JPH10287627A - Production of 3-nitro-ortho-toluic acid - Google Patents
Production of 3-nitro-ortho-toluic acidInfo
- Publication number
- JPH10287627A JPH10287627A JP9193192A JP19319297A JPH10287627A JP H10287627 A JPH10287627 A JP H10287627A JP 9193192 A JP9193192 A JP 9193192A JP 19319297 A JP19319297 A JP 19319297A JP H10287627 A JPH10287627 A JP H10287627A
- Authority
- JP
- Japan
- Prior art keywords
- nitro
- reaction
- xylene
- acid
- bromide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- CCXSGQZMYLXTOI-UHFFFAOYSA-N 13506-76-8 Chemical compound CC1=CC=CC([N+]([O-])=O)=C1C(O)=O CCXSGQZMYLXTOI-UHFFFAOYSA-N 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- FVHAWXWFPBPFOS-UHFFFAOYSA-N 1,2-dimethyl-3-nitrobenzene Chemical group CC1=CC=CC([N+]([O-])=O)=C1C FVHAWXWFPBPFOS-UHFFFAOYSA-N 0.000 claims abstract description 51
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 19
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 4
- 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 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000000034 method Methods 0.000 claims description 28
- YPQAFWHSMWWPLX-UHFFFAOYSA-N 1975-50-4 Chemical compound CC1=C(C(O)=O)C=CC=C1[N+]([O-])=O YPQAFWHSMWWPLX-UHFFFAOYSA-N 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 7
- -1 aliphatic carboxylate Chemical class 0.000 claims description 7
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 4
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 claims description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 3
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 3
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 claims description 3
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 229940107816 ammonium iodide Drugs 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 3
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 125000005609 naphthenate group Chemical group 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 abstract 1
- 229910052740 iodine Inorganic materials 0.000 abstract 1
- 239000011630 iodine Substances 0.000 abstract 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 18
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 12
- 208000012839 conversion disease Diseases 0.000 description 11
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229940011182 cobalt acetate Drugs 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- VLKYKLNZVULGQK-UHFFFAOYSA-N 1,2-dimethyl-3,4-dinitrobenzene Chemical group CC1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1C VLKYKLNZVULGQK-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KFIRODWJCYBBHY-UHFFFAOYSA-N 3-nitrophthalic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1C(O)=O KFIRODWJCYBBHY-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
- CALQKRVFTWDYDG-UHFFFAOYSA-N butan-1-amine;hydroiodide Chemical compound [I-].CCCC[NH3+] CALQKRVFTWDYDG-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000005608 naphthenic acid group Chemical class 0.000 description 1
- 150000005526 organic bromine compounds Chemical class 0.000 description 1
- 150000005527 organic iodine compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は３−ニトロ−ｏ−ト
ルイル酸の製造方法に関する。より詳細には、３−ニト
ロ−ｏ−キシレン（即ち、１，２−ジメチル−３−ニト
ロベンゼン）を酸素又は酸素含有ガスで酸化して３−ニ
トロ−ｏ−トルイル酸を高選択的に製造する方法に関す
る。The present invention relates to a method for producing 3-nitro-o-toluic acid. More specifically, 3-nitro-o-xylene (ie, 1,2-dimethyl-3-nitrobenzene) is oxidized with oxygen or an oxygen-containing gas to produce 3-nitro-o-toluic acid with high selectivity. About the method.
【０００２】[0002]
【従来の技術】３−ニトロ−ｏ−トルイル酸は医薬など
の原料として有用な化合物である。これまでに３−ニト
ロ−ｏ−トルイル酸の製造法として、 （Ａ）３−ニトロ−ｏ−キシレンを硝酸酸化する方法
（米国特許第４０６５４７７号公報）； （Ｂ）３−ニトロ−ｏ−キシレンを過マンガン酸酸化す
る方法(Zhurnal Obschchei Khimii, Vol.60, No.10, p2
370)； などが提案されている。しかしながら、（Ａ）法は３−
ニトロ−ｏ−キシレンの転化率が低く、６−ニトロ−ｏ
−トルイル酸及びジニトロ−ｏ−キシレンなどが副生し
３−ニトロ−ｏ−トルイル酸の選択率が低いほか、反応
中多量のＮＯｘガスが発生するなどの問題点を有する方
法である。また（Ｂ）法は３−ニトロ−ｏ−キシレンの
転化率は高いが３−ニトロ−フタル酸及び６−ニトロ−
ｏ−トルイル酸などが多く副生し３−ニトロ−ｏ−トル
イル酸の選択率が低いほか、過マンガン酸カリウム水溶
液を多量に使用し、反応終了後に二酸化マンガンの沈殿
が析出しその処理をしなければならないといった問題点
を有する方法である。従って、３−ニトロ−ｏ−キシレ
ンから高選択的に３−ニトロ−ｏ−トルイル酸を得る経
済的な製造法の開発が望まれている。2. Description of the Related Art 3-Nitro-o-toluic acid is a compound useful as a raw material for medicines and the like. Heretofore, as a method for producing 3-nitro-o-toluic acid, (A) a method of oxidizing 3-nitro-o-xylene with nitric acid (U.S. Pat. No. 4,065,477); (B) a method of producing 3-nitro-o-xylene Method of permanganate oxidation (Zhurnal Obschchei Khimii, Vol. 60, No. 10, p2
370); and the like. However, method (A) is based on 3-
Low conversion of nitro-o-xylene, 6-nitro-o
In this method, selectivity of 3-nitro-o-toluic acid is low due to by-products of toluic acid and dinitro-o-xylene, and a large amount of NOx gas is generated during the reaction. In the method (B), conversion of 3-nitro-o-xylene is high, but 3-nitro-phthalic acid and 6-nitro-
A large amount of o-toluic acid and the like are produced as by-products and the selectivity for 3-nitro-o-toluic acid is low. In addition, a large amount of potassium permanganate aqueous solution is used, and after the reaction is completed, manganese dioxide precipitates and is treated. This method has a problem that it must be performed. Therefore, development of an economical production method of obtaining 3-nitro-o-toluic acid from 3-nitro-o-xylene with high selectivity is desired.
【０００３】[0003]
【発明が解決しようとする課題】３−ニトロ−ｏ−キシ
レンを酸化して３−ニトロ−ｏ−トルイル酸を得る製造
方法において、本発明者らは、目的物を高選択的に得ら
れる方法を開発することを目的として鋭意検討し、酸素
又は酸素含有ガスによる３−ニトロ−ｏ−キシレンの酸
化において、低級脂肪族カルボン酸系溶媒中で特定の触
媒系を使用して反応させることによって所期の目的が達
成されることを見いだし、本発明に到達した。即ち、本
発明は、３−ニトロ−ｏ−キシレンの酸化において、従
来の技術よりも高選択的に３−ニトロ−ｏ−トルイル酸
を得ることのできる３−ニトロ−ｏ−トルイル酸の製造
方法を提供することを目的とする。SUMMARY OF THE INVENTION In a method for producing 3-nitro-o-toluic acid by oxidizing 3-nitro-o-xylene, the inventors of the present invention provide a method for obtaining a target product with high selectivity. The purpose of the present invention is to study diligently for the purpose of developing the compound, and to carry out the reaction in the oxidation of 3-nitro-o-xylene with oxygen or an oxygen-containing gas by using a specific catalyst system in a lower aliphatic carboxylic acid-based solvent. It has been found that the objectives of the present invention are achieved, and the present invention has been achieved. That is, the present invention provides a method for producing 3-nitro-o-toluic acid, which can obtain 3-nitro-o-toluic acid more selectively than conventional techniques in the oxidation of 3-nitro-o-xylene. The purpose is to provide.
【０００４】[0004]
【課題を解決するための手段】上記の課題を解決するた
めになされた本発明の要旨は、 ３−ニトロ−ｏ−キシレンを低級脂肪族カルボン酸溶
媒又は低級脂肪族カルボン酸と有機溶媒との混合溶媒
中、重金属触媒と反応促進剤の存在下で、酸素又は酸素
含有ガスによって酸化し、３−ニトロ−ｏ−トルイル酸
を得ることを特徴とする３−ニトロ−ｏ−トルイル酸の
製造方法； ３−ニトロ−ｏ−キシレンに対して５〜１００重量倍
の酢酸、プロピオン酸及び／又は酪酸を使用する上記
記載の方法； 重金属触媒として、コバルト、マンガン、セリウム又
は銅の臭化物や水酸化物、これら重金属との炭酸塩、低
級脂肪族カルボン酸塩又はナフテン酸塩、及びこれら重
金属のアセチルアセトナートからなる群より選ばれた１
乃至２種以上を、３−ニトロ−ｏ−キシレンに対して
０．００５〜１．０モル倍使用する上記又は記載の
方法； 反応促進剤として、臭素、臭化水素、臭化コバルト、
臭化アンモニウム、アルカリ金属臭素化合物、テトラ−
ｎ−ブチルアンモニウムブロマイド、テトラブロムエタ
ン、ブロム酢酸及び臭化ベンジルからなる群より選ばれ
た１乃至２種以上、又はヨウ素、ヨウ化水素、ヨウ化ア
ンモニウム、アルカリ金属ヨウ素化合物及びテトラ−ｎ
−ブチルアンモニウムヨージドからなる群より選ばれた
１乃至２種以上を、重金属触媒に対して１．０〜３２重
量％使用する上記、又は記載の方法； 反応促進剤と併用して、ホルムアルデヒド、パラホル
ムアルデヒド、アセトアルデヒド、パラアルデヒド、プ
ロピオンアルデヒド、ブチルアルデヒド、ベンズアルデ
ヒド、クロロベンズアルデヒド、フルオロベンズアルデ
ヒド、ニトロベンズアルデヒドなどのアルデヒド類、ア
セトン、メチルエチルケトン、ジエチルケトン、ベンゾ
フェノンなどのケトン類、塩酸及びモノクロル酢酸から
なる群より選ばれた１乃至２種以上を３−ニトロ−ｏ−
キシレンに対して０．０１〜５．０モル倍使用する上記
、、又はに記載の方法；である。The gist of the present invention made in order to solve the above-mentioned problems is that 3-nitro-o-xylene is used as a solvent for a lower aliphatic carboxylic acid or a lower aliphatic carboxylic acid and an organic solvent. A process for producing 3-nitro-o-toluic acid, comprising oxidizing in a mixed solvent with oxygen or an oxygen-containing gas in the presence of a heavy metal catalyst and a reaction accelerator to obtain 3-nitro-o-toluic acid. The above-mentioned method using acetic acid, propionic acid and / or butyric acid in an amount of 5 to 100 times by weight relative to 3-nitro-o-xylene; bromide or hydroxide of cobalt, manganese, cerium or copper as a heavy metal catalyst; , Selected from the group consisting of carbonates with these heavy metals, lower aliphatic carboxylates or naphthenates, and acetylacetonates of these heavy metals.
Or a method as described above or in which two or more kinds are used in an amount of 0.005 to 1.0 mol times based on 3-nitro-o-xylene; as a reaction accelerator, bromine, hydrogen bromide, cobalt bromide,
Ammonium bromide, alkali metal bromine compound, tetra-
One or more kinds selected from the group consisting of n-butylammonium bromide, tetrabromoethane, bromoacetic acid and benzyl bromide, or iodine, hydrogen iodide, ammonium iodide, an alkali metal iodine compound and tetra-n
The above-mentioned or the above-mentioned method, wherein 1 to 2 or more kinds selected from the group consisting of -butylammonium iodide are used in an amount of 1.0 to 32% by weight with respect to the heavy metal catalyst; From the group consisting of aldehydes such as paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, chlorobenzaldehyde, fluorobenzaldehyde, nitrobenzaldehyde, ketones such as acetone, methyl ethyl ketone, diethyl ketone, benzophenone, hydrochloric acid and monochloroacetic acid One or more selected ones are 3-nitro-o-
The method described in the above or the above, which is used in an amount of 0.01 to 5.0 times by mole to xylene.
【０００５】[0005]
【発明の実施の形態】本発明は上記の構成からなり、本
発明の方法は下記の反応式で示され、その基本的操作
は、３−ニトロ−ｏ−キシレン（１）を低級脂肪族カル
ボン酸系溶媒中で、触媒及び反応促進剤の存在下で酸素
又は酸素含有ガスと接触させ、３−ニトロ−ｏ−トルイ
ル酸（２）を得ることからなる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention has the above constitution, and the method of the present invention is represented by the following reaction formula. The basic operation is as follows: 3-nitro-o-xylene (1) Contacting with oxygen or an oxygen-containing gas in an acid solvent in the presence of a catalyst and a reaction accelerator to obtain 3-nitro-o-toluic acid (2).
【０００６】[0006]
【化１】 Embedded image
【０００７】本発明の方法において、溶媒としては、低
級脂肪族カルボン酸又は低級脂肪族カルボン酸と有機溶
媒との混合溶媒が使用される。低級脂肪族カルボン酸と
しては、酢酸、プロピオン酸、酪酸などが例示され、工
業的には酢酸が最も有利である。低級脂肪族カルボン酸
の使用量は３−ニトロ−ｏ−キシレンの５〜１００重量
倍、好ましくは２５〜６０重量倍の範囲で用いられる。
低級脂肪族カルボン酸の使用量が５重量倍以下の場合
は、酸化速度が小さく３−ニトロ−ｏ−キシレンの転化
率が低下する。一方低級脂肪族カルボン酸の使用量が１
００重量倍以上の場合は３−ニトロ−ｏ−キシレンの転
化率が低下すると共に生産性を低下させる原因となる。In the method of the present invention, a lower aliphatic carboxylic acid or a mixed solvent of a lower aliphatic carboxylic acid and an organic solvent is used as the solvent. Examples of the lower aliphatic carboxylic acid include acetic acid, propionic acid, and butyric acid, and acetic acid is most advantageous industrially. The lower aliphatic carboxylic acid is used in an amount of 5 to 100 times by weight, preferably 25 to 60 times by weight of 3-nitro-o-xylene.
When the amount of the lower aliphatic carboxylic acid used is not more than 5 times by weight, the oxidation rate is small and the conversion of 3-nitro-o-xylene decreases. On the other hand, the amount of lower aliphatic carboxylic acid used is 1
If the amount is more than 00 times by weight, the conversion of 3-nitro-o-xylene decreases and the productivity decreases.
【０００８】本発明の方法は、低級脂肪族カルボン酸と
有機溶媒との混合溶媒中で行うこともできる。低級脂肪
族カルボン酸としては上記の化合物が例示され、また有
機溶媒としては、例えば、テトラヒドロフラン、ジオキ
サン、塩化メチレン、ジメチルホルムアミドなどが例示
できる。低級脂肪族カルボン酸に対する有機溶媒の混合
比は、反応に悪影響を及ぼさない範囲であれば適宜選択
できるが、低級脂肪族カルボン酸に対して等容量以下と
するのが好ましい。３−ニトロ−ｏ−キシレンに対する
当該混合溶媒の使用量は、上述の低級脂肪族カルボン酸
を使用したときの条件を参照することができる。[0008] The method of the present invention can also be carried out in a mixed solvent of a lower aliphatic carboxylic acid and an organic solvent. Examples of the lower aliphatic carboxylic acid include the above compounds, and examples of the organic solvent include tetrahydrofuran, dioxane, methylene chloride, dimethylformamide and the like. The mixing ratio of the organic solvent to the lower aliphatic carboxylic acid can be appropriately selected as long as it does not adversely affect the reaction, but is preferably equal to or less than the lower aliphatic carboxylic acid. As for the amount of the mixed solvent to be used with respect to 3-nitro-o-xylene, the conditions when the above-mentioned lower aliphatic carboxylic acid is used can be referred to.
【０００９】重金属触媒としては、前記反応式の反応を
進行させ得る重金属触媒であればいずれのものも使用す
ることができ、例えば、コバルト・マンガン・セリウム
・銅などの重金属との臭化物や水酸化物；これら重金属
との炭酸塩、低級脂肪族カルボン酸（例えば、酢酸、プ
ロピオン酸等）の塩、ナフテン酸の塩；及びこれら重金
属のアセチルアセトナートなどが例示できる。特に目的
物の選択性から酢酸コバルトを使用するのが好ましい。
なお、上記の重金属触媒は２種以上を併用してもよい。
３−ニトロ−ｏ−キシレンに対する重金属触媒の使用量
は、０．００５〜１．０モル倍、好ましくは０．１〜
０．８倍モル、より好ましくは０．３〜０．６モル倍が
用いられる。重金属触媒の使用量が０．００５モル倍未
満では十分な反応速度が得られず、また１．０モル倍を
越えると反応物の二酸化炭素への分解が増加傾向になる
とともに触媒費の負担が増加し経済的に不利である。な
お、後記のアルデヒド類などの反応促進助剤を使用する
場合には、重金属触媒の使用量を低減することができ
る。As the heavy metal catalyst, any heavy metal catalyst capable of promoting the reaction of the above-mentioned reaction formula can be used. For example, bromide or hydroxide with a heavy metal such as cobalt, manganese, cerium, or copper can be used. Substances; carbonates with these heavy metals, salts of lower aliphatic carboxylic acids (eg, acetic acid, propionic acid, etc.), salts of naphthenic acids; and acetylacetonates of these heavy metals. It is particularly preferable to use cobalt acetate from the selectivity of the target product.
The above heavy metal catalysts may be used in combination of two or more.
The amount of the heavy metal catalyst used relative to 3-nitro-o-xylene is 0.005 to 1.0 mol times, preferably 0.1 to 1.0 times.
0.8 times mole, more preferably 0.3 to 0.6 times mole is used. If the amount of the heavy metal catalyst used is less than 0.005 mole times, a sufficient reaction rate cannot be obtained, and if it exceeds 1.0 mole times, the decomposition of the reactants into carbon dioxide tends to increase and the burden on the catalyst cost increases. Increasing and economically disadvantageous. In the case where a reaction promoting aid such as aldehydes described below is used, the amount of the heavy metal catalyst used can be reduced.
【００１０】反応促進剤としては、臭素、臭化水素、臭
化コバルト、臭化アンモニウム、アルカリ金属臭素化物
（例えば、臭化ソーダ、臭化カリ等）などの無機臭素化
合物及びテトラ−ｎ−ブチルアンモニウムブロマイド、
テトラブロムエタン、ブロム酢酸、臭化ベンジルなどの
有機臭素化合物；ヨウ素、ヨウ化水素、ヨウ化アンモニ
ウム、アルカリ金属ヨウ素化合物（例えば、ヨウ化ソー
ダ、ヨウ化カリ等）などの無機ヨウ素化合物及びテトラ
−ｎ−ブチルアンモニウムヨージド、ヨード酢酸などの
有機ヨウ素化合物が例示され、特に目的物の選択性から
臭化ソーダを使用するのが好ましい。なお、上記の反応
促進剤は２種以上を併用してもよい。重金属触媒に対す
る反応促進剤の使用量は、重金属触媒に対して１．０〜
３２重量％、好ましくは５〜２０重量％、より好ましく
は９〜１８重量％が用いられる。反応促進剤の使用量
が、１．０重量％未満の場合は十分な効果が得られず、
また３２重量％を越えると反応促進剤による生成物の汚
染や経済的な負担が著しくなり、好ましくない。Examples of the reaction accelerator include inorganic bromine compounds such as bromine, hydrogen bromide, cobalt bromide, ammonium bromide, and alkali metal bromides (eg, sodium bromide, potassium bromide, etc.) and tetra-n-butyl. Ammonium bromide,
Organic bromine compounds such as tetrabromoethane, bromoacetic acid, and benzyl bromide; inorganic iodine compounds such as iodine, hydrogen iodide, ammonium iodide, and alkali metal iodine compounds (eg, sodium iodide, potassium iodide, etc.); Examples thereof include organic iodine compounds such as n-butylammonium iodide and iodoacetic acid, and it is particularly preferable to use sodium bromide in view of the selectivity of the target product. In addition, two or more of the above reaction accelerators may be used in combination. The amount of the reaction accelerator used for the heavy metal catalyst is 1.0 to 1.0 for the heavy metal catalyst.
32% by weight, preferably 5 to 20% by weight, more preferably 9 to 18% by weight is used. If the amount of the reaction accelerator is less than 1.0% by weight, a sufficient effect cannot be obtained,
On the other hand, if the content exceeds 32% by weight, contamination of the product by the reaction accelerator and economic burden become remarkable, which is not preferable.
【００１１】また、反応促進剤と併用して、反応促進助
剤として、例えば、ホルムアルデヒド、パラホルムアル
デヒド、アセトアルデヒド、パラアルデヒド、プロピオ
ンアルデヒド、ブチルアルデヒド、ベンズアルデヒド、
クロロベンズアルデヒド、フルオロベンズアルデヒド、
ニトロベンズアルデヒドなどのアルデヒド類；アセト
ン、メチルエチルケトン、ジエチルケトン、ベンゾフェ
ノンなどのケトン類；塩酸、モノクロル酢酸などの酸類
からなる群より選ばれた１乃至２種以上を使用すること
で、３−ニトロ−ｏ−キシレンに対する重金属触媒の使
用量を低減でき、重金属触媒の使用量が０．０１〜０．
１モル倍の範囲でも十分な反応速度が得られ、経済的に
も有利である。３−ニトロ−ｏ−キシレンに対する上記
アルデヒド類、ケトン類及び／又は酸類の使用量は、
０．０１〜５．０モル倍、好ましくは０．０５〜０．５
モル倍が用いられる。[0011] Further, in combination with a reaction accelerator, as a reaction accelerator, for example, formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, butyraldehyde, benzaldehyde,
Chlorobenzaldehyde, fluorobenzaldehyde,
Aldehydes such as nitrobenzaldehyde; ketones such as acetone, methyl ethyl ketone, diethyl ketone, and benzophenone; and one or more selected from the group consisting of acids such as hydrochloric acid and monochloroacetic acid, whereby 3-nitro-o is used. -The amount of the heavy metal catalyst used with respect to xylene can be reduced, and the amount of the heavy metal catalyst used is from 0.01 to 0.1.
A sufficient reaction rate can be obtained even in the range of 1 mole, which is economically advantageous. The amount of the aldehydes, ketones and / or acids used for 3-nitro-o-xylene is as follows:
0.01-5.0 mole times, preferably 0.05-0.5
Molar times are used.
【００１２】酸化剤として用いる酸素又は酸素含有ガス
としては、分子状酸素を含有するガスであればよく、純
酸素、又は空気その他の分子状酸素を含有するものが使
用でき、より工業的には通常の空気が好ましい。また、
酸素又は酸素含有ガスは常圧又は加圧状態で導入するこ
とができる。酵素又は酵素含有ガスの導入方法は、常圧
状態では反応液中へ吹き込む方法が最もよく、また加圧
状態では全反応圧力が１〜５０気圧の範囲、好ましくは
２〜１０気圧の範囲で、かつ反応容器からの排ガスの酸
素濃度が１〜８容量％の範囲になるように操作する方法
が好ましい。反応圧力が５０気圧を越えると、設備費と
酸素又は酸素含有ガスを圧縮するための動力費が増加す
るにもかかわらず、格別の利点が得られず、逆に二酸化
炭素への分解が増加傾向となって不利である。また排ガ
スの酸素濃度が８容量％を越えると、反応器気相部が爆
発性混合気体を形成する可能性が強くなり、安全対策面
から排ガスの酸素濃度は８容量％以下にする必要があ
る。酸素又は酸素含有ガスの導入量及び反応時間は、ク
ロマトグラフィー等の手段で反応の進行をチェックする
ことにより調整できる。反応温度は、使用する重金属触
媒の種類及び量、反応促進剤の種類及び量、反応促進剤
と併用するアルデヒド類、ケトン類、塩酸、モノクロル
酢酸などの種類及び量、酸素又は酸素含有ガスの導入方
法などに応じて適宜設定できるが、一般に７０〜２５０
℃の間で行われ、特に３−ニトロ−ｏ−キシレンの反応
性から１００〜１６０℃の間が好ましい。As the oxygen or oxygen-containing gas used as the oxidizing agent, any gas containing molecular oxygen may be used, and pure oxygen or air or other gas containing molecular oxygen can be used. Normal air is preferred. Also,
Oxygen or an oxygen-containing gas can be introduced at normal pressure or under pressure. The method of introducing an enzyme or an enzyme-containing gas is most preferably a method of blowing into a reaction solution under a normal pressure state, and a total reaction pressure in a pressure state of 1 to 50 atm, preferably 2 to 10 atm. In addition, a method is preferred in which the operation is performed so that the oxygen concentration of the exhaust gas from the reaction vessel is in the range of 1 to 8% by volume. If the reaction pressure exceeds 50 atm, despite the increase in equipment costs and the power cost for compressing oxygen or oxygen-containing gas, no particular advantage is obtained, and on the contrary, the decomposition into carbon dioxide tends to increase. This is disadvantageous. When the oxygen concentration of the exhaust gas exceeds 8% by volume, the possibility that the gas phase of the reactor forms an explosive mixed gas increases, and the oxygen concentration of the exhaust gas must be 8% by volume or less from the viewpoint of safety measures. . The introduced amount of oxygen or oxygen-containing gas and the reaction time can be adjusted by checking the progress of the reaction by means such as chromatography. The reaction temperature depends on the type and amount of the heavy metal catalyst used, the type and amount of the reaction accelerator, the type and amount of aldehydes, ketones, hydrochloric acid, monochloroacetic acid and the like used together with the reaction accelerator, and the introduction of oxygen or an oxygen-containing gas. Although it can be set appropriately according to the method and the like, it is generally 70 to 250.
C., and particularly preferably between 100 and 160.degree. C. due to the reactivity of 3-nitro-o-xylene.
【００１３】反応終了後、反応液から目的物を採取する
方法は、前述の先行文献などに記載された常法に準じて
行うことができ、例えば、反応液を濃縮し、アルカリ水
を添加した後、疎水性有機溶媒で抽出することにより未
反応物を回収し、次いでアルカリ水溶液を酸性にして、
目的物を酸析することにより行うことができる。なお、
回収した未反応物は再使用することができる。After completion of the reaction, the target substance can be collected from the reaction solution according to a conventional method described in the above-mentioned prior art. For example, the reaction solution is concentrated and alkali water is added. Thereafter, the unreacted product was recovered by extraction with a hydrophobic organic solvent, and then the alkaline aqueous solution was acidified,
It can be carried out by subjecting the target substance to acid precipitation. In addition,
The recovered unreacted material can be reused.
【００１４】[0014]
【発明の効果】本発明の方法は、３−ニトロ−ｏ−キシ
レンの酸素酸化という簡便な方法であり、反応液の後処
理が容易であると共に有害ガスの発生がないなどの利点
を有し、しかも高い選択率で３−ニトロ−ｏ−トルイル
酸を得ることができる。従って、本発明の方法によれ
ば、３−ニトロ−ｏ−トルイル酸を工業的且つ経済的に
製造することができる。The method of the present invention is a simple method of oxidizing 3-nitro-o-xylene with oxygen, and has advantages such as easy post-treatment of the reaction solution and no generation of harmful gas. In addition, 3-nitro-o-toluic acid can be obtained with high selectivity. Therefore, according to the method of the present invention, 3-nitro-o-toluic acid can be industrially and economically produced.
【００１５】[0015]
【実施例】以下、実施例により本発明を詳細に説明する
が、本発明は実施例に限定されるものではない。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples.
【００１６】実施例１ 還流冷却器と回転羽根撹拌機及び酸素ガス導入口を備え
た反応器に、３−ニトロ−ｏ−キシレン１．３８ｇ
（９．１ミリモル）、酢酸７２ｇ（３−ニトロ−ｏ−キ
シレンに対し５２重量倍）、酢酸コバルト四水和物１．
１３ｇ（４．５５ミリモル：３−ニトロ−ｏ−キシレン
に対して０．５モル倍）、臭化ソーダ０．１６ｇ（１．
５９ミリモル：酢酸コバルト四水和物に対して１４．２
重量％）を仕込み、反応温度１０４〜１０８℃の間で酸
素ガスを７時間かけて吹き込んで酸化反応を行った。得
られた反応液をH.P.L.C.分析にて確認したところ、以下
の反応結果となった。 反応転化率 ９５モル％ 反応生成率 ５３モル％(反応に用いた３−ニトロ−ｏ
−キシレンに対して) 選択率 ５６％（反応した３−ニトロ−ｏ−キシレ
ンに対して） 反応液を通常の方法で処理して、純度９９％以上の３−
ニトロ−ｏ−トルイル酸を０．６５ｇ（３．６１ミリモ
ル：収率４０モル％）得た。Example 1 1.38 g of 3-nitro-o-xylene was placed in a reactor equipped with a reflux condenser, a rotary blade stirrer and an oxygen gas inlet.
(9.1 mmol), 72 g of acetic acid (52 times the weight of 3-nitro-o-xylene), cobalt acetate tetrahydrate 1.
13 g (4.55 mmol: 0.5 mol times based on 3-nitro-o-xylene), 0.16 g of sodium bromide (1.
59 mmol: 14.2 based on cobalt acetate tetrahydrate
% By weight), and oxygen gas was blown in at a reaction temperature of 104 to 108 ° C. for 7 hours to carry out an oxidation reaction. When the obtained reaction solution was confirmed by HPLC analysis, the following reaction results were obtained. Reaction conversion rate 95 mol% Reaction production rate 53 mol% (3-nitro-o used in the reaction)
Selectivity 56% (relative to reacted 3-nitro-o-xylene) The reaction mixture was treated in the usual way to give 3-
0.65 g (3.61 mmol: yield 40 mol%) of nitro-o-toluic acid was obtained.
【００１７】比較例１ 前述の米国特許第４０６５４７７号公報に基づき３−ニ
トロ−ｏ−キシレンの硝酸酸化を追試した。５０％硝酸
水溶液７５ｇ（５９５ミリモル）中に３−ニトロ−ｏ−
キシレンを７．６ｇ（５０ミリモル）添加し、１１０℃
まで昇温した後２４時間保温し反応を行った。得られた
反応液をH.P.L.C.分析にて確認したところ、以下の反応
結果となった。 反応転化率 ６５モル％ 反応生成率 ２４モル％(反応に用いた３−ニトロ−ｏ
−キシレンに対して) 選択率 ３７％（反応した３−ニトロ−ｏ−キシレ
ンに対して）Comparative Example 1 The nitric acid oxidation of 3-nitro-o-xylene was repeated based on the aforementioned US Pat. No. 4,065,477. 3-nitro-o- in 75 g (595 mmol) of a 50% aqueous nitric acid solution
7.6 g (50 mmol) of xylene was added, and 110 ° C.
Then, the reaction was carried out by keeping the temperature for 24 hours. When the obtained reaction solution was confirmed by HPLC analysis, the following reaction results were obtained. Reaction conversion rate 65 mol% Reaction production rate 24 mol% (3-nitro-o used in the reaction)
Selectivity 37% (relative to 3-nitro-o-xylene reacted)
【００１８】比較例２ 前述の文献(Zhurnal Obschchei Khimii, Vol.60, No.1
0, p2370)に基づき３−ニトロ−ｏ−キシレンの過マン
ガン酸酸化を追試した。３．２％過マンガン酸カリウム
水溶液３１０ｇ（６３．２ミリモル）に３−ニトロ−ｏ
−キシレンを２．４ｇ（１５．８ミリモル）、セチルト
リメチルアンモニウムブロマイド１．０ｇ（２．７３ミ
リモル）を添加し、７５℃まで昇温した後４時間保温し
反応を行った。得られた反応液をH.P.L.C.分析にて確認
したところ、以下の反応結果となった。 反応転化率 ９９モル％ 反応生成率 ３６モル％(反応に用いた３−ニトロ−ｏ
−キシレンに対して) 選択率 ３６％（反応した３−ニトロ−ｏ−キシレ
ンに対して）Comparative Example 2 The aforementioned document (Zhurnal Obschchei Khimii, Vol. 60, No. 1)
0, p2370), the permanganate oxidation of 3-nitro-o-xylene was repeated. 3-nitro-o was added to 310 g (63.2 mmol) of a 3.2% aqueous potassium permanganate solution.
2.4 g (15.8 mmol) of xylene and 1.0 g (2.73 mmol) of cetyltrimethylammonium bromide were added, and the temperature was raised to 75 ° C., and the reaction was carried out by keeping the temperature for 4 hours. When the obtained reaction solution was confirmed by HPLC analysis, the following reaction results were obtained. Conversion rate of reaction: 99 mol% Reaction production rate: 36 mol% (3-nitro-o used in the reaction)
Selectivity 36% (relative to 3-nitro-o-xylene reacted)
【００１９】実施例２ 溶媒を酢酸から酪酸に代え、また反応温度を１０８℃か
ら１４０℃に上げる以外は実施例１と同様にして反応を
行い、得られた反応液をH.P.L.C.分析にて確認したとこ
ろ、以下の反応結果となった。 反応転化率 ９１モル％ 反応生成率 ５１モル％(反応に用いた３−ニトロ−ｏ
−キシレンに対して) 選択率 ５６％（反応した３−ニトロ−ｏ−キシレ
ンに対して）Example 2 A reaction was carried out in the same manner as in Example 1 except that the solvent was changed from acetic acid to butyric acid, and the reaction temperature was increased from 108 ° C. to 140 ° C., and the resulting reaction solution was confirmed by HPLC analysis. However, the following reaction results were obtained. Reaction conversion rate 91 mol% Reaction production rate 51 mol% (3-nitro-o used in the reaction)
Selectivity 56% (relative to 3-nitro-o-xylene reacted)
【００２０】実施例３ 反応温度を１０８℃から８０℃に下げる以外は実施例１
と同様にして反応を行い、得られた反応液をH.P.L.C.分
析にて確認したところ、以下の反応結果となった。 反応転化率 ７９モル％ 反応生成率 ４４モル％(反応に用いた３−ニトロ−ｏ
−キシレンに対して) 選択率 ５６％（反応した３−ニトロ−ｏ−キシレ
ンに対して）Example 3 Example 1 except that the reaction temperature was lowered from 108 ° C. to 80 ° C.
The reaction was performed in the same manner as described above, and the obtained reaction solution was confirmed by HPLC analysis. The following reaction results were obtained. Conversion rate of reaction 79 mol% Reaction generation rate 44 mol% (3-nitro-o used in the reaction)
Selectivity 56% (relative to 3-nitro-o-xylene reacted)
【００２１】実施例４ 酢酸の使用量を９．４ｇ（３−ニトロ−ｏ−キシレンに
対して６．８重量倍）に減少する以外は実施例１と同様
にして反応を行い、得られた反応液をH.P.L.C.分析にて
確認したところ、以下の反応結果となった。 反応転化率 ２６モル％ 反応生成率 １０モル％(反応に用いた３−ニトロ−ｏ
−キシレンに対して) 選択率 ４０％（反応した３−ニトロ−ｏ−キシレ
ンに対して）Example 4 A reaction was carried out in the same manner as in Example 1 except that the amount of acetic acid used was reduced to 9.4 g (6.8 times by weight based on 3-nitro-o-xylene). When the reaction solution was confirmed by HPLC analysis, the following reaction results were obtained. Reaction conversion rate 26 mol% Reaction production rate 10 mol% (3-nitro-o used in the reaction)
Selectivity 40% (relative to 3-nitro-o-xylene reacted)
【００２２】実施例５ 酢酸コバルトの使用量を０．４４ｇ（３−ニトロ−ｏ−
キシレンに対して０．１９モル倍）に減少する以外は実
施例１と同様にして反応を行い、得られた反応液をH.P.
L.C.分析にて確認したところ、以下の反応結果となっ
た。 反応転化率 ５４モル％ 反応生成率 ２７モル％(反応に用いた３−ニトロ−ｏ
−キシレンに対して) 選択率 ５０％（反応した３−ニトロ−ｏ−キシレ
ンに対して）Example 5 The amount of cobalt acetate used was 0.44 g (3-nitro-o-
The reaction was carried out in the same manner as in Example 1 except that the reaction solution was reduced to 0.19 mol times with respect to xylene.
The following reaction results were obtained by LC analysis. Reaction conversion rate: 54 mol% Reaction production rate: 27 mol% (3-nitro-o used in the reaction)
Selectivity 50% (relative to reacted 3-nitro-o-xylene)
【００２３】実施例６ 酢酸コバルトに代えて酢酸マンガン四水和物１．１２ｇ
（４．５５ミリモル：３−ニトロ−ｏ−キシレンに対し
て０．５モル倍）を使用する以外は実施例１と同様にし
て反応を行い、得られた反応液をH.P.L.C.分析にて確認
したところ、以下の反応結果となった。 反応転化率 ４２モル％ 反応生成率 １７モル％(反応に用いた３−ニトロ−ｏ
−キシレンに対して) 選択率 ４０％（反応した３−ニトロ−ｏ−キシレ
ンに対して）Example 6 1.12 g of manganese acetate tetrahydrate instead of cobalt acetate
(4.55 mmol: 0.5 mol times based on 3-nitro-o-xylene) The reaction was carried out in the same manner as in Example 1 except that the obtained reaction solution was confirmed by HPLC analysis. However, the following reaction results were obtained. Reaction conversion rate 42 mol% Reaction production rate 17 mol% (3-nitro-o used in the reaction)
Selectivity 40% (relative to 3-nitro-o-xylene reacted)
【００２４】実施例７ 臭化ソーダの使用量を１５．８ｍｇ（０．１６ミリモ
ル：酢酸コバルト四水和物に対して１．４重量％）に減
少する以外は実施例１と同様にして反応を行い、得られ
た反応液をH.P.L.C.分析にて確認したところ、以下の反
応結果となった。 反応転化率 ４５モル％ 反応生成率 １８モル％(反応に用いた３−ニトロ−ｏ
−キシレンに対して) 選択率 ４０％（反応した３−ニトロ−ｏ−キシレ
ンに対して）Example 7 A reaction was carried out in the same manner as in Example 1 except that the amount of sodium bromide used was reduced to 15.8 mg (0.16 mmol: 1.4% by weight based on cobalt acetate tetrahydrate). Was performed, and the obtained reaction solution was confirmed by HPLC analysis. The following reaction results were obtained. Reaction conversion rate 45 mol% Reaction production rate 18 mol% (3-nitro-o used in the reaction)
Selectivity 40% (relative to 3-nitro-o-xylene reacted)
【００２５】実施例８ 臭化ソーダに代えて臭化アンモニウム０．１６ｇ（１．
５９ミリモル：酢酸コバルト四水和物に対して１４．２
重量％）を使用する以外は実施例１と同様にして反応を
行い、得られた反応液をH.P.L.C.分析にて確認したとこ
ろ、以下の反応結果となった。 反応転化率 ９８モル％ 反応生成率 ５５モル％(反応に用いた３−ニトロ−ｏ
−キシレンに対して) 選択率 ５６％（反応した３−ニトロ−ｏ−キシレ
ンに対して）Example 8 Instead of sodium bromide, 0.16 g of ammonium bromide (1.
59 mmol: 14.2 based on cobalt acetate tetrahydrate
(% By weight), and the reaction was carried out in the same manner as in Example 1. The obtained reaction solution was confirmed by HPLC analysis, and the following reaction results were obtained. Reaction conversion rate: 98 mol% Reaction production rate: 55 mol% (3-nitro-o used in the reaction)
Selectivity 56% (relative to 3-nitro-o-xylene reacted)
【００２６】実施例９ 酸素ガスに代えて通常の空気を使用する以外は実施例１
と同様にして反応を行い、得られた反応液をH.P.L.C.分
析にて確認したところ、以下の結果となった。 反応転化率 ５０．４モル％ 反応生成率 ２３．２モル％（反応に用いた３−ニトロ
−ｏ−キシレンに対して） 選択率 ４６．０％（反応した３−ニトロ−ｏ−キ
シレンに対して）Example 9 Example 1 except that ordinary air was used instead of oxygen gas.
The reaction was performed in the same manner as described above, and the obtained reaction solution was confirmed by HPLC analysis. The results were as follows. Reaction conversion rate 50.4 mol% Reaction production rate 23.2 mol% (based on 3-nitro-o-xylene used in the reaction) Selectivity 46.0% (based on reacted 3-nitro-o-xylene) hand)
【００２７】実施例１０ ガス導入口及び排気口を取り付けた容量３００ｍｌの撹
拌機付ガラス製オートクレーブに実施例１と同様に３−
ニトロ−ｏ−キシレン１．３８ｇ（９．１ミリモル）、
酢酸７２ｇ、酢酸コバルト四水和物１．１３ｇ、臭化ソ
ーダ０．１６ｇを仕込み、反応圧力８気圧ゲージ、反応
温度１４０℃において排ガス中の酸素濃度が８容量％以
下になるような流速で吹き込んだ空気と５時間接触させ
た。得られた反応液をH.P.L.C.分析にて確認したとこ
ろ、以下の反応結果となった。 反応転化率 ９３モル％ 反応生成率 ５２モル％（反応に用いた３−ニトロ−ｏ
−キシレンに対して） 選択率 ５６％（反応した３−ニトロ−ｏ−キシレ
ンに対して）Example 10 A 300-ml glass autoclave with a stirrer equipped with a gas inlet and an exhaust port was provided in the same manner as in Example 1,
1.38 g (9.1 mmol) of nitro-o-xylene,
72 g of acetic acid, 1.13 g of cobalt acetate tetrahydrate, and 0.16 g of sodium bromide are charged, and the mixture is blown at a reaction pressure of 8 atm at a flow rate such that the oxygen concentration in the exhaust gas becomes 8% by volume or less at a reaction temperature of 140 ° C. Contact for 5 hours. When the obtained reaction solution was confirmed by HPLC analysis, the following reaction results were obtained. Reaction conversion rate 93 mol% Reaction production rate 52 mol% (3-nitro-o used in the reaction)
Selectivity 56% (based on reacted 3-nitro-o-xylene)
【００２８】実施例１１〜１４ 実施例１０と同様な方法で、表１に示される原料及び条
件にて加圧下の反応を行った。反応結果（反応転化率、
反応生成率及び選択率）を表１に示した。なお、実施例
１３及び１４に示されるように、反応促進助剤（アルデ
ヒド類）を使用することにより、重金属触媒の使用量を
低減できることが判明した。Examples 11 to 14 In the same manner as in Example 10, the reaction was carried out under pressure under the raw materials and conditions shown in Table 1. Reaction results (reaction conversion,
Table 1 shows the reaction generation rate and selectivity). In addition, as shown in Examples 13 and 14, it was found that the use of the heavy metal catalyst can be reduced by using the reaction promoting assistant (aldehydes).
【００２９】[0029]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 駿河 寿秀 和歌山県和歌山市宇須４丁目４番６号 ス ガイ化学工業株式会社内 (72)発明者 芝本 信頼 和歌山県和歌山市宇須４丁目４番６号 ス ガイ化学工業株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshihide Suruga 4-4-6 Usu, Wakayama City, Wakayama Prefecture Inside Sugai Chemical Industry Co., Ltd. No. 6 Inside Sugai Chemical Industry Co., Ltd.
Claims (5)
肪族カルボン酸溶媒又は低級脂肪族カルボン酸と有機溶
媒との混合溶媒中、重金属触媒と反応促進剤の存在下
で、酸素又は酸素含有ガスによって酸化し、３−ニトロ
−ｏ−トルイル酸を得ることを特徴とする３−ニトロ−
ｏ−トルイル酸の製造方法。1. An oxygen or oxygen-containing gas containing 3-nitro-o-xylene in a lower aliphatic carboxylic acid solvent or a mixed solvent of a lower aliphatic carboxylic acid and an organic solvent in the presence of a heavy metal catalyst and a reaction accelerator. To obtain 3-nitro-o-toluic acid.
A method for producing o-toluic acid.
５〜１００重量倍の酢酸、プロピオン酸及び／又は酪酸
を使用する請求項１記載の方法。2. The method according to claim 1, wherein acetic acid, propionic acid and / or butyric acid are used in an amount of 5 to 100 times by weight relative to 3-nitro-o-xylene.
ガン、セリウム又は銅の臭化物や水酸化物、これら重金
属との炭酸塩、低級脂肪族カルボン酸塩又はナフテン酸
塩、及びこれら重金属のアセチルアセトナートからなる
群より選ばれた１乃至２種以上を、３−ニトロ−ｏ−キ
シレンに対して０．００５〜１．０モル倍使用する請求
項１又は２記載の方法。3. The heavy metal catalyst comprises a bromide or hydroxide of cobalt, manganese, cerium or copper, a carbonate with these heavy metals, a lower aliphatic carboxylate or a naphthenate, and acetylacetonate of these heavy metals. 3. The method according to claim 1, wherein one or two or more selected from the group are used in an amount of 0.005 to 1.0 mol times based on 3-nitro-o-xylene.
素、臭化コバルト、臭化アンモニウム、アルカリ金属臭
素化合物、テトラ−ｎ−ブチルアンモニウムブロマイ
ド、テトラブロムエタン、ブロム酢酸及び臭化ベンジル
からなる群より選ばれた１乃至２種以上、又はヨウ素、
ヨウ化水素、ヨウ化アンモニウム、アルカリ金属ヨウ素
化合物及びテトラ−ｎ−ブチルアンモニウムヨージドか
らなる群より選ばれた１乃至２種以上を、重金属触媒に
対して１．０〜３２重量％使用する請求項１、２又は３
記載の方法。4. A group consisting of bromine, hydrogen bromide, cobalt bromide, ammonium bromide, alkali metal bromine compounds, tetra-n-butylammonium bromide, tetrabromoethane, bromoacetic acid and benzyl bromide as reaction accelerators. One or two or more selected from iodine,
One to two or more selected from the group consisting of hydrogen iodide, ammonium iodide, an alkali metal iodine compound and tetra-n-butylammonium iodide are used in an amount of 1.0 to 32% by weight based on the heavy metal catalyst. Item 1, 2 or 3
The described method.
デヒド、パラホルムアルデヒド、アセトアルデヒド、パ
ラアルデヒド、プロピオンアルデヒド、ブチルアルデヒ
ド、ベンズアルデヒド、クロロベンズアルデヒド、フル
オロベンズアルデヒド、ニトロベンズアルデヒドなどの
アルデヒド類、アセトン、メチルエチルケトン、ジエチ
ルケトン、ベンゾフェノンなどのケトン類、塩酸及びモ
ノクロル酢酸からなる群より選ばれた１乃至２種以上を
３−ニトロ−ｏ−キシレンに対して０．０１〜５．０モ
ル倍使用する請求項１、２、３又は４に記載の方法。5. An aldehyde such as formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, chlorobenzaldehyde, fluorobenzaldehyde, nitrobenzaldehyde, acetone, methyl ethyl ketone, diethyl ketone in combination with a reaction accelerator. 3. One or two or more kinds selected from the group consisting of ketones such as benzophenone, hydrochloric acid and monochloroacetic acid are used in an amount of 0.01 to 5.0 mole times based on 3-nitro-o-xylene. 5. The method according to 3 or 4.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19319297A JP4148480B2 (en) | 1997-02-17 | 1997-07-02 | Method for producing 3-nitro-o-toluic acid |
| PCT/JP1998/000353 WO1998035932A1 (en) | 1997-02-17 | 1998-01-29 | PROCESS FOR PRODUCING 3-NITRO-o-TOLUIC ACID |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-49684 | 1997-02-17 | ||
| JP4968497 | 1997-02-17 | ||
| JP19319297A JP4148480B2 (en) | 1997-02-17 | 1997-07-02 | Method for producing 3-nitro-o-toluic acid |
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| Publication Number | Publication Date |
|---|---|
| JPH10287627A true JPH10287627A (en) | 1998-10-27 |
| JP4148480B2 JP4148480B2 (en) | 2008-09-10 |
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|---|---|---|---|
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| Country | Link |
|---|---|
| JP (1) | JP4148480B2 (en) |
| WO (1) | WO1998035932A1 (en) |
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| US4065477A (en) * | 1976-10-29 | 1977-12-27 | Bison-Werke Bahre & Greten Gmbh & Co. Kg | Process for preparing highly pure 1-nitroanthraquinone |
| JPS5951242A (en) * | 1982-09-14 | 1984-03-24 | Toray Ind Inc | Preparation of m-nitrobenzoic acid |
-
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| WO1998035932A1 (en) | 1998-08-20 |
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