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011964 heteropoly acid Substances 0.000 description 5
- IMRVRTDYOOJNHM-UHFFFAOYSA-N 4,5-dihydroxycyclohexane-1,2-dicarboxylic acid Chemical compound OC1CC(C(O)=O)C(C(O)=O)CC1O IMRVRTDYOOJNHM-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LWMIDUUVMLBKQF-UHFFFAOYSA-N 4-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC1CC=CC2C(=O)OC(=O)C12 LWMIDUUVMLBKQF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- CYYKNXGBUPVFHG-UHFFFAOYSA-N 4,5-dihydroxy-3-methylcyclohexane-1,2-dicarboxylic acid Chemical compound CC1C(O)C(O)CC(C(O)=O)C1C(O)=O CYYKNXGBUPVFHG-UHFFFAOYSA-N 0.000 description 1
- PGGASBAOLMMPHM-UHFFFAOYSA-N 5-chloro-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CC(Cl)CC2C(=O)OC(=O)C12 PGGASBAOLMMPHM-UHFFFAOYSA-N 0.000 description 1
- JDBDDNFATWXGQZ-UHFFFAOYSA-N 5-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CC(C)CC2C(=O)OC(=O)C12 JDBDDNFATWXGQZ-UHFFFAOYSA-N 0.000 description 1
- -1 Alkali metal salts Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000007039 two-step reaction Methods 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、環状不飽和二塩基酸無水物及び／又はその
有水酸をジオール化して環状ジヒドロキシジカルボン酸
を製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a cyclic dihydroxydicarboxylic acid by diolifying a cyclic unsaturated dibasic acid anhydride and / or its hydrous acid.
［従来の技術］ 環状不飽和二塩基酸のジオール化については、その二
重結合を臭素化した後、鹸化分解する方法（例えば、Ch
em.Abstr.,59,7382e（1963））、又は一旦無水酸の状態
でエポキシ化した化合物を酸で加水分解する方法（例え
ばChem.Abstr.,78,57600k（1973））等が知られてい
る。[Prior Art] Regarding the diolation of a cyclic unsaturated dibasic acid, a method in which the double bond is brominated and then saponified and decomposed (for example, Ch
em.Abstr., 59 , 7382e (1963)), or a method of hydrolyzing an epoxidized compound with an acid once with an acid (eg Chem.Abstr., 78 , 57600k (1973)), etc. are known. There is.
［発明が解決しようとする問題点］ 臭素付加の方法は、高価で、しかも腐食性がある臭素
を使用しなければならず、等モル以上のアルカリを必要
とする。又、エポキシ化合物を用いる方法は、エポキシ
化合物を得るために高価な過酢酸や過安息香酸を用いな
ければならない。[Problems to be Solved by the Invention] In the bromine addition method, expensive and corrosive bromine must be used, and an equimolar or more alkali is required. Further, in the method using an epoxy compound, expensive peracetic acid or perbenzoic acid must be used to obtain the epoxy compound.
かくの如く、これらはいずれも高価な試薬を必要とす
るし、しかも二段反応であって、工業的に環状ジヒドロ
キシジカルボン酸を得る方法としては満足できるもので
はない。As described above, all of these require expensive reagents and are two-step reactions, which are not satisfactory as methods for industrially obtaining cyclic dihydroxydicarboxylic acids.
本発明者らは、係る欠点を解消し、工業的に有利な環
状ジヒドロキシジカルボン酸の製造法を確立すべく鋭意
検討の結果、酸化剤として過酸化水素を使用し、特定の
触媒を用いることにより、環状不飽和二塩基酸無水物及
び／又はその有水酸から、環状ジヒドロキシジカルボン
酸が一段反応でかつ高収率で得られることを見い出し、
この知見に基づいて本発明を完成した。The present inventors have made extensive studies to eliminate such drawbacks and establish an industrially advantageous method for producing a cyclic dihydroxydicarboxylic acid. As a result, hydrogen peroxide is used as an oxidant and a specific catalyst is used. Found that a cyclic dihydroxydicarboxylic acid can be obtained in a high yield in a one-step reaction from a cyclic unsaturated dibasic acid anhydride and / or its hydrous acid,
The present invention has been completed based on this finding.
即ち、本発明は、一般式（１）で表される環状二塩基
酸無水物及び／又はその有水酸に対し、過酸化水素を作
用させて環状ジヒドロキシカルボン酸を製造するに際
し、リンタングステン酸ケイタングステン酸及びリンモ
リブデン酸からなる群から選ばれる１種若しくは２種以
上の触媒の存在下、反応溶媒中でジオール化することを
特徴とするヒドロキシカルボン酸の製造法を提供するこ
とを第１の目的とする。That is, the present invention is a method for producing cyclic dihydroxycarboxylic acid by reacting cyclic dibasic acid anhydride represented by the general formula (1) and / or its hydrous acid with hydrogen peroxide. To provide a method for producing a hydroxycarboxylic acid, which comprises diol-forming in a reaction solvent in the presence of one or more catalysts selected from the group consisting of silicotungstic acid and phosphomolybdic acid. The purpose of.
［式中、Ｒは水素原子、メチル基又は塩基原子を表
す。］ 更に引続く検討の中で、上記のヘテロポリ酸を触媒と
した場合には、特定の溶媒を使用することにより容易に
反応生成物の精製及び／又は触媒の分離・回収をなし得
ることを見い出し、この知見に基づいて本発明を完成し
た。 [In the formula, R represents a hydrogen atom, a methyl group or a base atom. In a further study, it was found that when the above-mentioned heteropolyacid was used as a catalyst, the reaction product could be easily purified and / or the catalyst could be separated and recovered by using a specific solvent. The present invention has been completed based on this finding.
即ち、本発明は、上記のジオール化反応後、水又は脂
肪族、脂環族若しくは芳香族のエーテル、脂肪族、脂環
族若しくは芳香族のエステルよりなる群から選ばれる１
種若しくは２種以上の有機溶媒を用いて反応生成物を精
製し、且つ反応生成物に混在する触媒を分離することを
特徴とするヒドロキシカルボン酸の製造法を提供するこ
とを第２の目的とする。That is, the present invention is selected from the group consisting of water or an aliphatic, alicyclic or aromatic ether, an aliphatic, alicyclic or aromatic ester after the above diol formation reaction.
A second object is to provide a method for producing a hydroxycarboxylic acid, characterized in that the reaction product is purified using one kind or two or more kinds of organic solvents, and the catalyst mixed in the reaction product is separated. To do.
［問題点を解決するための手段］ 一般式（１）で表される環状二塩基酸無水物は、例え
ば無水マレイン酸とジエン類とのディールス・アルダー
反応により容易に得ることができる。当該ジエン類とし
ては、ブタジエン、ピペリレン、イソプレン、クロロプ
レン等が例示され、夫々テトラヒドロフタル酸無水物、
３−メチルテトラヒドロフタル酸無水物、４−メチルテ
トラヒドロフタル酸無水物、４−クロロテトラヒドロフ
タル酸無水物が得られる。[Means for Solving Problems] The cyclic dibasic acid anhydride represented by the general formula (1) can be easily obtained by, for example, a Diels-Alder reaction between maleic anhydride and dienes. Examples of the dienes include butadiene, piperylene, isoprene, chloroprene and the like, and tetrahydrophthalic anhydride,
3-Methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride and 4-chlorotetrahydrophthalic anhydride are obtained.
本発明に係る反応原料としては上記酸無水物の他、こ
れらの有水酸も使用できる。As the reaction raw material according to the present invention, in addition to the above acid anhydride, these hydrous acids can be used.
本発明に係る触媒は、リンタングステン酸、ケイタン
グステン酸及びリンモリブデン酸からなる群から選ばれ
る１種若しくは２種以上の触媒である。The catalyst according to the present invention is one or more catalysts selected from the group consisting of phosphotungstic acid, silicotungstic acid and phosphomolybdic acid.
リンタングステン酸としては、H3（PW12O40）やH6（P
2W18O62）やH7（PW11O33）なる構造式を有するものが例
示される。又、ケイタングステン酸としては、H4（SiW
12O40）なる構造式を有するものが例示される。更に、
リンモリブデン酸としては、H3（PMo12O40）やH7（PMo
11O39）やH6（P2Mo18O62）なる構造式を有するものが例
示される。上記に例示したこれらヘテロポリ酸はいずれ
も公知のものである。合成の容易さ又は入手の容易さの
観点からは、ヘテロ原子としてＰ又はSiを含有するヘテ
ロポリ酸が好ましく、特に 12−タングストリン酸（H3PW12O40）、 12−タングストケイ酸（H3SiW12O40）、 12−モリブドリン酸（H3PMo12O40）等がより好ましい。Examples of phosphotungstic acid include H 3 (PW 12 O 40 ) and H 6 (PW
2 W 18 O 62 ) and H 7 (PW 11 O 33 ) are structural examples. As silicotungstic acid, H 4 (SiW
One having a structural formula of 12 O 40 ) is exemplified. Furthermore,
As phosphomolybdic acid, H 3 (PMo 12 O 40 ) and H 7 (PMo
Examples thereof include those having a structural formula such as 11 O 39 ) or H 6 (P 2 Mo 18 O 62 ). All of these heteropolyacids exemplified above are known. From the viewpoint of ease of synthesis or availability, a heteropoly acid containing P or Si as a hetero atom is preferable, and particularly 12-tungstophosphoric acid (H 3 PW 12 O 40 ), 12-tungstosilicic acid (H 3 SiW 12 O 40 ), 12-molybdophosphoric acid (H 3 PMo 12 O 40 ) and the like are more preferable.
又、本発明に係るヘテロポリ酸は、水和物であっても
よく、更に、反応系内でヘテロポリ酸を生成し得る化合
物の形態であってもよい。このような化合物としては、
カリウム、ナトリウム等のアルカリ金属塩、コバルト、
ニッケル、マンガン、銅等の重金属塩、アンモニウム
（NH4）塩等の塩類が挙げられ、この場合、例えばリン
酸、塩酸、硫酸等の鉱酸を反応系内に加え、pH7以下の
酸性条件下で反応を行うことが好ましい。Further, the heteropolyacid according to the present invention may be a hydrate, or may be in the form of a compound capable of producing a heteropolyacid in the reaction system. Such compounds include:
Alkali metal salts such as potassium and sodium, cobalt,
Examples include heavy metal salts such as nickel, manganese, and copper, and salts such as ammonium (NH 4 ) salt. In this case, for example, mineral acids such as phosphoric acid, hydrochloric acid, and sulfuric acid are added to the reaction system under acidic conditions of pH 7 or less. It is preferable to carry out the reaction.
上記に例示した触媒は、単独で使用しても２種以上を
併用してもよい。The catalysts exemplified above may be used alone or in combination of two or more kinds.
反応性の面においては、タングステン酸系触媒はモリ
ブデン酸系触媒より優れる傾向にある。In terms of reactivity, the tungstic acid-based catalyst tends to be superior to the molybdic acid-based catalyst.
触媒の使用量は、反応原料に対し、0.01〜30重量％好
ましくは0.05〜５重量％であることが反応速度並びに触
媒に要する経費上有利である。The amount of the catalyst used is 0.01 to 30% by weight, preferably 0.05 to 5% by weight, based on the reaction raw materials, in terms of the reaction rate and the cost required for the catalyst.
当該反応に必要な過酸化水素の化学量論量は等モルで
あるが、実際には反応速度及び収率向上の観点よりその
５〜50％過剰に用いるのが望ましい。The stoichiometric amount of hydrogen peroxide required for the reaction is equimolar, but in practice it is desirable to use 5 to 50% excess thereof from the viewpoint of improving the reaction rate and yield.
反応温度は20〜120℃、好ましくは40〜90℃が適当で
ある。20℃未満の温度では反応速度が遅く、逆に120℃
を越える温度では過酸化水素が分解する傾向にあり好ま
しくない。The reaction temperature is 20 to 120 ° C, preferably 40 to 90 ° C. The reaction rate is slow at temperatures below 20 ° C, and conversely 120 ° C.
At a temperature exceeding 1, the hydrogen peroxide tends to decompose, which is not preferable.
反応溶媒としては、水が適当であるが、tert−ブタノ
ール、ジメチルホルムアミド、ジメチルスルホキシド等
の水溶性極性溶媒を用いてもよい。アセトン等のケトン
類は生成物とケタールを形成するため好ましくない。こ
の場合、反応系における原料の濃度は５〜70重量％、好
ましくは15〜50重量％である。Water is suitable as the reaction solvent, but a water-soluble polar solvent such as tert-butanol, dimethylformamide or dimethylsulfoxide may be used. Ketones such as acetone are not preferred because they form a ketal with the product. In this case, the concentration of the raw materials in the reaction system is 5 to 70% by weight, preferably 15 to 50% by weight.
一般的に、反応は所定の原料及び触媒を仕込み、所定
量の過酸化水素水溶液を添加しつつ、加熱撹拌下進行さ
せる。Generally, the reaction is carried out by charging a predetermined raw material and a catalyst, adding a predetermined amount of aqueous hydrogen peroxide solution, and heating and stirring.
引続く検討の中で、本発明に係るヘテロポリ酸類は、
過酸化水素が希薄あるいは存在しない状態においても水
あるいは極性有機溶媒に溶解していて、反応溶媒を留去
して濃縮すれば、目的物であるジヒドロキシジカルボン
酸は晶出し、又、触媒であるヘテロポリ酸は母液中に溶
存していることが判明した。この母液は生成物を多量に
溶解しているが、再度反応に供することが可能である。In the subsequent study, the heteropolyacids according to the present invention,
Even if hydrogen peroxide is diluted or absent, it is dissolved in water or a polar organic solvent, and if the reaction solvent is distilled off and concentrated, the target dihydroxydicarboxylic acid crystallizes, and the catalyst heteropoly The acid was found to be dissolved in the mother liquor. This mother liquor dissolves a large amount of the product, but can be reused for the reaction.
更に、それ等のヘテロポリ酸は優れた触媒能を保持し
つつ、水又は特定の有機溶媒により容易に抽出除去する
ことができるという驚くべき事実が判明し、この知見に
基づいて優れた精製工程を含む環状ジヒドロキシジカル
ボン酸の製造方法を確立した。Furthermore, the surprising fact that these heteropolyacids can be easily extracted and removed with water or a specific organic solvent while retaining excellent catalytic ability was found, and based on this finding, an excellent purification step was conducted. A method for producing a cyclic dihydroxydicarboxylic acid containing is established.
本発明に適用される特定の有機溶媒とは、脂肪族、脂
環族若しくは芳香族のエーテル、脂肪族、脂環族若しく
は芳香族のエステルよりなる群から選ばれる１種若しく
は２種以上の有機溶媒であり、具体的にはジエチルエー
テル、テトラヒドロフラン、ジオキサン、エチレングリ
コールジメチルエーテル、アニソール、ジフェニルエー
テル、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブ
チル、コハク酸ジメチル、アジピン酸ジメチル、安息香
酸メチル、ｏ−フタル酸ジメチル等が例示される。これ
等の有機溶媒は、生成物である環状ジヒドロシジカルボ
ン酸を溶解しない又は溶解性に乏しい一方で、当該反応
の副生成物であるラクトン類や二量化エステル類等を良
く溶解するという特徴を有しており、触媒の除去と同時
に反応生成物の精製を行うことができるという利点を有
する。The specific organic solvent applied to the present invention is one or more organic compounds selected from the group consisting of aliphatic, alicyclic or aromatic ethers, aliphatic, alicyclic or aromatic esters. Solvents, specifically diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, anisole, diphenyl ether, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, dimethyl succinate, dimethyl adipate, methyl benzoate, o-phthalate Examples include dimethyl acid and the like. These organic solvents are characterized in that they do not dissolve or have poor solubility in the product cyclic dihydrosidicarboxylic acid, while they dissolve the lactones and dimerized esters that are by-products of the reaction well. It has the advantage that the reaction product can be purified simultaneously with the removal of the catalyst.
係る有機溶媒の適用方法の具体例を以下に示す。 A specific example of the method of applying the organic solvent is shown below.
即ち、ヘテロポリ酸を触媒としてジオール化後、反応
溶媒の大部分を除去して得た反応生成物に有機溶媒を加
えて撹拌する。当該有機溶媒の添加量としては、反応原
料の仕込み重量／（反応原料の仕込み重量＋有機用媒の
仕込み重量）＝15〜50重量％を満足する量であることが
好ましい。このとき、生成物中に混在していた触媒等は
当該有機溶媒層に移行し、目的とする環状ジヒドロキシ
ジカルボン酸が析出する。撹拌中の温度は室温から溶媒
の沸点まで適宜選択できる。例えばジエチルエーテルで
は室温が好ましく、又、反応溶媒として水を用いた場合
に、酢酸エチルを加熱還流しながら撹拌すれば、水を共
沸脱水することにより除くことも可能である。That is, after a diol is formed using a heteropolyacid as a catalyst, most of the reaction solvent is removed, and an organic solvent is added to the reaction product obtained by stirring. The amount of the organic solvent added is preferably an amount satisfying the charged weight of the reaction raw material / (the charged weight of the reaction raw material + the charged weight of the organic medium) = 15 to 50% by weight. At this time, the catalyst and the like mixed in the product migrate to the organic solvent layer, and the target cyclic dihydroxydicarboxylic acid is deposited. The temperature during stirring can be appropriately selected from room temperature to the boiling point of the solvent. For example, diethyl ether is preferably used at room temperature, and when water is used as a reaction solvent, it can be removed by azeotropic dehydration of water by stirring ethyl acetate while heating under reflux.
［実施例］ 以下に実施例を示し、本発明を詳しく説明する。[Examples] The present invention will be described in detail below with reference to Examples.
実施例１ 500mlのガラス製４つ口フラスコにテトラヒドロフタ
ル酸無水物100g、水160g、リンタングステン酸（半井化
学薬品（株）製）0.33gを入れて、70℃で30％過酸化水
素水90gを滴下し、そのまま６時間反応させた。反応液
は終始均一であった。水の大部分を留去し、ジエチルエ
ーテル300mlを入れ、撹拌すると白色固体を生じた。こ
れを濾過、乾燥して4,5−ジヒドロキシシクロヘキサン
−1,2−ジカルボン酸112g（収率84モル％）を得た。こ
のものの中和価は540（理論値550）、隣接水酸基価は54
0（理論値550）であった。この固体をツボに入れ、燃焼
灰化させ、生成物のWO3含有量を測定したところ20ppmで
あった。Example 1 Tetrahydrophthalic anhydride 100 g, water 160 g, and phosphotungstic acid (manufactured by Hanai Chemical Co., Ltd.) 0.33 g were put into a 500 ml glass four-necked flask, and 30% hydrogen peroxide water 90 g at 70 ° C. Was added dropwise and the reaction was allowed to proceed for 6 hours. The reaction solution was homogeneous throughout. Most of the water was distilled off, 300 ml of diethyl ether was added, and the mixture was stirred to give a white solid. This was filtered and dried to obtain 112 g (yield 84 mol%) of 4,5-dihydroxycyclohexane-1,2-dicarboxylic acid. This product has a neutralization value of 540 (theoretical value of 550) and an adjacent hydroxyl value of 54.
It was 0 (theoretical value 550). This solid was put into a pot, burned and incinerated, and the WO 3 content of the product was measured and found to be 20 ppm.
実施例２ 実施例１と同様の反応器を用い、３−メチルテトラヒ
ドロフタル酸無水物110g、tert−ブタノール130g、ケイ
タングステン酸（半井化学薬品（株）製）0.40gを溶解
し、30％過酸化水素水90gを滴下した。65℃で14時間反
応後、tert−ブタノールと水とを留去した。酢酸エチル
200mlを加え、加熱しながら撹拌した。析出物を濾過、
乾燥して4,5−ジヒドロキシ−３−メチルシクロヘキサ
ン−1,2−ジカルボン酸114g（収率80モル％）を得た。
このものの中和価は493（理論値515）、隣接水酸基価は
496（理論値515）であった。実施例１と同様の操作で生
成物中のWO3含有量を測定したところ30ppmであった。Example 2 Using a reactor similar to that of Example 1, 110 g of 3-methyltetrahydrophthalic anhydride, 130 g of tert-butanol, and 0.40 g of silicotungstic acid (manufactured by Hanai Chemical Co., Ltd.) were dissolved to give a 30% excess. 90 g of hydrogen oxide water was added dropwise. After reacting at 65 ° C. for 14 hours, tert-butanol and water were distilled off. Ethyl acetate
200 ml was added and stirred with heating. The precipitate is filtered,
It was dried to obtain 114 g of 4,5-dihydroxy-3-methylcyclohexane-1,2-dicarboxylic acid (yield 80 mol%).
This product has a neutralization value of 493 (theoretical value of 515) and a neighboring hydroxyl value of
It was 496 (theoretical value 515). When the WO 3 content in the product was measured by the same operation as in Example 1, it was 30 ppm.
実施例３ 実施例１と同様な反応を行った後、水110gを減圧留去
した。これを加熱して均一溶液とした後、冷却して結晶
化させ、次いで濾過、乾燥して4,5−ジヒドロキシシク
ロヘキサン−1,2−ジカルボン酸80g（収率60モル％）を
得た。このものの中和価は540、隣接水酸基価は536であ
った。実施例１と同様の操作でWO3の含有量を測定した
ところ80ppmであった。Example 3 After performing the same reaction as in Example 1, 110 g of water was distilled off under reduced pressure. This was heated to a uniform solution, cooled to crystallize, then filtered and dried to obtain 4,5-dihydroxycyclohexane-1,2-dicarboxylic acid 80 g (yield 60 mol%). This product had a neutralization value of 540 and an adjacent hydroxyl value of 536. When the content of WO 3 was measured by the same operation as in Example 1, it was 80 ppm.
実施例４ 実施例１と同様の反応器にテトラヒドロフタル酸無水
物100g、水160g、リンモリブデン酸（半井化学薬品
（株）製）0.40g、30％過酸化水素水90gを入れ、80℃、
14時間反応させたところ、ガスクロマトグラフィー（内
部標準法）による4,5−ジヒドロキシシクロヘキサン−
1,2−ジカルボン酸の生成率は34モル％であった。Example 4 100 g of tetrahydrophthalic anhydride, 160 g of water, 0.40 g of phosphomolybdic acid (manufactured by Hanai Chemical Co., Ltd.), 90 g of 30% hydrogen peroxide were put in the same reactor as in Example 1, and the mixture was heated at 80 ° C.
After reacting for 14 hours, 4,5-dihydroxycyclohexane-by gas chromatography (internal standard method)
The production rate of 1,2-dicarboxylic acid was 34 mol%.
実施例５ 触媒としてリンモリブデン酸2.0gを使用した以外は実
施例４と同様の操作を行なったところ、ガスクロマトグ
ラフィー（内部標準法）による4,5−ジヒドロキシシク
ロヘキサン−1,2−ジカルボン酸の生成率は88モル％で
あった。Example 5 The same operation as in Example 4 was carried out except that 2.0 g of phosphomolybdic acid was used as a catalyst, whereby 4,5-dihydroxycyclohexane-1,2-dicarboxylic acid of 4,5-dihydroxycyclohexane-1,2-dicarboxylic acid obtained by gas chromatography (internal standard method) was analyzed. The production rate was 88 mol%.
［発明の効果］ 本発明方法によれば、高価な酸化剤を使うこともな
く、一段反応でしかも収率良く目的とする環状ジヒドロ
キシジカルボン酸を製造することができる。しかも本発
明に係る触媒を使用し、反応後水又は特定の有機溶媒を
使用することにより、経済的に触媒除去並びに生成物の
精製を行うとができる。[Effects of the Invention] According to the method of the present invention, the desired cyclic dihydroxydicarboxylic acid can be produced in a one-step reaction and in good yield without using an expensive oxidizing agent. Moreover, by using the catalyst according to the present invention and using water or a specific organic solvent after the reaction, it is possible to economically remove the catalyst and purify the product.
───────────────────────────────────────────────────── 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 51/367 Ｃ０７Ｃ 51/367 // 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 51/367 C07C 51/367 // C07B 61/00 300 C07B 61/00 300
Claims (6)
物及び／又はその有水酸に対し、過酸化水素を作用させ
て環状ジヒドロキシジカルボン酸を製造するに際し、リ
ンタングステン酸、ケイタングステン酸及びリンモリブ
デン酸からなる群から選ばれる１種若しくは２種以上の
触媒の存在下、反応溶媒中でジオール化することを特徴
とする環状ジヒドロキシジカルボン酸の製造法。 ［式中、Ｒは水素原子、メチル基又は塩基原子を表
す。］1. When producing cyclic dihydroxydicarboxylic acid by reacting hydrogen peroxide with cyclic dibasic acid anhydride represented by the general formula (1) and / or its hydrous acid, phosphotungstic acid, A process for producing a cyclic dihydroxydicarboxylic acid, which comprises diol-forming in a reaction solvent in the presence of one or more catalysts selected from the group consisting of silicotungstic acid and phosphomolybdic acid. [In the formula, R represents a hydrogen atom, a methyl group or a base atom. ]
範囲第１項に記載の環状ジヒドロキシジカルボン酸の製
造法。2. The method for producing a cyclic dihydroxydicarboxylic acid according to claim 1, wherein the reaction temperature is 20 to 120 ° C.
特許請求の範囲第１項又は第２項に記載の環状ジヒドロ
キシジカルボン酸の製造法。3. The method for producing a cyclic dihydroxydicarboxylic acid according to claim 1 or 2, wherein the reaction solvent is water or a water-soluble polar solvent.
／又はその有水酸の濃度が、５〜70重量部である特許請
求の範囲第１〜３項のいずれかの項に記載の環状ジヒド
ロキシジカルボン酸の製造法。4. The concentration of the cyclic dibasic acid anhydride and / or its hydrous acid in the reaction system is 5 to 70 parts by weight, according to any one of claims 1 to 3. Process for producing cyclic dihydroxydicarboxylic acid.
物及び／又はその有水酸に対し、過酸化水素を作用させ
て環状ジヒドロキシジカルボン酸を製造するに際し、リ
ンタングステン酸、ケイタングステン酸及びリンモリブ
デン酸からなる群から選ばれる１種若しくは２種以上の
触媒の存在下、反応溶媒中でジオール化し、その後、水
又は脂肪族若しくは芳香族のエーテル、脂肪族、脂環族
若しくは芳香族のエステルよりなる群から選ばれる１種
若しくは２種以上の有機溶媒を用いて反応生成物を精製
し、且つ反応生成物中に混在する触媒を分離することを
特徴とする環状ジヒドロキシジカルボン酸の製造法。 ［式中、Ｒは水素原子、メチル基又は塩基原子を表
す。］5. When producing cyclic dihydroxydicarboxylic acid by reacting hydrogen peroxide with cyclic dibasic acid anhydride represented by the general formula (1) and / or its hydrous acid, phosphotungstic acid, Diolization in a reaction solvent in the presence of one or more catalysts selected from the group consisting of silicotungstic acid and phosphomolybdic acid, and then water or an aliphatic or aromatic ether, aliphatic, or alicyclic Alternatively, a reaction product is purified by using one or more kinds of organic solvents selected from the group consisting of aromatic esters, and a catalyst mixed in the reaction product is separated. Acid manufacturing method. [In the formula, R represents a hydrogen atom, a methyl group or a base atom. ]
ドロフラン、ジオキサン、エチレングリコールジメチル
エーテル、アニソール、ジフェニルエーテル、酢酸メチ
ル、酢酸エチル、酢酸プロピル、酢酸ブチル、コハク酸
ジメチル、アジピン酸ジメチル、安息香酸メチル又はｏ
−フタル酸ジメチルである特許請求の範囲第５項に記載
の環状ジヒドロキシジカルボン酸の製造法。6. The organic solvent is diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, anisole, diphenyl ether, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, dimethyl succinate, dimethyl adipate, methyl benzoate or o.
A process for producing a cyclic dihydroxydicarboxylic acid according to claim 5, which is dimethyl phthalate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-222579 | 1985-10-04 | ||
| JP22257985 | 1985-10-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62174038A JPS62174038A (en) | 1987-07-30 |
| JP2546992B2 true JP2546992B2 (en) | 1996-10-23 |
Family
ID=16784679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61235281A Expired - Lifetime JP2546992B2 (en) | 1985-10-04 | 1986-10-02 | Method for producing cyclic dihydroxydicarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2546992B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4743060B2 (en) * | 2005-09-21 | 2011-08-10 | 住友化学株式会社 | Tungsten recovery method |
| US7993614B2 (en) | 2005-09-21 | 2011-08-09 | Sumitomo Chemical Company, Limited | Method for recovering tungsten |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4932521A (en) * | 1972-07-25 | 1974-03-25 | ||
| JPS49132015A (en) * | 1973-03-19 | 1974-12-18 | ||
| JPS591254B2 (en) * | 1976-01-08 | 1984-01-11 | 日本パ−オキサイド株式会社 | Production method of tartaric acid |
| JPS6094938A (en) * | 1983-10-28 | 1985-05-28 | Agency Of Ind Science & Technol | Hydroxy dibasic acid salt compound having cyclohexane ring and rustproofing agent composed thereof |
-
1986
- 1986-10-02 JP JP61235281A patent/JP2546992B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62174038A (en) | 1987-07-30 |
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